KR100698916B1 - Adhesive composition, circuit connecting material, structure of connecting circuit terminal and semiconductor device - Google Patents

Abstract

The adhesive composition of the present invention comprises a thermoplastic resin, a radically polymerizable compound, a first radical polymerization initiator having a half-life temperature of 90 to 145 ° C for 1 minute, and a second radical polymerization having a half-life temperature of 150 to 175 ° C for 1 minute. It contains an initiator. ADVANTAGE OF THE INVENTION According to this invention, the connection structure of the adhesive composition, circuit connection material, and circuit member which can harden | cure quickly and rapidly at low temperature, and the process margin at the time of hardening process is wide and a sufficiently stable adhesive strength and connection resistance are obtained. And a semiconductor device.

Description

Adhesive composition, circuit connection material, connection structure of circuit member and semiconductor device {ADHESIVE COMPOSITION, CIRCUIT CONNECTING MATERIAL, STRUCTURE OF CONNECTING CIRCUIT TERMINAL AND SEMICONDUCTOR DEVICE}

1 is a schematic cross-sectional view showing one embodiment of a connection structure of a circuit member of the present invention.

2 is a schematic cross-sectional view showing one embodiment of a semiconductor device of the present invention.

The present invention relates to an adhesive composition, a circuit connection material, a connection structure of a circuit member, and a semiconductor device.

Conventionally, thermosetting resins, such as an epoxy resin which is excellent in adhesiveness and especially excellent in high temperature, high humidity conditions, are used as an adhesive agent for semiconductor elements and a liquid crystal display element (for example, Japanese Patent Laid-Open No. 01-113480). Publication). Such an adhesive is cured by heating at a temperature of 170 to 250 ° C. for 1 to 3 hours to obtain adhesiveness.

Background Art In recent years, as the integration of semiconductor devices and the definition of liquid crystal devices are increased, narrower pitches between devices and wirings have been developed. In the case of using the above-described adhesive such as a semiconductor device, since the heating temperature at the time of curing and the curing speed are low, not only the desired connecting portion but also the peripheral member is heated to affect the damage of the peripheral member. There is a tendency. Furthermore, due to the low cost, the throughput needs to be improved, and low temperature (100 to 170 ° C), short time (within 1 hour), in other words, adhesion to "low temperature hardening" is required.

On the other hand, the radical curable adhesive which used together the acrylate derivative, the methacrylate derivative, and the peroxide which is a radical polymerization initiator is attracting attention recently. Since this adhesive agent is hardened | cured and adhere | attached using the polymerization reaction of the radical which is reactive reactive species excellent in reactivity, it can harden | cure in a comparatively short time (for example, refer Unexamined-Japanese-Patent No. 2002-203427).

However, since radical curable adhesives are excellent in reactivity, there exists a tendency for the process margin at the time of hardening process to become narrow. For example, in the case of using the above-mentioned radical curable adhesive to electrically connect a semiconductor device or a liquid crystal display device, if the process conditions such as temperature and time when obtaining the cured product vary slightly, characteristics of adhesive strength, connection resistance, etc. This tends not to be stably obtained.

Accordingly, the present invention provides a connection structure of an adhesive composition, a circuit connection material, and a circuit member, which can be sufficiently cured at a low temperature quickly and have a wide process margin in the case of performing a curing process, thereby obtaining sufficiently stable adhesive strength and connection resistance. And a semiconductor device.

The adhesive composition of this invention which solves the said subject is a thermoplastic resin, a radically polymerizable compound, the 1st radical polymerization initiator whose half life temperature is 90-145 degreeC for 1 minute, and the half life temperature is 150-175 degreeC for 1 minute. It is characterized by containing a 2nd radical polymerization initiator.

Here, "1 minute half-life temperature" means the temperature at which a half-life becomes 1 minute, and "half-life" means time until the concentration of a compound decreases to half of an initial value.

The adhesive composition of this invention is what is called radical curable adhesive composition containing a thermoplastic resin, a radically polymerizable compound, and a radical polymerization initiator. Thus, since the adhesive composition containing a radically polymerizable compound is excellent in reactivity, even if it is low temperature, it can be hardened enough in a short time. Furthermore, by using two kinds of radical polymerization initiators having different half-life temperatures for one minute as the radical polymerization initiator, it becomes possible to widen the process margin in the case of performing the curing treatment. Therefore, the hardened | cured material obtained from such an adhesive composition can make stable characteristics, such as adhesive strength and connection resistance, even if the process temperature and time at the time of obtaining the hardened | cured material change. In addition, the deterioration of the cured product over time can also be suppressed.

Furthermore, radical curable adhesives having a half-life temperature of 1 minute in the above-described range generally have low activation energy, and thus tend to be inferior in storage stability. However, the hardened | cured material obtained from the adhesive composition of this invention can also be equipped with the storage stability which was further excellent compared with the conventional thing. The inventors believe that this is due to the use of two kinds of radical polymerization initiators having different half-life temperatures in the adhesive composition of the present invention for one minute.

In addition, the adhesive composition of the present invention can be cured in a short time, and the process margin can be widened. Therefore, even if the pitch between elements such as semiconductor elements, liquid crystal elements, and wirings is narrowed, not only the desired connection portion can be used. By heating up to the peripheral member, it is possible to prevent the influence of the peripheral member from being damaged or the like, and the throughput can be improved.

Moreover, in the adhesive composition of this invention, it is preferable that a radically polymerizable compound has two or more (meth) acryloyl groups in a molecule | numerator. By using such an adhesive composition, hardening process can be performed in a short time. This inventor is guessing that this is because a radically polymerizable compound has two or more (meth) acryloyl groups which are a reactive radical rich reactive group.

Moreover, since such a radically polymerizable compound uses a (meth) acryloyl group as a reactive group, firm adhesiveness can be obtained regardless of the material of the adherend. Therefore, the adhesive composition of this invention containing such a radically polymerizable compound is excellent in versatility, and even when it is used for a semiconductor element or a liquid crystal display element, more stable adhesive strength, connection resistance, etc. can be acquired.

Moreover, it is preferable that both the 1st radical polymerization initiator and the 2nd radical polymerization initiator are peroxy ester derivatives whose molecular weight is 180-1000.

Since either the 1st radical polymerization initiator and the 2nd radical polymerization initiator are peroxy ester derivatives of the same kind, and if it is a molecular weight in the said numerical range, since it is excellent in compatibility with each other, the hardened | cured material obtained will be over the whole It becomes more stable and exhibits characteristics, such as adhesive strength and connection resistance.

Moreover, the adhesive composition of this invention contains 50-250 weight part of radically polymerizable compounds with respect to 100 weight part of thermoplastic resins, and also 0.05-30 weight of 1st radical polymerization initiator and 2nd radical polymerization initiator, respectively. It is preferable to contain. The adhesive composition of this invention can exhibit the effect of this invention more remarkably by making the composition material into the compounding ratio of the said range.

Moreover, it is preferable to contain electroconductive particle in this adhesive composition. Such an adhesive composition becomes electroconductive. Then, this adhesive composition can be used as a conductive adhesive in the field of electrical industry and electronic industry, such as a circuit electrode and a semiconductor. In addition, in this case, since an adhesive composition is electroconductive, it becomes possible to make connection resistance after hardening much lower.

Moreover, about the compounding ratio of this electroconductive particle, it is preferable to contain 0.5-30 weight part of electroconductive particles with respect to 100 weight part of thermoplastic resins. By making electroconductive particle into the compounding ratio of the said range, such an adhesive composition can exhibit the effect of electroconductive particle further. For example, when it is used for connection of circuit electrodes, it is possible to prevent the conduction between opposing circuit electrodes or the short circuit (short) between adjacent circuit electrodes. Moreover, the adhesive composition containing electroconductive particle in said compounding ratio can also show the anisotropy of an electrical connection, and can be used as an anisotropic conductive adhesive composition.

And the circuit connection material of this invention is a circuit connection material for electrically connecting the opposing circuit electrodes, It is characterized by the circuit connection material containing the adhesive composition mentioned above.

Such a circuit connection material can fully adhere | attach opposing circuit electrodes even in low temperature in a short time, and can also enlarge a process margin. Furthermore, the cured product obtained from such a circuit connecting material can be made stable in characteristics such as adhesive strength and connection resistance even if the process temperature and time when obtaining the cured product vary. In addition, the deterioration of the cured product over time can also be suppressed. Moreover, when this circuit connection material contains electroconductive particle in said compounding ratio, it can show the anisotropy of an electrical connection, and it can also use as an anisotropic conductive circuit connection material for circuit electrodes.

Moreover, it is preferable that the adhesive composition or circuit connection material mentioned above is formed in the film form. Since the adhesive composition or circuit connection material which made into a film is excellent in handleability, the throughput can be improved further.

In addition, the connection structure of the circuit member of the present invention includes a first circuit member in which a first circuit electrode is formed on a main surface of a first circuit board, and a second circuit electrode on a main surface of a second circuit board. It is provided between the formed second circuit member and the main surface of the first circuit board and the main surface of the second circuit board, and is electrically connected with the first circuit electrode and the second circuit electrode. A circuit member connection structure including a circuit connection member to be connected, wherein the circuit connection member is a cured product of the circuit connection material described above.

As such a circuit member connection structure, an electrically connected circuit electrode can be effectively used. That is, since the above-described circuit connection material is used to electrically connect the first circuit electrode and the second circuit electrode, the circuit member having the connection structure of the present invention has a sufficiently stable characteristic due to a small gap in quality. Can be represented. Furthermore, when the hardened | cured material of a circuit connection material contains electroconductive particle, connection resistance can be made low. By mix | blending this electroconductive particle, it can prevent that it does not conduct between opposing circuit electrodes, or short circuits (short) between adjacent circuit electrodes. Moreover, when electroconductive particle is contained in said compounding ratio, it can also show the anisotropy of an electrical connection, and can also set it as an anisotropic circuit connection material.

Moreover, the semiconductor device of this invention is a semiconductor device provided with a semiconductor element, the board | substrate which mounts a semiconductor element, and the semiconductor element connection member provided between the semiconductor element and the board | substrate, and electrically connecting a semiconductor element and a board | substrate, A semiconductor The element connecting member is a cured product of the adhesive composition described above or a film adhesive.

Such a semiconductor device is hardened | cured from the adhesive composition mentioned above since the hardened | cured material of the adhesive composition which electrically connects a semiconductor element and a board | substrate has a small quality difference, and can exhibit the characteristic which is sufficiently stable. Furthermore, when the hardened | cured material of an adhesive composition contains electroconductive particle, connection resistance can be made low. By mix | blending this electroconductive particle, it can prevent that it does not conduct between an opposing semiconductor element and a board | substrate. Moreover, when electroconductive particle is contained in said compounding ratio, it can also show the anisotropy of an electrical connection, and can also be set as an anisotropic semiconductor.

Description of the Preferred Embodiments

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described with reference to an accompanying drawing in some cases. In addition, the same code | symbol is used for the same element, and the overlapping description is abbreviate | omitted. In addition, in the following description, (meth) acrylate shall mean an acrylate or a methacrylate corresponding to it.

(Adhesive Composition)

The adhesive composition of the present invention comprises a thermoplastic resin, a radically polymerizable compound, a first radical polymerization initiator having a half-life temperature of 90 to 145 ° C for 1 minute, and a second radical polymerization initiator having a half-life temperature of 150 to 175 ° C for 1 minute. It is to contain.

Here, the thermoplastic resin which concerns on this invention is used in order to make the adhesion | attachment of the object to adhere | attach (Hereinafter, only a "substrate") to be firm.

As a thermoplastic resin used by this invention, a well-known thing can be used without a restriction | limiting in particular. Specifically, polyimide, polyamide, phenoxy resins, poly (meth) acrylates, polyimides, polyurethanes, polyesters, polyvinyl butyrals and the like can be used. These can be used individually or in mixture of 2 or more types. Furthermore, these resins may have a siloxane bond or a fluorine substituent in the molecule. These resins can be suitably used as long as the resins to be mixed are completely compatible or have a microphase separation.

In addition, the larger the molecular weight of the thermoplastic resin, the more easily the film described later can be formed, and the melt viscosity that affects the fluidity as the adhesive can be set widely. If the melt viscosity can be set in a wide range, when used for connection of semiconductor elements, liquid crystal elements, etc., even if the pitch between elements and wirings is narrowed, it is possible to further prevent the adhesive from adhering to the peripheral member, thereby improving throughput. It becomes possible to make it. However, when the value of this molecular weight exceeds 150000, there exists a tendency for compatibility with other components to be inferior, and when less than 5000, when used as a film mentioned later, there exists a tendency for film formation to become inadequate. Therefore, this molecular weight is preferable in it being 5000-150000 as a weight average molecular weight, and more preferable in it being 10000-80000.

In addition, the radically polymerizable compound which concerns on this invention says the compound which has the ability to generate | occur | produce a radical by what energy is provided, and the radical superposes | polymerizes by a chain reaction and forms a polymer. The radical polymerization reaction generally proceeds faster than cationic polymerization or anionic polymerization. Therefore, in this invention using a radically polymerizable compound, superposition | polymerization in a comparatively short time becomes possible.

As a radically polymerizable compound used by this invention, if it is a compound which has an olefin in a molecule | numerator, such as a (meth) acryl group, a (meth) acryloyl group, and a vinyl group, a well-known thing can be used without a restriction | limiting in particular. Among these, it is preferable that it is a radically polymerizable compound which has a (meth) acryloyl group.

Specifically as a radically polymerizable compound which has a (meth) acryloyl group, it is an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, and polyester (meth) acryl Oligomers, such as a rate oligomer, trimetholpropane tri (meth) acrylate, polyethyleneglycol di (meth) acrylate, polyalkylene glycoldi (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclophene Tenyloxyethyl (meth) acrylate, neopentylglycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) Polyfunctional (meth) acrylates, such as an acrylate, 2,2'- di (meth) acryloyloxy diethyl phosphate, and 2- (meth) acryloyloxyethyl acid phosphate Agent may be a compound or the like. You may use these compounds individually or in mixture of 2 or more types as needed.

Thus, when using a (meth) acryloyl group as a reactive group, firm adhesion can be performed regardless of the material of a to-be-adhered body. Examples of the adherend include organic substrates such as printed wiring boards and polyimides, as well as metals such as copper and aluminum, indium tin oxide (ITO), silicon nitride (SiN), and silicon dioxide (SiO ₂ ).

Moreover, when a radically polymerizable compound has two or more (meth) acryloyl groups in a molecule | numerator, since the heating time required for adhesion | attachment can be shortened and the heating temperature required for adhesion | attachment can be made preferable, it is preferable. This is considered to be due to having more (meth) acryloyl groups which are radical reactive groups in the molecule | numerator of a radically polymerizable compound.

Moreover, it is preferable that it is 50-250 weight part with respect to 100 weight part of thermoplastic resins, and, as for the compounding ratio of this radically polymerizable compound, it is more preferable that it is 60-150 weight part. If the blending ratio of the radically polymerizable compound is less than 50 parts by weight, the heat resistance of the cured product of the adhesive composition applied to the adherend tends to decrease, and if it exceeds 250 parts by weight, the film formation is insufficient when the adhesive composition is used as a film to be described later. Tend to be done.

In addition, the adhesive composition of the present invention includes a radical polymerization initiator. The radically polymerizable compound, once the radical polymerization reaction starts, the chain reaction proceeds and firm curing becomes possible, but since it is relatively difficult to generate radicals at first, a radical polymerization initiator capable of generating radicals relatively easily It contains.

In this invention, as a radical polymerization initiator, the 1st radical polymerization initiator whose half life temperature is 90-145 degreeC for 1 minute, and the 2nd radical polymerization initiator whose half life temperature is 150-175 degreeC for 1 minute are used together.

As such a 1st radical polymerization initiator, a well-known compound can be used as long as the half-life temperature is 90-145 degreeC for 1 minute, and a well-known compound can be used as a 1st half-life temperature as 150-175 degreeC as a 2nd radical polymerization initiator. It is available.

Among these, it is preferable that both a 1st radical polymerization initiator and a 2nd radical polymerization initiator are peroxy ester derivatives. Since any of them are excellent in compatibility with each other as long as they are peroxy ester derivatives, the resulting cured product exhibits properties such as more stable adhesive strength and connection resistance throughout its entirety.

Specifically as a 1st radical polymerization initiator, cumyl peroxy neodecanoate, 1,1,3,3- tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neo Decanoate, t-hexyl peroxy neodecanoate, t-butylperoxy neodecanoate, t-butylperoxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Noate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate , t-butylperoxy neoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexa Noate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxyneodecano Et, t-amylperoxy-2-ethylhexanoate , 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 1,1 ' -Azobis (1-cyclohexanecarbonitrile), etc. are mentioned.

As the second radical polymerization initiator, specifically, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy maleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t- Butyl peroxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2, 5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyl adipate, t-amylperoxy normal octoate, t-amylperoxy isocyanate, t-amyl peroxybenzoate, etc. are mentioned.

Moreover, the adhesive composition of this invention should just use together the 1st radical polymerization initiator and the 2nd radical polymerization initiator, You may use 2 or more types of 1st radical polymerization initiators, and 2 types of 2nd radical polymerization initiators It is also possible to use more than.

It is preferable that the molecular weight of a 1st radical polymerization initiator and a 2nd radical polymerization initiator is 180-1000 as a weight average molecular weight. If either the first radical polymerization initiator or the second radical polymerization initiator is a molecular weight within the above numerical range, the compatibility is excellent, and thus the resulting cured product will have properties such as more stable adhesive strength and connection resistance throughout the whole. It is shown.

As for the addition amount of a 1st radical polymerization initiator and a 2nd radical polymerization initiator, it is preferable that all are 0.05-30 weight part with respect to 100 weight part of thermoplastic resin, and it is more preferable that all are 0.05-30 weight part. Moreover, it is especially preferable that all are 0.1-20 weight part. When the addition amount of any of the first radical polymerization initiator and the second radical polymerization initiator is less than 0.05 part by weight, radical polymerization tends not to be sufficiently initiated, and any of the first radical polymerization initiator and the second radical polymerization initiator When the addition amount of a thing exceeds 30 weight part, there exists a tendency for storage stability to fall.

Moreover, although it does not specifically limit as a form of energy imparted in this invention, Heat, an electron beam, a gamma ray, an ultraviolet-ray, an infrared ray, etc. are mentioned.

When the adhesive composition of the present invention is used, the factor of obtaining a cured product having sufficiently stable adhesive strength and connection resistance is not known at present. However, the present inventors consider that, as one of the factors, a relatively stable radical polymerization rate can be obtained under different process conditions by using two kinds of radical polymerization initiators having different half-life temperatures for one minute. However, the factor is not limited to this.

It is preferable to contain electroconductive particle in the adhesive composition of this invention. By containing electroconductive particle, electroconductivity can be provided to this adhesive composition. In this way, it becomes possible to use as a conductive adhesive in the field of electrical industry and electronic industry, such as a circuit electrode and a semiconductor.

Although the electroconductive particle used here will not have a restriction | limiting in particular if it has electroconductivity which can acquire an electrical connection, For example, metals, such as Au, Ag, Ni, Cu, solder, carbon, etc. are mentioned. In addition, a non-conductive glass, ceramic, plastic, or the like may be used as a nucleus, and the nucleus may be coated with the above metal or carbon. Among these, it is preferable that the metal itself is a heat-melt metal, or a case in which plastic is used as a nucleus and coated with metal or carbon. In these cases, since it becomes easier to deform the hardened | cured material of an adhesive composition by heating or pressurization, when electrically connecting electrodes, the contact area of an electrode and an adhesive composition can be increased, and electroconductivity between electrodes can be improved. have.

Moreover, you may use the layered particle | grains which coat | covered the surface of this electroconductive particle with the polymeric resin. When the conductive particles are added to the adhesive composition in the state of the layered particles, even when the compounding amount of the conductive particles is increased, the conductive particles are coated with the resin, further suppressing the occurrence of a short circuit due to contact between the conductive particles and improving the insulation between the electrode circuits. You can. Moreover, you may use these electroconductive particle and layered particle individually or in mixture of 2 or more types.

It is preferable that the average particle diameter of electroconductive particle is 1-18 micrometers from a viewpoint of dispersibility and electroconductivity. It is preferable that it is 0.1-30 volume% with respect to 100 volume% of adhesive compositions, and, as for the compounding ratio of electroconductive particle, it is more preferable that it is 0.1-10 volume%. If this value is less than 0.1 volume%, there exists a tendency for electroconductivity to not fully be acquired, and when it exceeds 30 volume%, there exists a tendency for a short circuit to occur. In addition, although the compounding ratio (vol%) of electroconductive particle is determined based on the volume of each component before hardening an adhesive composition at 23 degreeC, the volume of each component is converted into volume from volume using specific gravity, It can be obtained by a method of adding the component to a container such as a measuring cylinder containing a suitable solvent (water, alcohol, etc.) that wets the component well without dissolving or swelling the component, and calculating it from the increased volume. .

Moreover, it is preferable to add the coupling agent represented by an alkoxysilane derivative and a silazane derivative, and adhesion | attachment adjuvant, such as an adhesion promoter and a leveling agent, to the adhesive composition of this invention. Thereby, the effect of this invention can be exhibited more remarkably, and also more favorable adhesiveness and handleability can also be provided. It is preferable to add the compound specifically, represented by following General formula (1).

In the formula, R ¹ , R ² and R ³ each independently represent hydrogen, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxycarbonyl group of 1 to 5 carbon atoms, or an aryl group, and R ⁴ represents Hydrogen or a methyl group is represented, n represents the integer of 1-10.

Furthermore, in this general formula (1), when R <^1> is a C1-C5 alkyl group or an aryl group, R <^2> and R <^3> is respectively independently a C2-C3 alkoxy group, and n is 2-4, adhesive It is preferable because of its superiority and connection resistance. In addition, the compound represented by General formula (1) may be used individually by 1 type, or may mix and use 2 or more types.

Moreover, the adhesive composition of this invention can add another material according to a use purpose besides this. For example, you may use together the adhesive improver which improves the crosslinking rate of an adhesive agent. Thereby, adhesive strength can be raised further. That is, in addition to the radically polymerizable compound which has a (meth) acryloyl group, you may add the compound which has radically polymerizable functional groups, such as an allyl group, a maleimide group, and a vinyl group. Specifically, N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinyl caprolactam, 4,4'- vinylidenebis (N, N-dimethylaniline ), N-vinylacetamide, N, N-dimethyl acrylamide, N-isopropyl acrylamide, N, N-diethyl acrylamide, etc. are mentioned. In addition, these adhesive improving agents may be used individually by 1 type, or may mix and use 2 or more types.

Moreover, you may use together fluidity improving agents, such as monofunctional (meth) acrylate. Thereby, fluidity | liquidity can be improved. Specifically, pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meta ) Acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) a Relate, there may be mentioned N, N- dimethylaminopropyl (meth) acrylate, N, N- dimethylaminopropyl (meth) acrylate, (meth) acryloyl morpholine sunset. In addition, these fluidity improving agents may be used individually by 1 type, or may mix and use 2 or more types.

Moreover, you may use together the rubber type material which improves adhesiveness. This also makes it possible to relieve stress. Specifically, polyisoprene, polybutadiene, carboxyl terminal polybutadiene, hydroxyl terminal polybutadiene, 1,2-polybutadiene, carboxyl terminal terminal 1,2-polybutadiene, hydroxyl terminal terminal 1,2-polybutadiene, acrylic rubber, styrene- Butadiene rubber, hydroxyl group terminal styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or an acrylonitrile-butadiene rubber which contains a (meth) acryloyl group or a morpholine group in a polymer terminal, carboxylated nitrile rubber And hydroxyl terminal terminal poly (oxypropylene), alkoxysilyl group terminal poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, and poly-ε-caprolactone.

In addition, the rubber-based material is preferably a rubber-based material including a cyano group and a carboxyl group, which are highly polar functional groups, in the side chain or the terminal from the viewpoint of adhesion improvement, and more preferably in the liquid phase from the viewpoint of fluidity improvement. Do. Specific examples include liquid acrylonitrile-butadiene rubber and liquid carboxylated nitrile rubber containing a liquid acrylonitrile-butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer terminal, It is further more preferable that the acrylonitrile content which is a polar group is 10 to 60 weight% of all these rubber materials. Moreover, these rubber type materials may be used individually by 1 type, or may mix and use 2 or more types.

Moreover, you may use together additives, such as a polymerization inhibitor represented by t-butyl pyrocatechol, t-butylphenol, p-methoxyphenol. As a result, storage stability can be further improved.

When the adhesive composition of the present invention is a liquid at normal temperature, it can be used as a paste. In the case of a solid at normal temperature, in addition to heating and pasting, you may paste into a solvent. The solvent that can be used is not particularly limited as long as it does not react with the adhesive composition and exhibits sufficient solubility at the same time, but the boiling point at normal pressure is preferably 50 to 150 ° C. If the boiling point is less than 50 ° C., there is a tendency to volatilize easily at room temperature. Therefore, a radical polymerization reaction must be performed in a sealed environment, and the use tends to be restricted. Moreover, when a boiling point exceeds 150 degreeC, it is difficult to volatilize a solvent and there exists a tendency for sufficient adhesive strength to not be obtained after adhesion | attachment.

Moreover, the adhesive composition of this invention can also be used as a film form. In the method for producing the film, a mixed solution obtained by adding a solvent to the adhesive composition is applied onto a release base such as a fluororesin film, polyethylene terephthalate film, and release paper, or the base such as a nonwoven fabric is impregnated with a mixed solution to form a release base. The film can be obtained by mounting on and removing a solvent and the like. Thus, when an adhesive composition is made into a film form, it is excellent in handleability and is more convenient.

Moreover, when an electroconductive particle is added to the adhesive composition of this invention and a film is produced, it can be set as an anisotropic conductive film. For example, the anisotropic conductive film can be electrically connected to both electrodes by placing them between opposing electrodes on a substrate, and heating and pressing them. As the substrate for forming the electrode, combinations of these composites, such as inorganic materials such as semiconductors, glass and ceramics, organic materials such as polyimide and polycarbonate, and glass / epoxy, can be applied.

Moreover, the adhesive composition of this invention can be bonded together using heating and pressurization. As for heating temperature, the temperature of 50-190 degreeC is preferable. The pressure may be in a range that does not damage the adherend, and is preferably 0.1 to 10 MPa. It is preferable to perform these heating and pressurization in the range for 0.5 second-120 second.

Moreover, since the adhesive composition of this invention can react in a short time and is excellent also in storage stability, it can use suitably as a circuit connection material. For example, when electrically connecting the circuit electrode of a 1st circuit member and the circuit electrode of a 2nd circuit member, the adhesive composition of this invention is provided to one circuit electrode in the state which arrange | positioned these circuit members, and It can be electrically connected with the other circuit electrode by a radical polymerization reaction. Thus, when an adhesive composition is used as a circuit connection material, it can electrically connect in a short time, and even if the process temperature and time in the case of making a connection change, characteristics, such as adhesive strength and connection resistance, can be made stable. . In addition, the deterioration of the cured product of the circuit connecting material over time can be suppressed. Moreover, when this circuit connection material contains electroconductive particle, it can show the anisotropy of an electrical connection, and it can also use as an anisotropic conductive circuit connection material for circuit electrodes.

The circuit connecting material can also be used as a circuit connecting material for heterogeneous adherends having different thermal expansion coefficients. Specifically, it can be used as a circuit connecting material represented by anisotropic conductive adhesive, silver paste, silver film, or the like, semiconductor device adhesive material represented by CSP elastomer, CSP underfill material, LOC tape, or the like.

(Connection structure of circuit member)

Next, a preferred embodiment of the connection structure of the circuit member of the present invention will be described. 1 is a schematic sectional view showing one embodiment of a connection structure of a circuit member of the present invention. As shown in FIG. 1, the connection structure 1 of the circuit member of this embodiment is equipped with the 1st circuit member 20 and the 2nd circuit member 30 which mutually oppose, and is a 1st circuit Between the member 20 and the 2nd circuit member 30, the circuit connection member 10 which electrically connects these is provided. The first circuit member 20 includes a first circuit board 21 and a first circuit electrode 22 formed on the main surface 21a of the circuit board 21. In addition, an insulating layer (not shown) may be formed on the main surface 21a of the circuit board 21 in some cases.

On the other hand, the second circuit member 30 includes a second circuit board 31 and a second circuit electrode 32 formed on the main surface 31a of the second circuit board 31. have. In addition, an insulating layer (not shown) may be formed on the main surface 31a of the circuit board 31 in some cases.

The first circuit member 20 and the second circuit member 30 are not particularly limited as long as an electrode that requires electrical connection is formed. Specifically, a glass or plastic substrate, a printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor silicon chip, etc., on which electrodes are formed of ITO or the like used in a liquid crystal display, may be used. Can be. As described above, in the present embodiment, a material made of organic material such as a printed wiring board or polyimide, as well as metals such as copper and aluminum, indium tin oxide (ITO), silicon nitride (SiN _x ), and silicon dioxide (SiO ₂ ) As the inorganic material, a circuit member having various surface states can be used.

The circuit connection member 10 contains the insulating material 11 and the electroconductive particle 7. The electroconductive particle 7 is arrange | positioned not only between the opposing 1st circuit electrode 22 and the 2nd circuit electrode 32, but also between the main surface 21a and the main surface 31a. In the connection structure 1 of the circuit member of this embodiment, the 1st circuit electrode 22 and the 2nd circuit electrode 32 are electrically connected through the electroconductive particle 7. For this reason, the connection resistance between the 1st circuit electrode 22 and the 2nd circuit electrode 32 is fully reduced. Therefore, the flow of electric current between the first circuit electrode 22 and the second circuit electrode 32 can be smoothed, and the function of the circuit can be sufficiently exhibited. Moreover, it is also possible to show the anisotropy of electrical connection by making this electroconductive particle 7 into the compounding ratio mentioned above.

Moreover, when the circuit connection member 10 does not contain the electroconductive particle 7, so that a desired amount of electric current may flow between the 1st circuit electrode 22 and the 2nd circuit electrode 32, Electrically connected by direct contact or close enough to them.

Since the circuit connection member 10 is comprised by the hardened | cured material of the circuit connection material containing the said adhesive composition, the circuit connection member with respect to the 1st circuit member 20 or the 2nd circuit member 30 ( The adhesive strength of 10) is sufficiently high, and this state can be maintained for a long time. Accordingly, it becomes possible to sufficiently increase the long-term reliability of the electrical characteristics between the first circuit electrode 22 and the second circuit electrode 32.

(Semiconductor device)

Next, an embodiment of the semiconductor device of the present invention will be described. 2 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention. As shown in FIG. 2, the semiconductor device 2 of the present embodiment includes a semiconductor element 50 and a substrate 60 serving as a support member of the semiconductor. The semiconductor element 50 and the substrate 60 are provided with a semiconductor element 50. The semiconductor element connection member 40 which electrically connects these is provided in between. The semiconductor element connection member 40 is laminated on the main surface 60a of the substrate 60, and the semiconductor element 50 is laminated on the semiconductor element connection member 40. FIG.

The substrate 60 has a circuit pattern 61, and the circuit pattern 61 is electrically connected to the semiconductor element 50 or directly through the semiconductor connection member 40 on the main surface 60a of the substrate 60. Connected. Then, these are sealed by the encapsulant 70 to form the semiconductor device 2.

Although it does not restrict | limit especially as a material of the semiconductor element 50, The semiconductor element of group 4 of silicon and germanium, GaAs, InP, GaP, InGaAs, InGaAsP, AlGaAs, InAs, GaInP, AlInP, AlGaInP, GaNAs, GaNP, GaInNAs, GaInNPs Group III-V compound semiconductor devices such as GaSb, InSb, GaN, AlN, InGaN, InNAsP, HgTe, HgCdTe, CdMnTe, CdS, CdSe, MgSe, MgS, ZnSe, ZeTe, etc. And CuInSe (ClS) can be used.

The semiconductor element connection member 40 contains the insulating material 11 and the electroconductive particle 7. The electroconductive particle 7 is arrange | positioned not only between the semiconductor element 50 and the circuit pattern 61, but also between the semiconductor element 50 and the main surface 60a. In the semiconductor device 2 of this embodiment, the semiconductor element 50 and the circuit pattern 61 are electrically connected through the electroconductive particle 7. For this reason, the connection resistance between the semiconductor element 50 and the circuit pattern 61 is fully reduced. Therefore, the current flows between the semiconductor element 50 and the circuit pattern 61 can be made smooth, and the function which a semiconductor has can fully be exhibited. Moreover, it is also possible to show the anisotropy of electrical connection by making this electroconductive particle 7 into the compounding ratio mentioned above.

In the case where the semiconductor element connecting member 40 does not contain the conductive particles 7, the semiconductor element 50 and the circuit pattern 61 are brought into direct contact with or close enough to allow a desired amount of current to flow. Electrically connected.

Since the semiconductor element connection member 40 is comprised by the hardened | cured material of the adhesive composition containing the said adhesive composition, the adhesive strength of the semiconductor element connection member 40 with respect to the semiconductor element 50 and the board | substrate 60 is strong. It becomes high enough and can maintain this state for a long time. Therefore, it becomes possible to sufficiently increase the long-term reliability of the electrical characteristics between the semiconductor element 50 and the substrate 60.

EXAMPLE

EMBODIMENT OF THE INVENTION Although this invention is demonstrated concretely based on an Example below, this invention is not limited to this.

(Adjustment of conductive particles)

A nickel layer was provided on the surface of the polystyrene particles so as to have a thickness of 0.2 μm, and a gold layer was further provided outside the nickel layer so as to have a thickness of 0.02 μm, thereby producing electroconductive particles having an average particle diameter of 4 μm and a specific gravity of 2.5.

Example 1

50 weight part of phenoxy resins (average molecular weight 45000, Union Carbide make, brand name: PKHC) were melt | dissolved in 75 weight part of methyl ethyl ketone, and it was made into the solution of 40 weight% of solid content.

And as a radically polymerizable compound, 25 weight part of isocyanuric acid EO modified diacrylate (made by Dong-A Synthetic Co., Ltd., brand name: M-215) and urethane acrylate (made by Kyoeisha Chemical Co., Ltd., brand name: AT-600) ) 20 parts by weight, 5 parts by weight of 2- (meth) acryloyloxyethyl phosphate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Lightester P-2M) and t-hexyl peroxy-2-ethyl as a radical polymerization initiator 1.5 parts by weight of hexanoate (half life temperature of 132.6 ° C, manufactured by Nippon Oil Holding Co., Ltd., product name: perhexyl 0), and t-hexyl peroxybenzoate (half life temperature of 160.3 ° C, manufactured by Nippon Oil Company, Ltd. ) Was combined with 1.5 parts by weight. The electroconductive particle was mix | blended and dispersed so that electroconductive particle might be set to 1.5 volume% in the obtained liquid mixture, and adhesive composition A was obtained.

Subsequently, the adhesive composition A obtained was applied to a 80-micrometer-thick fluororesin film which surface-treated on one side using a well-known coating apparatus, and hot-air-dried at 70 degreeC for 10 minutes, and the layer thickness is 15 micrometers. The film-form circuit connection material A was obtained.

Example 2

Except having made the compounding ratio of t-hexyl peroxy 2-ethylhexanoate which is a radical polymerization initiator into 1 weight part, and the compounding ratio of t-hexyl peroxy benzoate into 2 weight part, it carried out similarly to Example 1, The film-form circuit connection material B was obtained.

Comparative Example 1

A film-like circuit connecting material was prepared in the same manner as in Example 1 except that the blending ratio of t-hexylperoxy-2-ethylhexanoate as a radical polymerization initiator was 3 parts by weight and no t-hexylperoxybenzoate was used. C was obtained.

Comparative Example 2

A film-like circuit connecting material was produced in the same manner as in Example 1 except that t-hexylperoxy-2-ethylhexanoate, which is a radical polymerization initiator, was used and the blending ratio of t-hexylperoxybenzoate was 3 parts by weight. D was obtained.

Comparative Example 3

As a radical polymerization initiator, diisopropyl peroxydicarbonate (half life temperature 88.3 degreeC, the Japan oil company make, brand name: paroyl IPP instead of t-hexyl peroxy-2-ethylhexanoate and t-hexyl peroxy benzoate) ) Was obtained in the same manner as in Example 1, except that 3 parts by weight of) were obtained.

Evaluation Method 1

[Measurement of connection resistance]

A flexible circuit board (FPC) having 500 copper circuit wirings having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm using film-like circuit connecting materials A to D obtained by the above-mentioned manufacturing method, and 0.2 μm of indium oxide The glass (thickness 1.1mm, surface resistance 20Ω / square) in which the thin layer of (ITO) was formed was electrically connected over 2 mm in width by the thermocompression bonding apparatus (heating method: constant heat type, Dore Engineering Co., Ltd.). The conditions of the heating pressurization at this time made heating temperature 160 degreeC, 170 degreeC, 190 degreeC, pressurization pressure 3 Mpa, and heating pressurization time for 15 second. The resistance value between these electrically connected circuits was measured using a multimeter immediately after adhesion | attachment, and after hold | maintaining for 120 hours in 85 degreeC and the high temperature, high humidity tank of 85% RH. The resistance value was represented by the average (x + 3σ) of 150 resistance points between adjacent circuits. The obtained results are shown in Table 1.

Evaluation Method 2

[Measurement of Adhesive Strength]

The adhesive strength of the film-form circuit connection materials A-D obtained by the said manufacturing method was measured and evaluated by the 90 degree peeling method according to JIS-ZO237. Herein, Tensilon UTM-4 (peel rate 50 mm / min, 25 ° C, manufactured by Dongyang Baldwin Co., Ltd.) was used as a measuring apparatus for adhesive strength. The obtained results are shown in Table 2.

The film-like circuit connecting members A and B of Examples 1 and 2 exhibited good connection resistance and adhesive strength even at the heating temperature of 160 to 190 ° C., even after holding for 120 hours immediately after the adhesion and in a high temperature and high humidity bath at 85 ° C. and 85% RH. It turns out that it shows a favorable characteristic with respect to the heating temperature of wide area | region. On the other hand, in the film-form circuit connection material C of the comparative example 1 which is not based on this invention, connection resistance becomes high after 85 degreeC, 85% RH, 120 hours hold | maintenance at 170 degreeC heating, and 190 degreeC heating, and also adheres The strength showed a low value in comparison with Examples 1 and 2 immediately after adhesion and after holding for 120 hours in a high temperature, high humidity bath at 85 ° C and 85% RH. Moreover, in the film-form circuit connection material D of the comparative example 2, the connection resistance at the time of 160-170 degreeC heating became high, and the adhesive strength showed lower value.

Evaluation Method 3

The film-form circuit connection members A and E obtained in Example 1 and Comparative Example 3 were housed in a vacuum packaging material and allowed to stand at 40 ° C. for 3 days, and then the FPC and ITO were described at 160 ° C., 3 MPa, and 10 by the above-mentioned hot pressing apparatus. Heat compression was performed under the conditions for a second. About the obtained film, connection resistance and adhesive strength were measured according to evaluation methods 1 and 2. The results are shown in Table 2.

In Table 2, the film-form circuit connection material A of Example 1 shows favorable connection resistance and adhesive strength before and after 40 degreeC standing, and it turns out that it is excellent in storage stability. On the other hand, in the film-form circuit connection material E of the comparative example 3 which does not depend on this invention, it turned out that a connection resistance rises, adhesive strength is halved, and stability is not favorable after leaving for 3 days at 40 degreeC.

ADVANTAGE OF THE INVENTION According to this invention, the connection structure of the adhesive composition, circuit connection material, and circuit member which can harden | cure quickly at low temperature sufficiently, and the process margin at the time of hardening process is wide and a sufficiently stable adhesive strength and connection resistance are obtained. And a semiconductor device.

Claims (33)

A thermoplastic resin, a radically polymerizable compound, a first radical polymerization initiator having a half-life temperature of 90 to 145 ° C for 1 minute, and a second radical polymerization initiator having a half-life temperature of 150 to 175 ° C for 1 minute, Adhesive composition. The adhesive composition according to claim 1, wherein the radically polymerizable compound has two or more (meth) acryloyl groups in its molecule. The adhesive composition according to claim 1, wherein both the first radical polymerization initiator and the second radical polymerization initiator are peroxyester derivatives having a molecular weight of 180 to 1000. delete delete delete delete delete delete delete delete The adhesive composition according to claim 2, wherein both of the first radical polymerization initiator and the second radical polymerization initiator are peroxyester derivatives having a molecular weight of 180 to 1000. The said radically polymerizable compound is contained 50-250 weight part with respect to 100 weight part of said thermoplastic resins, Furthermore, the said 1st radical polymerization initiator and the said 2nd radical polymerization initiator are 0.05-30, respectively. An adhesive composition comprising a weight part. The said radical polymerizable compound is contained 50-250 weight part with respect to 100 weight part of said thermoplastic resins, Furthermore, 0.05-30 of said 1st radical polymerization initiator and the said 2nd radical polymerization initiator are respectively An adhesive composition comprising a weight part. The method according to claim 3, wherein 50 to 250 parts by weight of the radically polymerizable compound is contained per 100 parts by weight of the thermoplastic resin, and the first and second radical polymerization initiators are respectively 0.05 to 30. An adhesive composition comprising a weight part. The said radical polymerizable compound is contained 50-250 weight part with respect to 100 weight part of said thermoplastic resins, The said 1st radical polymerization initiator and the said 2nd radical polymerization initiator are 0.05-30, respectively. An adhesive composition comprising a weight part. The adhesive composition according to any one of claims 1 to 3 and 12 to 16, further comprising conductive particles. The adhesive composition of Claim 17 containing 0.5-30 weight part of said electroconductive particles with respect to 100 weight part of said thermoplastic resins. As a circuit connecting material for electrically connecting opposed circuit electrodes, The circuit connection material contains the adhesive composition according to any one of claims 1 to 3 and 12 to 16. As a circuit connecting material for electrically connecting opposed circuit electrodes, Said circuit connection material contains the adhesive composition of Claim 17, The circuit connection material characterized by the above-mentioned. As a circuit connecting material for electrically connecting opposed circuit electrodes, Said circuit connection material contains the adhesive composition of Claim 18, The circuit connection material characterized by the above-mentioned. The adhesive agent as described in any one of Claims 1-3, 12-16 is formed in a film form, The film adhesive characterized by the above-mentioned. The adhesive agent composition of Claim 17 is formed in a film form, The film adhesive characterized by the above-mentioned. The adhesive agent composition of Claim 18 is formed in film form, The film adhesive characterized by the above-mentioned. A film-form circuit connection material formed by forming the circuit connection material according to claim 19 in a film form. The film-form circuit connection material formed by forming the circuit connection material of Claim 20 into a film form. The circuit connecting material of Claim 21 is formed in the film form, The film-form circuit connecting material characterized by the above-mentioned. A first circuit member having a first circuit electrode formed on a main surface of the first circuit board, A second circuit member having a second circuit electrode formed on a main surface of the second circuit board, A circuit connecting member which is provided between the main surface of the first circuit board and the main surface of the second circuit board and electrically connects the first circuit electrode and the second circuit electrode in a state in which the second circuit electrode is disposed to face each other. A connecting member for a circuit member having a The circuit connecting member is a cured product of the circuit connecting material according to claim 19, wherein the circuit member connecting structure. A first circuit member having a first circuit electrode formed on a main surface of the first circuit board, A second circuit member having a second circuit electrode formed on a main surface of the second circuit board, A circuit connecting member which is provided between the main surface of the first circuit board and the main surface of the second circuit board and electrically connects the first circuit electrode and the second circuit electrode in a state in which the second circuit electrode is disposed to face each other. A connecting member for a circuit member having a The said circuit connection member is a hardened | cured material of the circuit connection material of Claim 20, The connection structure of the circuit member characterized by the above-mentioned. A first circuit member having a first circuit electrode formed on a main surface of the first circuit board, A second circuit member having a second circuit electrode formed on a main surface of the second circuit board, A circuit connecting member which is provided between the main surface of the first circuit board and the main surface of the second circuit board and electrically connects the first circuit electrode and the second circuit electrode in a state in which the second circuit electrode is disposed to face each other. A connecting member for a circuit member having a Said circuit connection member is a hardened | cured material of the circuit connection material of Claim 21, The connection structure of the circuit member characterized by the above-mentioned. A semiconductor device, A substrate on which the semiconductor element is mounted; A semiconductor element connecting member provided between the semiconductor element and the substrate to electrically connect the semiconductor element and the substrate A semiconductor device comprising: The said semiconductor element connection member is a hardened | cured material of the adhesive composition in any one of Claims 1-3, 12-16. The semiconductor device characterized by the above-mentioned. A semiconductor device, A substrate on which the semiconductor element is mounted; A semiconductor element connecting member provided between the semiconductor element and the substrate to electrically connect the semiconductor element and the substrate A semiconductor device comprising: The said semiconductor element connection member is a hardened | cured material of the adhesive composition of Claim 17, The semiconductor device characterized by the above-mentioned. A semiconductor device, A substrate on which the semiconductor element is mounted; A semiconductor element connecting member provided between the semiconductor element and the substrate to electrically connect the semiconductor element and the substrate A semiconductor device comprising: The said semiconductor element connection member is a hardened | cured material of the adhesive composition of Claim 18, The semiconductor device characterized by the above-mentioned.

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