JP2015030745A - Resin composition, semiconductor device, multilayer circuit board, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can prevent generation of a void between a circuit member and the resin composition and in the resin composition, and can prevent a protrusion of the resin composition from the edge of the circuit member, and to provide a semiconductor device, a multilayer circuit board and an electronic component which are obtained by using the resin composition.SOLUTION: The resin composition is used for sticking the circuit members to each other and electrically connecting circuit electrodes, which belong to the respective circuit members, to each other, and has a flux function. The resin composition contains: a thermosetting resin; a compound having flux activity; and a core-shell particle having a core layer comprising a rubber component and a shell layer which comprises an acrylic component and is formed to cover the core layer. It is preferable that the content of the core-shell particle is 0.5-15 mass%.

Description

  The present invention relates to a resin composition, a semiconductor device, a multilayer circuit board, and an electronic component.

  Along with the recent demand for higher functionality and lighter, thinner and smaller electronic devices, semiconductor packages (semiconductor devices) used in these electronic devices are becoming smaller and more pins than ever before. . In order to obtain an electrical connection between these electronic components, solder bonding is used. As this solder bonding, for example, a conductive bonding portion between semiconductor chips, a conductive bonding portion between a semiconductor chip such as a package (semiconductor device) mounted on a flip chip and a circuit board, a conductive bonding portion between circuit boards, etc. Examples include a joint portion between members. In order to ensure electrical connection strength and mechanical connection strength, a sealing resin generally called an underfill material is injected into the solder joint portion (underfill sealing).

When the gap (gap) generated by the solder joint is reinforced with a liquid sealing resin (underfill material), the liquid sealing resin (underfill material) is supplied after the solder joint, and the solder is bonded by curing it. The part is reinforced. However, as the electronic components become thinner and smaller, the solder joints are narrowed in pitch / narrow gap. Therefore, even if liquid sealing resin (underfill material) is supplied after soldering, the liquid sealing between the gaps There is a problem that the stop resin (underfill material) does not spread and it becomes difficult to completely fill the resin. In order to solve such a problem, a method is known in which solder bonding and adhesion are collectively performed through a resin composition having a flux function (see, for example, Patent Document 1).
However, the conventional resin composition has a high filling property, but has a problem in that minute voids are generated between the circuit member and the resin composition and in the resin composition. Further, the conventional resin composition has a problem that the resin composition protrudes from the edge of the circuit member.

JP 2007-107006 A

  An object of the present invention is to prevent voids from being generated between and within a circuit member and a resin composition, and to prevent the resin composition from protruding from the edge of the circuit member. It is to provide a resin composition, and to provide a semiconductor device, a multilayer circuit board, and an electronic component using such a resin composition.

Such an object is achieved by the present invention described in the following (1) to (12).
(1) A resin composition having a flux function, which is used for bonding circuit members together and electrically connecting circuit electrodes of each circuit member,
A thermosetting resin;
A compound having flux activity;
A resin composition comprising: a core layer composed of a rubber-based component; and a core-shell particle having a shell layer composed of an acrylic component and formed to cover the core layer.

(2) The resin composition according to (1), wherein the content of the core-shell particles is 0.1% by mass or more and 15% by mass or less.
(3) The resin composition according to (1) or (2), wherein the average particle diameter of the core-shell particles is 10 nm or more and 1000 nm or less.
(4) The resin composition according to any one of (1) to (3), wherein the rubber component and the acrylic component constitute a copolymer.

(5) The resin composition according to any one of (1) to (4), wherein the thermosetting resin includes an epoxy resin.
(6) The said epoxy resin is a resin composition as described in said (5) containing a liquid epoxy resin at 25 degreeC.
(7) The resin composition according to any one of the above (1) to (6), comprising an inorganic filler having an average particle size of 500 nm or less.

(8) Content of the said inorganic filler is a resin composition as described in said (7) which is 0.1 to 80 mass%.
(9) The resin composition according to any one of (1) to (8), wherein the compound having the flux activity is a compound having a carboxyl group and / or a phenolic hydroxyl group.

(10) A semiconductor device having a cured product of the resin composition according to any one of (1) to (9).
(11) A multilayer circuit board having a cured product of the resin composition according to any one of (1) to (9).
(12) An electronic component having a cured product of the resin composition according to any one of (1) to (9).

  According to the present invention, it is possible to prevent voids between the circuit member and the resin composition and in the resin composition, and to prevent the resin composition from protruding from the edge of the circuit member. And a semiconductor device, a multilayer circuit board, and an electronic component using such a resin composition can be provided.

It is sectional drawing which shows an example of the manufacturing method of a semiconductor device. It is sectional drawing which shows an example of the manufacturing method of a multilayer circuit board.

Hereinafter, the present invention will be described in detail.
<Resin composition>
First, the resin composition of the present invention will be described.
The resin composition of the present invention is used, for example, when electrically connecting circuit members, such as a substrate, a semiconductor chip, and a semiconductor package (semiconductor device), which can be soldered together. Moreover, the resin composition of this invention has a flux function. In the present specification, the circuit member means, for example, a semiconductor wafer, a rigid substrate, a flexible substrate, a rigid flexible substrate, or the like on which a wiring circuit is formed.

The resin composition of the present invention has a flux function, and includes a thermosetting resin, a compound having flux activity, a core layer composed of a predetermined material and a core-shell particle including a shell layer. Yes.
By the way, although the conventional resin composition has high filling properties, there is a problem that minute voids are generated between the circuit member and the resin composition and in the resin composition. Further, the conventional resin composition has a problem that the resin composition protrudes from the edge of the circuit member.

  On the other hand, as in the present invention, a core layer composed of a rubber component together with a thermosetting resin and a compound having flux activity (hereinafter also simply referred to as “flux active compound”), and an acrylic component The generation of voids can be prevented by adding the core-shell particles having a shell layer formed so as to cover the core layer, and the resin composition protrudes from the edge of the circuit member. Can be prevented. Further, since no void is generated between the circuit member and the resin composition, adhesion between the circuit members is facilitated.

Hereinafter, each component will be described in detail.
[Thermosetting resin]
The resin composition of the present invention contains a thermosetting resin. Thereby, circuit members can be joined, filling the gap between circuit members.
As the thermosetting resin, known resins can be used, and are not particularly limited. For example, epoxy resin, phenoxy resin, silicone resin, oxetane resin, phenol resin, (meth) acrylate resin, polyester resin (unsaturated) Polyester resin), diallyl phthalate resin, maleimide resin, polyimide resin (polyimide precursor resin), bismaleimide-triazine resin, and the like. In particular, the use of a thermosetting resin containing at least one selected from the group consisting of epoxy resins, (meth) acrylate resins, phenoxy resins, polyester resins, polyimide resins, silicone resins, maleimide resins, and bismaleimide-triazine resins. preferable. Among these, an epoxy resin is preferable from the viewpoint of excellent curability and storage stability, heat resistance, moisture resistance, and chemical resistance of a cured product.

As the epoxy resin, one having two or more epoxy groups in one molecule can be used. Specifically, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cresol naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene skeleton type epoxy resin, diallyl bisphenol A type epoxy resin, bisphenol A diester Glycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol S diglycidyl ether type epoxy, o-allylbisphenol A type diglycidyl ether, 3,3 ′, 5,5′-tetramethyl 4,4′-dihydroxybiphenyl Diglycidyl ether type epoxy, 4,4′-dihydroxybiphenyl diglycidyl ether type epoxy, 1,6-dihydroxybiphenyl diglycidyl ether type epoxy, Fe Examples of the epoxy resin include a novolac type epoxy, a bromine type cresol novolac type epoxy, a bisphenol D diglycidyl ether type epoxy, a glycidyl ether of 1,6 naphthalenediol, and a triglycidyl ether of aminophenols. These may be used alone or in combination. In order to obtain a resin composition having excellent reliability, it is preferable that the ionic impurities such as Na ⁺ and Cl ⁻ of the epoxy resin are as small as possible.

  The epoxy resin preferably contains a liquid at 25 ° C. Thereby, the filling property between the circuit members of a resin composition can be improved. Moreover, when joining circuit members, the unevenness | corrugation (gap) produced by the some wiring circuit etc. on a circuit member can be embedded more effectively. In addition, when the resin composition is formed into a film, flexibility and flexibility can be imparted to the film, so that a film having excellent handling properties can be obtained. Further, the electrical connection between the circuit members can be made better. Specific examples of the epoxy resin that is liquid at 25 ° C. include bisphenol A diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol S diglycidyl ether type epoxy, o-allylbisphenol A type diglycidyl ether, 3, 3 ', 5,5'-tetramethyl 4,4'-dihydroxybiphenyl diglycidyl ether type epoxy, 4,4'-dihydroxybiphenyl diglycidyl ether type epoxy, 1,6-dihydroxybiphenyl diglycidyl ether type epoxy, phenol novolac type Epoxy, bromine-type cresol novolak-type epoxy, bisphenol D diglycidyl ether-type epoxy, 1,6-naphthalenediol glycidyl ether, aminophenol triglycidyl ether Ether, mono-epoxy compounds having one epoxy group in the molecule.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, and the like. Among these, it is preferable to use bisphenol A type epoxy resin and bisphenol F type epoxy resin. Thereby, the adhesiveness with respect to the circuit member of a resin composition and the mechanical characteristic after hardening of a resin composition can be made excellent.

The epoxy resin that is liquid at 25 ° C. is more preferably one having a viscosity at 25 ° C. of 500 mPa · s or more and 50,000 mPa · s or less, more preferably 800 mPa · s or more and 40,000 mPa · s. The following are mentioned. By making the viscosity at 25 ° C. within the above range, the produced film has appropriate flexibility and excellent handling properties.
Although content of the thermosetting resin in a resin composition is not specifically limited, It is preferable that they are 10 mass% or more and 75 mass% or less, and it is more preferable that they are 15 mass% or more and 45 mass% or less. Thereby, the heat resistance after hardening and mechanical characteristics can be made particularly excellent.

[Compound with flux activity]
The resin composition of the present invention includes a compound having a flux activity (hereinafter also referred to as a flux active compound), thereby removing the oxide film on the solder surface of the terminal of the circuit member, and ensuring that the circuit members are connected to each other. Since it can be soldered, a multilayer circuit board, an electronic component, a semiconductor device, etc. with high connection reliability can be obtained.

The flux active compound is not particularly limited as long as it has a function of removing an oxide film on the surface of the solder, but it is either a carboxyl group or a phenolic hydroxyl group, or a compound having both a carboxyl group and a phenol hydroxyl group Is preferred.
The blending amount of the flux active compound is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 20% by mass or less. When the blending amount of the flux active compound is within the above range, the flux activity can be improved, and when the resin composition is cured, the unreacted epoxy resin and the flux active compound are prevented from remaining. Migration resistance can be improved.

  Further, among the compounds that act as curing agents for epoxy resins, there are compounds having flux activity (hereinafter, such compounds are also referred to as curing agents having flux activity). For example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids and the like that act as curing agents for epoxy resins also have a flux action. In the present invention, a curing agent having such a flux activity that acts as a flux and also acts as a curing agent for an epoxy resin can be suitably used.

  The flux active compound having a carboxyl group means a compound having one or more carboxyl groups in the molecule, and may be liquid or solid. Further, the flux active compound having a phenolic hydroxyl group means a compound having one or more phenolic hydroxyl groups in the molecule, and may be liquid or solid. Further, the flux active compound having a carboxyl group and a phenolic hydroxyl group means a compound having one or more carboxyl groups and phenolic hydroxyl groups in the molecule, and may be liquid or solid.

Among these, examples of the flux active compound having a carboxyl group include aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, aliphatic carboxylic acids, and aromatic carboxylic acids.
Examples of the aliphatic acid anhydride related to the flux active compound having a carboxyl group include succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, and the like.

Examples of the alicyclic acid anhydride related to the flux active compound having a carboxyl group include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and trialkyl. Examples include tetrahydrophthalic anhydride and methylcyclohexene dicarboxylic acid anhydride.
Examples of the aromatic acid anhydride related to the flux active compound having a carboxyl group include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tris trimellitate. Etc.

Examples of the aliphatic carboxylic acid related to the flux active compound having a carboxyl group include compounds represented by the following general formula (1), formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid pivalate, and caprylic acid. , Lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, oleic acid, fumaric acid, maleic acid, oxalic acid, malonic acid, oxalic acid and the like.
_{HOOC- (CH 2) n -COOH (} 1)
(In formula (1), n represents an integer of 1 or more and 20 or less.)

  As the aromatic carboxylic acid related to the flux active compound having a carboxyl group, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, Mellitic acid, xylic acid, hemelic acid, mesitylene acid, prenylic acid, toluic acid, cinnamic acid, salicylic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid ), 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid (3,4,5-trihydroxybenzoic acid), 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy -2-Naphthoic acid derivatives such as naphthoic acid, phenolphthaline, diphenolic acid, etc. It is.

  Among these flux active compounds having the carboxyl group, the balance of the activity of the flux active compound, the amount of outgas generated when the resin composition is cured, and the elastic modulus and glass transition temperature of the cured resin composition However, the compound represented by the general formula (1) is preferable. And among the compounds shown by the general formula (1), the compound in which n is 3 to 10 can suppress an increase in the elastic modulus in the resin composition after curing, and the semiconductor chip and the substrate It is particularly preferable in that the adhesion between circuit members such as the above can be improved.

Among the compounds represented by the general formula (1), examples of the compound in which n is 3 to 10 include, for example, n = 3 glutaric acid (HOOC— (CH ₂ ) ₃ —COOH), n = 4 adipic acid _{(HOOC- (CH 2) 4 -COOH} ), n = 5 of pimelic acid _{(HOOC- (CH 2) 5 -COOH} ), sebacic acid of _{n = 8 (HOOC- (CH 2} ) 8 -COOH) , and n = 10 HOOC— (CH ₂ ) ₁₀ —COOH— and the like.

Examples of the flux active compound having the phenolic hydroxyl group include phenols. Specifically, for example, phenol, o-cresol, 2,6-xylenol, p-cresol, m-cresol, o-ethylphenol, 2,4-xylenol, 2,5 xylenol, m-ethylphenol, 2, 3-xylenol, meditol, 3,5-xylenol, p-tertiarybutylphenol, catechol, p-tertiaryamylphenol, resorcinol, p-octylphenol, p-phenylphenol, bisphenol A, bisphenol F, bisphenol AF, biphenol, diallyl Examples thereof include monomers containing a phenolic hydroxyl group such as bisphenol F, diallyl bisphenol A, trisphenol, and tetrakisphenol.
A compound having either a carboxyl group or a phenol hydroxyl group as described above, or a compound having both a carboxyl group and a phenol hydroxyl group is incorporated three-dimensionally by reaction with an epoxy resin.

Therefore, from the viewpoint of improving the formation of a three-dimensional network of the epoxy resin after curing, as the flux active compound, a curing agent having a flux activity and acting as a curing agent for the epoxy resin is used. It is preferable to use it. As a curing agent having flux activity, for example, 1 or more phenolic hydroxyl groups that can be added to an epoxy resin in one molecule and an aromatic group that directly binds to an aromatic that exhibits a flux action (oxide film removal action) And compounds having two or more carboxyl groups. Examples of the curing agent having such flux activity include 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), 2,6-dihydroxybenzoic acid, 3, Benzoic acid derivatives such as 4-dihydroxybenzoic acid and gallic acid (3,4,5-trihydroxybenzoic acid); 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3, Examples thereof include naphthoic acid derivatives such as 7-dihydroxy-2-naphthoic acid; phenolphthaline; and diphenolic acid. These may be used alone or in combination of two or more.
Among these, it is preferable to use 2,3-dihydroxybenzoic acid, gentisic acid, and phenolphthaline, which are excellent in the effect of removing the oxide film on the solder surface and the reactivity with the epoxy resin.

  Further, the blending amount of the curing agent having flux activity in the resin composition is preferably 1% by mass or more and 30% by mass or less, and particularly preferably 3% by mass or more and 20% by mass or less. When the blending amount of the curing agent having the flux activity in the resin composition is within the above range, the flux activity of the resin composition can be improved, and the epoxy resin and the unreacted flux are contained in the resin composition. It is prevented that the curing agent having activity remains. Note that migration occurs when the curing agent having unreacted flux activity remains.

  The compounding ratio of the epoxy resin and the flux active compound is not particularly limited, but (epoxy resin / flux active compound) is preferably 0.5 or more and 12 or less, particularly preferably 2 or more and 10 or less. By setting (epoxy resin / flux active compound) to be equal to or higher than the above lower limit value, when the resin composition is cured, unreacted flux active compound can be reduced, and thus migration resistance can be improved. . Moreover, since it is possible to reduce unreacted epoxy resin when the resin composition is cured by setting the upper limit value or less, migration resistance can be improved.

[Core shell particles]
The resin composition of the present invention contains core-shell particles.
The core-shell particles have a core layer composed of a rubber component and a shell layer composed of an acrylic component and formed so as to cover the core layer.
By including such core-shell particles, the pressure on the resin composition between the circuit members can be relieved when the circuit members are bonded together. As a result, it is possible to effectively prevent the resin composition from protruding from the edge of the circuit member.

Moreover, the viscosity of the whole resin composition can be made moderate by including the core shell particle | grains mentioned above. As a result, generation of voids between the circuit member and the resin composition can be effectively prevented. Moreover, the unevenness | corrugation of the circuit member surface can be embedded favorably.
In addition, when there is no shell layer and the particles are only the core layer of the rubber component, there are problems such as insufficient dispersibility in the resin composition and unevenness in the film. By providing a shell layer composed of a system component, homogeneous dispersion is possible, and a film having no variation in the protrusion prevention effect, void prevention effect, and solder connectivity effect can be produced.

Examples of the rubber component constituting the core layer include conjugated diene rubbers such as butadiene rubber, isoprene rubber, and chloroprene rubber, acrylic rubber, silicon rubber, styrene rubber, acrylonitrile rubber, nitrile rubber, fluorine rubber, and a combination thereof. Examples thereof include a polymer or a composite.
Moreover, as an acryl-type component which comprises a shell layer, (meth) acrylic acid which uses (meth) acrylic acid methyl, (meth) acrylic acid butyl, (meth) acrylic acid, (meth) acrylonitrile etc. as a monomer component, for example An ester copolymer etc. are mentioned.

Further, the rubber component constituting the core layer and the acrylic component constituting the shell layer may constitute a copolymer. That is, the core-shell particles are composed of a copolymer of a rubber component and an acrylic component, the comb component portion of the copolymer is on the core layer side (center side), and the acrylic component portion is on the shell layer side. You may be comprised so that it may be located in (outside). Thereby, it can prevent effectively that a core layer and a shell layer isolate | separate unintentionally, and can make durability of a core-shell particle higher.
Examples of the copolymer of the rubber component and the acrylic component include, for example, methyl (meth) acrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, and acryl-butadiene. Examples include copolymers, acrylic-silicon copolymers, (meth) acrylic acid methyl-isoprene-styrene copolymers, and the like.

  The content of the core-shell particles in the resin composition is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less. Thereby, generation | occurrence | production and protrusion of a void can be prevented more efficiently, making the solder connectivity of circuit members favorable. On the other hand, when the content of the core-shell particles is less than the lower limit, depending on the content of the inorganic filler, the viscosity of the resin composition may be reduced, and the handleability of the resin composition may be reduced. Moreover, when content of core-shell particles exceeds the said upper limit, depending on the particle size etc. of core-shell particles, the solder connectivity of circuit members may fall. Moreover, the visibility of the junction location of a circuit member may fall.

  The lower limit of the average particle diameter of the core-shell particles is preferably 10 nm or more, more preferably 50 nm or more, and particularly preferably 100 nm or more. The upper limit is preferably 1000 nm or less, particularly preferably 500 nm or less. Thereby, when adhering circuit members, the pressure with respect to the resin composition between circuit members can be relieve | moderated more effectively. As a result, the protrusion of the resin composition from the edge of the circuit member can be more effectively prevented. On the other hand, when the average particle diameter of the core-shell particles is less than the lower limit, the pressure on the resin composition between the circuit members may not be sufficiently relaxed depending on the content of the core-shell particles. Moreover, when the average particle diameter of the core-shell particles exceeds the upper limit, depending on the content of the core-shell particles, the solder connectivity between the circuit members may be deteriorated.

[Inorganic filler]
The resin composition of the present invention may contain an inorganic filler. By including the inorganic filler, the linear expansion coefficient of the cured resin composition can be reduced, thereby improving the reliability. Moreover, the viscosity of a resin material can be made more moderate because a resin composition contains an inorganic filler with the core-shell particle mentioned above. As a result, generation of voids between the circuit member and the resin composition can be more effectively prevented.

  In addition, the inorganic filler preferably has an average particle size of 500 nm or less, and more preferably 300 nm or less. By including the inorganic filler of such a size, the viscosity of the resin composition at the time of joining circuit members can be made more appropriate, and the joining can be performed satisfactorily. Moreover, aggregation of an inorganic filler within a resin composition can be suppressed and an external appearance can be improved. Further, when light passes through the resin composition, it is possible to reduce the inhibition of visible light transmission by the inorganic filler. As a result, the circuit member is bonded to the circuit member when the resin composition is applied to the circuit member. The location visibility is further improved, positioning becomes easier, and the circuit members can be electrically connected to each other well by the flux function.

The inorganic filler is not particularly limited as long as the above conditions are satisfied, and examples thereof include silver, titanium oxide, silica, and mica. Of these, silica is preferably used. Thereby, it can be made the thing excellent in the thermal characteristic of the resin composition after hardening. Moreover, the visibility of the joining location of the circuit member when the resin composition is applied to the circuit member can be improved. As a result, alignment can be performed more easily.
Moreover, as a shape of a silica filler, although there exists crushing silica and spherical silica, spherical silica is preferable.

  Although content of an inorganic filler is not specifically limited, It is preferable that it is 0.1 to 80 mass% with respect to the whole resin composition, and it is more preferable that it is 20 to 70 mass%. . Thereby, it can be made excellent in the thermal characteristic of the resin composition after hardening, making the visibility of the joint location of a circuit member good when giving a resin composition to a circuit member. In addition, by setting the above range, the difference in linear expansion coefficient between the cured resin composition and the circuit member is reduced, and the stress generated during the thermal shock can be reduced. Can be more reliably suppressed. Furthermore, since it can suppress that the elasticity modulus of the resin composition after hardening becomes high too much, the reliability of a semiconductor device rises.

[Other ingredients]
Moreover, the resin composition of this invention may contain components other than the above.
For example, the resin composition of the present invention may contain a phenolic curing agent having a weight average molecular weight of 300 or more and 2500 or less. Thereby, the glass transition temperature of the hardened | cured material of a resin composition can be raised, and also it becomes possible to improve ion migration resistance. Moreover, moderate softness | flexibility can be provided to a resin composition. Further, the electrical connection between the circuit members can be made better.

  The phenolic curing agent is not particularly limited, and examples thereof include phenol novolak resin, cresol novolak resin, bisphenol A type novolak resin, bisphenol F type novolak resin, and bisphenol AF type novolak resin. Among them, it is preferable to use a phenol novolac resin or a cresol novolac resin that can satisfy the above-described relationship more easily and can effectively increase the glass transition temperature of the cured product.

  The content of the phenolic curing agent in the resin composition is not particularly limited, but is preferably 1% by mass or more and 30% by mass or less, and preferably 3% by mass or more and 25% by mass or less. More preferred. By setting the content of the phenolic curing agent in the above range, the resin composition can more effectively fill the unevenness (gap) generated by a plurality of wiring circuits on the circuit member. Moreover, the glass transition temperature of the hardened | cured material of a resin composition can be raised effectively.

  When the total content of mononuclear to trinuclear in the phenolic curing agent is less than 20% by mass with respect to the phenolic curing agent (the total content of four or more nuclei is 80% by mass or more) The reactivity with the epoxy resin is lowered, and the unreacted phenolic novolak resin remains in the cured product of the resin composition, so that the migration resistance may be lowered. Further, the total content of mononuclear to trinuclear in the phenolic curing agent is greater than 70% by mass with respect to the phenolic curing agent (the total content of four or more nuclei is 30% by mass or less). In this case, the amount of outgas at the time of curing the resin composition increases, which may cause a problem that the surface of a circuit member such as a semiconductor chip or a substrate is contaminated or migration resistance is lowered.

Although the total content of the binuclear body and the trinuclear body in the phenol-based curing agent is not particularly limited, it is preferably 10 mass% or more and 70 mass% or less. Thereby, the amount of outgas at the time of hardening a resin composition increases, and it can prevent more effectively that the surface of circuit members, such as a semiconductor chip and a circuit board, is contaminated.
Although content of the mononuclear body in the said phenol type hardening | curing agent is not specifically limited, It is preferable that it is 25 mass% or less with respect to a phenol type hardening | curing agent, and it is especially preferable that it is 20 mass% or less. By setting the content of the mononuclear body within the above range, the amount of outgas when the resin composition is cured can be reduced, and contamination of circuit members such as semiconductor chips and circuit boards can be suppressed. Furthermore, the migration resistance can be improved.

  Although the weight average molecular weight of the said phenol type hardening | curing agent is not specifically limited, It is preferable that it is 300 or more and 2500 or less, and it is especially preferable that it is 400 or more and 2300 or less. Thereby, the amount of outgas at the time of hardening a resin composition increases, and it can prevent more effectively that the surface of circuit members, such as a semiconductor chip and a circuit board, is contaminated. Here, the weight average molecular weight can be measured by GPC (gel permeation chromatogram).

  The resin composition may further contain a curing accelerator. A hardening accelerator can be suitably selected according to the kind etc. of curable resin. As the curing accelerator, for example, an imidazole compound having a melting point of 150 ° C. or higher can be used. When the melting accelerator used has a melting point of 150 ° C. or higher, the solder component constituting the solder bump can move to the surface of the internal electrode provided on the semiconductor chip before the curing of the resin composition is completed. The electrical connection between the internal electrodes can be made good. Examples of the imidazole compound having a melting point of 150 ° C. or higher include 2-phenyl-4-methylimidazole, 2-phenylhydroxyimidazole, 2-phenyl-4-methylhydroxyimidazole, and the like. They can be used in combination.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.005% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass. preferable. As a result, the function as a curing accelerator can be exhibited more effectively, the curability of the resin composition can be improved, and the melt viscosity of the resin at the melting temperature of the solder component constituting the solder bump is increased. However, a good solder joint structure can be obtained. Moreover, the preservability of the resin composition can be further improved.
These curing accelerators may be used alone or in combination of two or more.

  The melt viscosity at 100 ° C. of the resin composition as described above was measured for 5 minutes using “MARS” manufactured by Thermo Fisher Scientific at a parallel plate of 20 mmφ, a gap of 0.05 mm, a frequency of 1 Hz and a constant temperature of 100 ° C. And the viscosity in the state where the viscosity after 5 minutes was stabilized was made into the melt viscosity in 100 degreeC. The melt viscosity at 100 ° C. is preferably 1000 Pa · s or more and 10,000 Pa · s or less, and more preferably 1500 Pa · s or more and 7000 Pa · s or less. Thereby, the protrusion of the resin composition from the edge part of a circuit member and generation | occurrence | production of a void can be prevented more effectively. In addition, gaps caused by a plurality of wiring circuits on the circuit member can be more effectively embedded.

  The resin composition of the present invention may further contain a silane coupling agent. By including a silane coupling agent, the adhesiveness of the resin composition with respect to circuit members, such as a semiconductor chip and a board | substrate, can be improved. As the silane coupling agent, for example, an epoxy silane coupling agent, an aromatic-containing aminosilane coupling agent and the like can be used. These may be used alone or in combination of two or more. The blending amount of the silane coupling agent may be appropriately selected, but is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.05% by mass or more and 5% by mass with respect to the entire resin composition. It is not more than mass%, more preferably not less than 0.1 mass% and not more than 2 mass%.

Moreover, when using the resin composition of this invention as an adhesive film, the resin composition of this invention may contain film-forming resin.
Examples of the film-forming resin include (meth) acrylic resin, phenoxy resin, polyester resin, polyurethane resin, polyimide resin, siloxane-modified polyimide resin, polybutadiene, polypropylene, styrene-butadiene-styrene copolymer, styrene-ethylene- Butylene-styrene copolymer, polyacetal resin, polyvinyl butyral resin, polyvinyl acetal resin, butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-acrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer Examples include coalescence, polyvinyl acetate, and nylon. These may be used alone or in combination of two or more. Among these, as the (D) film-forming resin, it is preferable to use at least one selected from the group consisting of (meth) acrylic resins, phenoxy resins, and polyimide resins.

The weight average molecular weight of the film-forming resin is not particularly limited, but is preferably 10,000 or more, more preferably 20,000 to 1,000,000, and even more preferably 30,000 to 900,000. When the weight average molecular weight is in the above range, the film forming property of the resin composition can be further improved.
When the resin composition is used as an adhesive film, the content of the film-forming resin is not particularly limited, but is preferably 0.5% by mass to 50% by mass in the resin composition, and preferably 1% by mass to 40%. More preferably, it is at most 3% by mass and at most 35% by mass. When the content is within the above range, the fluidity of the resin composition can be suppressed, and the handling of the adhesive film becomes easy.

When the resin composition is used as an adhesive film, the thickness of the adhesive film is not particularly limited, but is preferably 1 μm or more and 300 μm or less, and more preferably 5 μm or more and 200 μm or less. When the thickness is within the above range, the gap between the circuit members can be sufficiently filled with the resin component, and the mechanical adhesive strength after curing of the resin component can be ensured.
In addition, when a resin composition is a film form, it is preferable that it is a film form at 25 degreeC. Thereby, the handleability of a film improves.

<< Semiconductor Device Manufacturing Method and Semiconductor Device >>
Next, a method for manufacturing a semiconductor device using the resin composition of the present invention and a semiconductor device will be described.
FIG. 1 is a cross-sectional view showing an example of a method for manufacturing a semiconductor device.
As shown in FIG. 1, a circuit board 4 (circuit member) having a base material 41, a wiring circuit 42, an insulating portion 43, and a pad portion 44 is prepared (FIG. 1A).

The average thickness of the wiring circuit 42 on the circuit board 4 is preferably 1 μm or more and 30 μm or less, and more preferably 5 μm or more and 20 μm or less. Thereby, the resin composition 1 can more reliably bury the irregularities (gap) generated by the plurality of wiring circuits 42 on the circuit board 4.
The distance between the centers of the adjacent wiring circuits 42 is preferably 1 μm or more and 500 μm or less, and more preferably 5 μm or more and 300 μm or less. As a result, the resin composition 1 can reliably bury the unevenness (gap) generated between the circuit board 4 and the semiconductor chip 5 (other circuit member).

On the other hand, a semiconductor wafer provided with a plurality of solder bumps 51 is prepared.
The resin composition 1 (the resin composition of the present invention) is applied so as to cover the entire surface of the semiconductor wafer on which the solder bumps 51 are provided. As a method of applying on the wafer, a printing method using a metal mask or a mesh mask, a spin coating method, a method of attaching a sheet formed on a release film, or the like can be used.

Next, the semiconductor wafer with a coating film made of the resin composition is divided into pieces by dicing to obtain the semiconductor chip 5 (other circuit member). In this process, it is possible to divide into pieces by using a general dicing apparatus and performing dry or wet dicing.
Next, while aligning the solder bumps 51 of the semiconductor chip 5 and the pad portions 44 of the circuit board 4 (FIG. 1B), the semiconductor chip 5 and the circuit board 4 are temporarily placed through the resin composition 1. The semiconductor chip 5 is fixed on the circuit board 4 by pressure bonding (FIG. 1C).

  A method for temporary pressure bonding is not particularly limited, but a pressure bonding machine, a flip chip bonder, or the like can be used. The conditions for temporary pressure bonding are not particularly limited, but the temperature is preferably 60 ° C. or higher, more preferably 80 ° C. or higher. Moreover, it is preferable to set it as 220 degrees C or less, and it is more preferable to set it as 180 degrees C or less. The time is preferably from 0.1 second to 60 seconds, particularly preferably from 1 second to 60 seconds. The pressure is preferably 0.005 MPa or more, and more preferably 0.05 MPa or more. Further, it is preferably 2 MPa or less, and more preferably 0.5 MPa or less. As a result, the semiconductor chip 5 can be securely temporarily bonded to the circuit board 4.

Next, the solder bump 51 is melted to form a solder connection portion 511 to be soldered to the pad portion 44 (FIG. 1D).
The temperature for solder connection is preferably a temperature at which the solder layer melts, for example, 110 ° C. or higher and 280 ° C. or lower, although the temperature depends on the type of solder used. The time is preferably from 5 seconds to 500 seconds, particularly preferably from 10 seconds to 100 seconds. Furthermore, the pressure is preferably 0.005 MPa or more, and more preferably 0.05 MPa or more. Further, it is preferably 2 MPa or less, and more preferably 0.5 MPa or less. The conditions for solder connection can be appropriately selected depending on the solder used.

  This solder bonding is preferably performed under conditions such that the resin composition 1 is cured after the solder bumps 51 are melted. That is, the solder bonding is preferably performed under the condition that the solder bump 51 is melted but the curing reaction of the resin composition 1 does not proceed so much. Thereby, the shape of the solder connection part at the time of soldering can be made into the stable shape which is excellent in connection reliability.

  Next, the resin composition 1 is heated and cured. The conditions for curing are not particularly limited, but the temperature is preferably 130 ° C. or higher and 220 ° C. or lower, and particularly preferably 140 ° C. or higher and 200 ° C. or lower. The time is preferably from 30 minutes to 600 minutes, particularly preferably from 60 minutes to 500 minutes. Further, the resin composition 1 may be cured under a pressurized atmosphere. Although it does not specifically limit as a pressurization method, It can carry out by introduce | transducing pressurized fluids, such as nitrogen and argon, in oven. The pressure is preferably from 0.1 MPa to 10 MPa, particularly preferably from 0.5 MPa to 5 MPa. Thereby, the void in the resin composition 1 can be reduced.

Next, bumps 45 for mounting the semiconductor device are formed on the mother board (FIG. 1E). The bump 45 is not particularly limited as long as it is a metal material having conductivity, but solder having excellent conductivity and stress relaxation properties is preferable. The method for forming the bump 45 is not particularly limited, but can be formed by connecting solder balls using a flux.
In this way, a semiconductor device 10 in which the circuit board 4 and the semiconductor chip 5 are bonded with the cured product 1 ′ of the resin composition as shown in FIG. 1E can be obtained. Since the semiconductor device 10 is bonded with the cured product 1 ′ of the resin composition 1 as described above, it has excellent electrical connection reliability.
In the above description, the case where the resin composition of the present invention is applied to a semiconductor wafer has been described. However, the present invention is not limited to this, and it may be applied on the circuit board 4 or both of the semiconductor wafer and the circuit board 4. You may give to.

<< Multilayer Circuit Board Manufacturing Method and Multilayer Circuit Board >>
Next, a method for producing a multilayer circuit board using the resin composition of the present invention and the multilayer circuit board will be described.
FIG. 2 is a cross-sectional view illustrating an example of a method for manufacturing a multilayer circuit board.
First, a circuit board 6 (circuit member) having a substrate 61, a wiring circuit 62, an insulating part 63, and a pad part 64 is prepared (FIG. 2A).

  On the other hand, a circuit board 7 (another circuit member) having a base 71, a wiring circuit 72, an insulating part 73, a solder bump 75, and a pad part 74 is prepared, and the resin composition 1 is coated so as to cover the entire circuit board 7. After applying in the same manner as described above (FIG. 2B), the circuit board 6 and the circuit board 7 are connected to each other while the pad portion 64 of the circuit board 6 and the solder bump 75 of the circuit board 7 are aligned. Temporary pressure bonding is performed under the same conditions as in FIG. 2 (c).

Next, the solder bumps 75 are melted under the same conditions as the above-described solder joints to form solder joints 711 that are soldered to the respective pad parts 64 (FIG. 2D).
Thereafter, the resin composition 1 is cured under the same conditions as those for the resin composition 1 described above, and the circuit board 6 and the circuit board 7 are cured as shown in FIG. The multilayer circuit board 100 bonded with the object 1 ′ can be obtained. Since the multilayer circuit board 100 is bonded with the cured product 1 ′ of the resin composition 1 as described above, the electrical connection reliability is excellent.

In the present embodiment, an embodiment in which two layers of circuit boards are stacked has been described, but the number of boards to be stacked may be three or more.
Moreover, the electronic component which adhere | attached the semiconductor chip and the semiconductor chip with the hardened | cured material 1 'of the resin composition 1 by the method similar to the above can be obtained.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, a method for manufacturing a semiconductor device, a multilayer circuit board, and an electronic component is not limited to the above method.
The resin composition of each Example and each comparative example was manufactured as follows, respectively.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.
[Preparation of adhesive film]
Example 1
8.2 parts by weight of phenol novolac resin (Sumitomo Bakelite, PR-55617), 12.6 parts by weight of bisphenol F type epoxy resin (DIC, EXA-830LVP), and 33% core-shell particles having an average particle size of 100 nm -Containing epoxy resin (manufactured by Kaneka Corporation, MX-138) 15.1 parts by weight, trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.4 parts by weight as a compound having a flux function, and epoxy group as a film-forming resin And 4.2 parts by weight of an amide group-containing acrylate copolymer (manufactured by Nagase ChemteX Corporation, SG-80H) and 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0 as a curing accelerator .1 part by weight and 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent KBE-503) 0.4 part by weight and silica filler (manufactured by Admatechs, SC1050, average particle size 0.25 μm) 55.0 parts by weight are dissolved and dispersed in methyl ethyl ketone, and a resin varnish having a solid content concentration of 50%. Was prepared.
The obtained adhesive film varnish was applied to a base polyester film (base film, manufactured by Teijin DuPont Films, trade name: Purex A53) to a thickness of 50 μm, and dried at 100 ° C. for 5 minutes. An adhesive film (hereinafter referred to as film A) having a thickness of 25 μm was obtained. The content of the core-shell particles was 5.0% by mass in the adhesive film.

(Example 2)
6.3 parts by weight of phenol novolac resin (Sumitomo Bakelite, PR-55617), 10.0 parts by weight of epoxy resin (MX-138, manufactured by Kaneka Corporation) containing 33% core-shell particles having an average particle size of 100 nm, and bisphenol A Type epoxy resin (DIC Corporation, EPICLON 840-S) 11.2 parts by weight, naphthalene type epoxy resin (DIC Corporation, EPICLON HP-4770) 5.3 parts by weight, phenol which is a compound having a flux function 7.0 parts by weight of phthaline (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.6 parts by weight of 3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-) as a film-forming resin 6954) 3.6 parts by weight and a carboxyl-terminated butadiene-acrylonitrile copolymer (PTI Japan) CTBN1008SP) 0.6 parts by weight, 0.1 part by weight of 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) as a curing accelerator, and N-phenyl-3-amino as a silane coupling agent 0.4 parts by weight of propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573) and 55.0 parts by weight of silica filler (manufactured by Admatechs, SC1050, average particle size 0.25 μm) are dissolved in methyl ethyl ketone. A resin varnish having a solid content concentration of 50% was prepared by dispersing.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1. The content of the core-shell particles was 3.3% by mass in the adhesive film.

Example 3
9.8 parts by weight of a phenol aralkyl resin (Mitsui Chemicals, Millex XLC-4L), 7.9 parts by weight of an epoxy resin containing 33% core-shell particles having an average particle size of 100 nm (MX-138, manufactured by Kaneka Corporation), and bisphenol A type epoxy resin (DIC Corporation, EPICLON 840-S) 14.0 parts by weight, naphthalene type epoxy resin (DIC Corporation, EPICLON HP-4770) 2.3 parts by weight, and a compound having a flux function 6.2 parts by weight of phenolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.2 parts by weight of phenoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., FX-280S) as a film-forming resin, and 2-phenyl- as a curing accelerator 0.1 part by weight of 4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) and N-phenyl-3-amino as a silane coupling agent 0.4 parts by weight of nopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573) and 55.0 parts by weight of silica filler (manufactured by Admatechs, SC1050, average particle size of 0.25 μm) are dissolved in methyl ethyl ketone. Then, a resin varnish having a solid content concentration of 50% was prepared.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1. The content of the core-shell particles was 2.6% by mass in the adhesive film.

Example 4
7.9 parts by weight of cresol novolac resin (DIC, KA-1160), 13.0 parts by weight of bisphenol F type epoxy resin (DIC, EXA-830LVP), and containing 25% of core-shell particles having an average particle diameter of 100 nm 14.6 parts by weight of an epoxy resin (manufactured by Kaneka Corporation, MX-960), 7.8 parts by weight of phenolphthalin (manufactured by Tokyo Chemical Industry Co., Ltd.) which is a compound having a flux function, and an epoxy group containing as a film-forming resin 6.2 parts by weight of acrylic ester copolymer (manufactured by Nagase ChemteX Corporation, SG-P3) and 0.1 parts by weight of 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) as a curing accelerator And 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-503) 0.5 as a silane coupling agent And amount unit, silica filler (Admatechs Co., SC1050, average particle diameter 0.25 [mu] m) 50.0 parts by weight dissolved in methyl ethyl ketone dispersed, to prepare a solid concentration of 50.0% of the resin varnish.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1. The content of the core-shell particles was 3.6% by mass in the adhesive film.

(Example 5)
9.2 parts by weight of epoxy resin containing 33% core shell particles having an average particle size of 100 nm (manufactured by Kaneka Corporation, MX-138) and 9.2 weights of tris (hydroxyphenyl) methane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER 1032H60) And 6.5 parts by weight of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) which is a compound having a flux function, and 18.1 weights of phenoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., FX-280S) as a film-forming resin And 6.5 parts by weight of a microcapsule type curing agent (manufactured by Asahi Kasei E-materials, NovaCure HX-3941P) as a curing accelerator, and 3-methacryloxypropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent Manufactured by KBE-503) and 0.5 parts by weight of silica filler (manufactured by Admatechs, SC1050, average particle size 0. 25 μm) 50.0 parts by weight were dissolved and dispersed in methyl ethyl ketone to prepare a resin varnish having a solid concentration of 50%.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1. The content of the core-shell particles was 3.0% by mass in the adhesive film.

(Example 6)
<Preparation of adhesive film>
4.1 parts by weight of a biphenyl aralkyl type phenol resin (Maywa Kasei Co., Ltd., MEH-7851), 10.1 parts by weight of an epoxy resin containing 33% core-shell particles having an average particle size of 100 nm (MX-138, manufactured by Kaneka Corporation), 6.8 parts by weight of tris (hydroxyphenyl) methane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER 1032H60) and 4- (4-hydroxyphenoxy) benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 7 which is a compound having a flux function 2 parts by weight, 21.1 parts by weight of an epoxy group-containing acrylic ester copolymer (manufactured by Nagase ChemteX Corporation, SG-P3) as a film-forming resin, and triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd.) as a curing accelerator , TPP) 0.2 part by weight and 3-glycidoxypropyltrimethoxysilane (Shin-Etsu) as silane coupling agent Chemical Industry Co., Ltd., KBM-403) 0.5 part by weight and silica filler (manufactured by Admatechs, SC1050, average particle size 0.25 μm) 50.0 parts by weight are dissolved and dispersed in methyl ethyl ketone, solid content concentration A 50% resin varnish was prepared.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1. The content of the core-shell particles was 3.3% by mass in the adhesive film.

(Example 7)
Cresol novolak resin (manufactured by DIC, KA-1160) 4.0 parts by weight, acid anhydride (manufactured by Mitsubishi Chemical Corporation, jER Cure YH307) 1.7 parts by weight, and epoxy containing 25% core-shell particles having an average particle size of 100 nm 9.0 parts by weight of resin (manufactured by Kaneka Co., MX-960), 4.5 parts by weight of dicyclopentadiene type epoxy resin (manufactured by DIC, EPICLON HP-7200H), and naphthalene type epoxy resin (manufactured by DIC, EPICLON) HP4770) 9.0 parts by weight, diphenolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.6 parts by weight as a compound having a flux function, and epoxy group and amide group-containing acrylate copolymer as a film-forming resin 11.1 parts by weight (manufactured by Nagase ChemteX Corp., SG-80H) and 2-methylimidazole ( 0.1 parts by weight from Kokusei Kogyo Co., Ltd., 2MZ-H), 1.1 parts by weight of 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-503) as a silane coupling agent, and as a filler 50.0 parts by weight of silica filler (manufactured by Admatechs, SC1050, average particle size of 0.25 μm) and acrylic rubber particles (manufactured by Mitsubishi Rayon Co., Ltd., Metabrene W-450, average particle size of 0.2 μm) 4.9 weight A part was dissolved and dispersed in methyl ethyl ketone to prepare a resin varnish having a solid concentration of 50%.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1. The content of the core-shell particles was 2.3% by mass in the adhesive film.

(Comparative Example 1)
7.4 parts by weight of phenol novolac resin (manufactured by Sumitomo Bakelite, PR-55617), 19.6 parts by weight of bisphenol A type epoxy resin (DIC, EPICLON840-S), and naphthalene type epoxy resin (manufactured by DIC, EPICLON HP4770) 2.5 parts by weight, 5.4 parts by weight of phenolphthaline (manufactured by Tokyo Chemical Industry Co., Ltd.) which is a compound having a flux function, and 0.5 weight of 3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Parts, 9.2 parts by weight of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-6594) as a film-forming resin, and 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) as a curing accelerator. 1 part by weight and 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent (KBE-503) 0.4 parts by weight and 55.0 parts by weight of silica filler (manufactured by Admatechs, SC1050, average particle size of 0.25 μm) as a filler are dissolved and dispersed in methyl ethyl ketone, and the solid content concentration is 50%. A resin varnish was prepared.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1.

(Comparative Example 2)
Cresol novolak resin (DIC, KA-1160) 8.2 parts by weight, bisphenol F type epoxy resin (DIC, EXA-830LVP) 22.7 parts by weight, trimellitic acid which is a compound having a flux function 6.0 parts by weight (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.9 parts by weight of phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-6594) as a film-forming resin, and 2-phenyl-4-methylimidazole as a curing accelerator (Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.1 parts by weight, 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403) 0.2 parts by weight as a silane coupling agent, and filler Dissolve 60.0 parts by weight of silica filler (manufactured by Admatechs, SC4050, average particle size 1.0 μm) in methyl ethyl ketone. And, to prepare a solid concentration of 50% resin varnish.
Using the obtained adhesive film varnish, an adhesive film having a thickness of 25 μm (hereinafter referred to as film A) was obtained in the same manner as in Example 1.
Table 1 shows the compositions of the resin compositions (adhesive films) of the examples and comparative examples.

[Evaluation of adhesive film]
[1] Measurement of melt viscosity at 100 ° C. A sample for measurement having a thickness of 100 μm was prepared by laminating the adhesive films obtained in the respective examples and comparative examples, and a viscoelasticity measuring device (“MARS” manufactured by Thermo Fisher Scientific Co., Ltd.). )), The melt viscosity was measured under the conditions of a parallel plate of 20 mmφ, a gap of 0.05 mm, a frequency of 1 Hz, and a constant temperature of 100 ° C. for 5 minutes, and the stable melt viscosity after 5 minutes was taken as a measured value. The results are shown in Table 1.

[2] Evaluation of flux activity The resin compositions of the above examples and comparative examples were attached to a Cu plate piece (manufactured by Hirai Seimitsu Kogyo Co., Ltd.) at about 50 ° C. Five solder balls (Sn-3Ag-0.5Cu, manufactured by Senju Metal Industry Co., Ltd.) having a diameter of 500 μm were placed on the adhesive film, and pressure-bonded at 50 N and 80 ° C. for 7 seconds using a pressure bonding device (manufactured by Tsukuba Mechanics). Thereafter, the Cu plate piece was placed on a hot plate of 235 degrees for 10 seconds. Using a microscope, the height X of the solder ball was measured. The value was calculated as a solder wetting spread rate = (0.5−X / 0.5) × 100 and evaluated according to the following criteria.
A: Solder wetting spread ratio is 60% or more.
○: Solder wetting spread ratio is 40% or more and less than 60%.
Δ: Solder wetting spread ratio is 20% or more and less than 40%.
X: Solder wetting spread rate is smaller than 20%.
The results are shown in Table 2.

[3] Manufacture of Semiconductor Device Adhesive film obtained in Example or Comparative Example on semiconductor chip A (size 5 mm × 5 mm, thickness 0.15 mm) having solder bumps (Sn-3.5 Ag, melting point 221 ° C.) Was laminated with a vacuum laminator at a temperature of 100 ° C., a pressure of 0.8 MPa, and an atmospheric pressure of 400 Pa to obtain a semiconductor chip A with an adhesive film.

Next, an electrode portion of a semiconductor chip B (size 7 mm × 7 mm, thickness 0.15 mm) having a copper electrode in which the outermost surface is a gold layer and a nickel layer is formed below the gold layer, and solder bumps of the semiconductor chip A The semiconductor chip A and the semiconductor chip B were temporarily pressure-bonded at 100 ° C. for 30 seconds using a flip chip bonder (Panasonic Factory Solutions Co., Ltd., FCB3) while aligning them so that they contact each other. Subsequently, it heated at 235 degreeC for 30 second using the flip chip bonder, the solder bump was melted, and the solder connection was performed.
Furthermore, it heated at 180 degreeC for 60 minutes, the adhesive film was hardened, and the semiconductor device with which the semiconductor chip A and the semiconductor chip B were adhere | attached with the hardened | cured material of the adhesive film was obtained.

[4] Evaluation [4-1] Evaluation of Void In the semiconductor device manufactured in [3] above, the presence or absence of voids between the resin compositions of the examples and comparative examples and the circuit board or the semiconductor chip was determined. Observation and evaluation were performed using a sound image inspection apparatus.
○: No void was observed.
X: A void was observed.

[4-2] Evaluation of protrusion In the semiconductor device manufactured in the above [3], the presence or absence of protrusion of the resin compositions of Examples and Comparative Examples was observed and evaluated with a microscope.
○: No protrusion was observed.
X: The protrusion was observed.

[4-3] Connectivity The connection resistance value of a semiconductor device obtained using the resin composition of each example and each comparative example was measured with a digital multimeter to evaluate the connection reliability. Each code is as follows.
○: Connection resistance value is less than 30Ω.
×: Connection resistance value of 30Ω or more.
The results are shown in Table 2.

As is clear from Table 2, the semiconductor device manufactured using the resin composition according to the present invention was one in which the generation of voids was suppressed. Further, in the semiconductor device manufactured using the resin composition according to the present invention, no protrusion of the resin composition was observed. Moreover, the semiconductor device manufactured using the resin composition according to the present invention has high connectivity.
On the other hand, in the comparative example, a satisfactory result was not obtained.

DESCRIPTION OF SYMBOLS 1 Resin composition 1 'Hardened | cured material 4 Circuit board 41 Base material 42 Wiring circuit 43 Insulation part 44 Pad part 45 Bump 5 Semiconductor chip 51 Solder bump 511 Solder connection part 6 Circuit board 61 Base material 62 Wiring circuit 63 Insulation part 64 Pad part 7 substrate 71 base material 72 wiring circuit 73 insulating part 74 pad part 75 solder bump 711 solder joint part 10 semiconductor device 100 multilayer circuit board

Claims (12)

A resin composition having a flux function, which is used for bonding circuit members together and electrically connecting circuit electrodes of each circuit member,
A thermosetting resin;
A compound having flux activity;
A resin composition comprising: a core layer composed of a rubber component; and a core-shell particle having a shell layer composed of an acrylic component and formed to cover the core layer.   2. The resin composition according to claim 1, wherein the content of the core-shell particles is 0.5% by mass or more and 15% by mass or less.   The resin composition according to claim 1 or 2, wherein an average particle size of the core-shell particles is 10 nm or more and 1000 nm or less.   The resin composition according to any one of claims 1 to 3, wherein the rubber component and the acrylic component constitute a copolymer.   The resin composition according to claim 1, wherein the thermosetting resin contains an epoxy resin.   The resin composition according to claim 5, wherein the epoxy resin contains an epoxy resin that is liquid at 25 ° C. 6.   The resin composition according to any one of claims 1 to 6, comprising an inorganic filler having an average particle size of 500 nm or less.   The resin composition according to claim 7, wherein the content of the inorganic filler is 0.1% by mass or more and 80% by mass or less.   The resin composition according to any one of claims 1 to 8, wherein the compound having flux activity is a compound having a carboxyl group and / or a phenolic hydroxyl group.   A semiconductor device comprising a cured product of the resin composition according to claim 1.   A multilayer circuit board comprising a cured product of the resin composition according to any one of claims 1 to 9.   An electronic component comprising a cured product of the resin composition according to any one of claims 1 to 9.

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