JP2005311204A - Resin material, varnish solution, b-stage material, laminated body, wiring board, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin material for forming the insulation layer of a semiconductor device, having superior adhesiveness with other resin materials and with a metal foil or an alloy foil, and a high breaking elongation and stress relaxing properties, to provide a varnish solution and a B stage material for forming the resin material, a laminate provided with the resin material, and to provide a wiring board and a semiconductor device. <P>SOLUTION: The resin material has a 50% of the breaking elongation amount or over and a 1 GPa or lower of the Young's modulus at a temperature range of 10 to 30 °C. The resin material contains a reactive elastomer (A) capable of reacting with an epoxy resin, an epoxy resin (B), and a curing agent (C) for the epoxy resin. Further, the curing agent (C) for the epoxy resin contains a resin (D), the distance of function groups of which is larger than that of phenol novolak resin. Then value (A×100)/(A+B+C) is selected to be 60 mass% or higher and 100 mass% of lower. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin material containing an epoxy resin and a rubber component having a functional group capable of reacting with the epoxy resin (reactive elastomer), a varnish solution and a B stage material for forming the resin material, and the resin material The present invention relates to a laminated body, a wiring board and a semiconductor device.

  Recently, in the electronics field, electronic devices have become smaller, lighter, thinner, and higher in density, and the reliability required for these devices has become stricter than before. In response to such demands, a flexible wiring board has flexibility and can withstand repeated bending, so that it is not only used as a wiring board mainly for connecting components, but recently, a semiconductor device. It has begun to be used as a wiring layer constituting a part of the circuit. For example, it is beginning to be used as a wiring layer of a package substrate on which a semiconductor chip is mounted.

  Conventionally, as a material of a flexible wiring board, a two-layer flexible copper-clad laminate (also referred to as two-layer FCCL) in which a polyimide resin layer is directly bonded to a copper foil, and a resin layer made of polyimide or polyethylene naphthalate (PEN) are used. A three-layer flexible copper-clad laminate (also referred to as a three-layer FCCL) bonded to a copper foil via an epoxy resin layer is generally used.

  Generally, the polyimide resin forming these FCCLs is a material having a large amount of elongation at break during a tensile test. For example, the polyimide resin that forms the insulating layer of Ube Kosan Nyupicel N (trade name), which is a non-adhesive type two-layer FCCL, has a tensile test at a normal temperature, that is, a tensile rate of about 8% / min at around 25 ° C The elongation at break is a little less than 80%, the Young's modulus is about 7 GPa, and the break strength is about 450 MPa, both of which show high numerical values.

  However, in the two-layer FCCL using such a polyimide resin, since the adhesion between the polyimide resin layer and the copper foil is low, when the wiring layer of the semiconductor device is formed, the strain generated due to the thermal history during mounting Due to (deformation), there was a problem that the polyimide resin layer and the copper foil peeled at the interface.

  In the three-layer FCCL, as described above, an epoxy resin composition is generally used as an adhesive between a resin layer made of polyimide or PEN and a copper foil. The adhesive layer made of this epoxy resin composition is excellent in adhesion between the resin layer made of polyimide or PEN, and adhesion between the copper foil, but the elongation at break of the epoxy resin composition itself Is insufficient. For this reason, when a force is applied to the three-layer FCCL, there is a problem that strain concentrates on the adhesive layer and breaks, and the resin layer made of polyimide or PEN and the copper foil are peeled off. For example, ABF-GX (trade name) manufactured by Ajinomoto Fine Techno Co., Ltd., representative of such an epoxy resin composition, has an elongation at break of about 12% in a normal temperature tensile test.

  In contrast, Patent Document 1 contains an epoxy resin (a), a curing agent (b), and a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer (c. Hereinafter referred to as a reactive polyamide elastomer). An epoxy resin composition, a flexible printed wiring board using the epoxy resin composition, a coverlay material, and a bonding sheet are disclosed. Patent Document 1 describes that this epoxy resin composition has excellent resistance to repeated bending, adhesiveness, heat resistance, and moisture resistance.

JP 2001-81282 A

  However, the above-described conventional techniques have the following problems. In a semiconductor device, thermal stress is generated when a semiconductor chip is mounted and used. Therefore, a high stress relaxation property is required for the resin material forming the insulating layer of the semiconductor device. On the other hand, the epoxy resin composition described in Patent Document 1 is an invention made on the assumption of a flexible wiring board, a coverlay material, and a bonding sheet, and is assumed to be applied to an insulating layer of a semiconductor device. Since it was not designed, no consideration was given to elongation at break during a tensile test at room temperature, which is an index of stress relaxation.

  For this reason, the semiconductor device in which the epoxy resin composition disclosed in Patent Document 1 is applied to the insulating layer has insufficient stress relaxation properties. As a result, connection reliability at a joint portion between a plurality of members formed of different materials is insufficient. For example, when mounting a semiconductor chip using lead-free solder on the insulating layer of a wiring board, it will be mounted at a high temperature and then cooled to room temperature, but if the insulating layer is difficult to deform at that time, residual stress As a result, the connection reliability between the insulating layer and the lead-free solder becomes insufficient.

  Thus, conventionally, the adhesiveness between the resin layer made of polyimide or PEN is high, the adhesiveness with the copper foil is high, and the elongation at break of itself is high, and the stress relaxation property is excellent. There has been no resin material (high toughness resin material) that improves the reliability of the semiconductor device when applied to the insulating layer of the semiconductor device.

  The present invention has been made in view of such problems, and in a resin material forming an insulating layer of a semiconductor device, adhesion between other resin materials and adhesion between a foil made of a metal or an alloy. Resin material with good breakage, high elongation at break and excellent stress relaxation, varnish solution and B-stage material for forming this resin material, and laminates, wiring boards and the like provided with this resin material An object is to provide a semiconductor device.

  The resin material according to the present invention includes an epoxy resin and a reactive elastomer that can react with the epoxy resin in a resin material that forms an insulating layer of a semiconductor device, and has an elongation at break of 50% or more. The Young's modulus in a temperature range of 30 ° C. to 30 ° C. is 1 GPa or less.

  In the present invention, since the resin material contains an epoxy resin, the adhesion between other resin materials, for example, a resin material made of polyimide, PEN, or the like is good, and a foil made of a metal or an alloy, for example, copper Adhesion between the foil is good. In addition, since the elongation at break is 50% or more, the stress relaxation property is high, and the resin material itself does not break when stress is applied. Furthermore, since the Young's modulus in the temperature range of 10 to 30 ° C. is 1 GPa or less, the stress applied to the semiconductor device can be relaxed by deformation of the resin material when applied to the insulating layer of the semiconductor device. .

  The resin material contains an epoxy resin curing agent, the epoxy resin curing agent contains a resin having a longer distance between functional groups than the phenol novolac resin, and the content of the reactive elastomer is A, When the content of the epoxy resin is B and the content of the curing agent for epoxy resin is C, the value of (A × 100) / (A + B + C) may be 60% by mass or more and less than 100% by mass. At this time, the resin having a longer distance between functional groups than the phenol novolac resin may be an ethylene oxide compound.

  Or, in the resin material, when the epoxy resin contains an epoxy resin having a longer distance between functional groups than the phenol novolac resin, the content of the reactive elastomer is A, and the content of the epoxy resin is B. , (A × 100) / (A + B) may be 60% by mass or more and less than 100% by mass.

  Or the said resin material contains the hardening | curing agent for epoxy resins, the said epoxy resin contains the epoxy resin in which the distance between functional groups is longer than a phenol novolak resin, the content of the said reactive elastomer is A, the said epoxy resin When the content of B is B and the content of the curing agent for epoxy resin is C, the value of (A × 100) / (A + B + C) may be 60 mass% or more and less than 100 mass%. At this time, the epoxy resin having a longer distance between functional groups than the phenol novolac resin may be an epoxidized product of an ethylene oxide compound.

  Alternatively, the resin material contains an epoxy resin curing agent, the epoxy resin contains an epoxidized product of an ethylene oxide compound, the epoxy resin curing agent contains an ethylene oxide compound, and the content of the reactive elastomer Is A, the content of the epoxy resin is B, and the content of the curing agent for epoxy resin is C, the value of (A × 100) / (A + B + C) is 60% by mass or more and less than 100% by mass. Also good.

  Alternatively, in the resin material, when the content of the reactive elastomer is A and the content of the epoxy resin is B, the value of (A × 100) / (A + B) is 70% by mass or more and less than 100% by mass. There may be.

  Alternatively, when the resin material contains an epoxy resin curing agent, the content of the reactive elastomer is A, the content of the epoxy resin is B, and the content of the epoxy resin curing agent is C, The value of (A × 100) / (A + B + C) may be 70% by mass or more and less than 100% by mass.

  The varnish solution according to the present invention is characterized in that the resin material is dissolved or dispersed in a solvent.

  The B stage material according to the present invention is obtained by heating the varnish solution. The B stage material may be applied on a foil made of a metal or an alloy. The B stage material is a semi-cured resin material.

  The laminated body which concerns on this invention has foil which consists of a metal or an alloy, and the resin layer provided on this foil, The said resin layer is formed with the said resin material, It is characterized by the above-mentioned. The laminate may have another resin layer formed on the resin layer, or may have a foil made of another metal or alloy formed on the resin layer. Also good.

  The wiring board according to the present invention includes one or a plurality of wiring layers, and the wiring layer includes a wiring and the resin material in which the wiring is embedded. The wiring board may have a cover layer made of an insulating material and covering the wiring.

  The semiconductor device according to the present invention has an insulating layer formed of the resin material. The semiconductor device may include a wiring board and a semiconductor chip mounted on the wiring board, and the insulating layer may be provided in the wiring board.

  According to the present invention, since it contains an epoxy resin, the adhesion between other resin materials is good, the adhesion between the metal or alloy foil is good, and the elongation at break is 50. %, And the Young's modulus in the temperature range of 10 to 30 ° C. is 1 GPa or less. Therefore, it is possible to obtain a resin material that has high stress relaxation properties and does not break itself.

  Hereinafter, embodiments of the present invention will be described. First, a first embodiment of the present invention will be described. The resin material according to this embodiment has an elongation at break of 50% or more and a Young's modulus in a temperature range of 10 to 30 ° C. of 1 GPa or less. The resin material contains an elastomer that can react with the epoxy resin (A, hereinafter referred to as a reactive elastomer), an epoxy resin (B), and a curing agent for epoxy resin (C). When the content of the reactive elastomer is A, the content of the epoxy resin is B, and the content of the curing agent for epoxy resin is C, the value of (A × 100) / (A + B + C) is 60 mass% or more 100 It is less than mass%. Moreover, the hardening | curing agent (C) for epoxy resins contains resin (D) whose distance between functional groups is longer than a phenol novolak resin.

  The reason for limiting the numerical values of the present invention will be described below. When the resin material has an elongation at break of less than 50%, when the resin material is used as an insulating layer of a semiconductor device, if a force such as thermal stress or external force is applied to the semiconductor device, the resin material itself It may break. On the other hand, if the Young's modulus is higher than 1 GPa, the resin material is not easily deformed when a force is applied to the semiconductor device, so that residual stress is generated. For this reason, stress is applied to a member other than the insulating layer, for example, a connecting member such as a solder ball, and this connecting member may be destroyed. Thereby, the connection reliability of the semiconductor device using the resin material is lowered. Therefore, in the present invention, the elongation at break of the resin material is 50% or more, and the Young's modulus in the temperature range of 10 to 30 ° C. is 1 GPa or less.

  Further, if the value of (A × 100) / (A + B + C) is less than 60% by mass, the reactive elastomer that ensures the toughness of the resin material is insufficient, and sufficient elongation at break cannot be obtained. is there. Therefore, the value is preferably 60% by mass or more.

  The reactive elastomer (A) is, for example, a polyamide-polybutadiene-acrylonitrile copolymer containing a phenolic hydroxyl group. This phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer (hereinafter also simply referred to as copolymer) is a dicarboxylic acid having a phenolic hydroxyl group represented by the following chemical formula 1 and a phenolic compound represented by the following chemical formula 2. It was obtained by reacting a dicarboxylic acid having no hydroxyl group, a diamine represented by the following chemical formula 3, and a polybutadiene-acrylonitrile copolymer having a carboxylic acid at both ends represented by the following chemical formula 4. is there. This phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer is represented by the following general formula (5).

R ¹ described in Chemical Formula 1 and Chemical Formula 5 below represents a divalent aromatic compound having 6 to 12 carbon atoms having a phenolic hydroxyl group. Examples of the dicarboxylic acid having a phenolic hydroxyl group represented by the above chemical formula 1 include 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid, and 2-hydroxyterephthalic acid. Can be mentioned.

R ² described in Chemical Formula 2 and Chemical Formula 5 below is a divalent aromatic compound having 6 to 12 carbon atoms and having no phenolic hydroxyl group, or a divalent aliphatic compound having 1 to 10 carbon atoms. Represents. Examples of the dicarboxylic acid having no phenolic hydroxyl group represented by the chemical formula 2 include phthalic acid, isophthalic acid, terephthalic acid, dicarboxyl naphthalene, succinic acid, fumaric acid, glutaric acid, adipic acid, and 1,3-cyclohexane. Examples thereof include dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 3,3′-methylene dibenzoic acid and the like.

R ³ described in Chemical Formula 3 and Chemical Formula 5 below represents a divalent aromatic compound having 6 to 12 carbon atoms or a divalent aliphatic compound having 1 to 10 carbon atoms. Among the diamines represented by the above Chemical Formula 3, as diamines containing phenolic hydroxyl groups, 3,3′-diamine-4,4′-dihydroxyphenylmethane, 2,2′-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, 2,2′-bis (3-amino-4-hydroxyphenyl) difluoromethane, 3,4′-diamino-1,5′-benzenediol, 3,3′-dihydroxy-4,4 ′ -Diaminobisphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,2'-bis (3-amino-4-hydroxyphenyl) ketone, 2,2'-bis (3-amino-4 -Hydroxyphenyl) sulfide, 2,2'-bis (3-amino-4-hydroxyphenyl) ether, 2,2'-bis (3-amino-4-hydroxyphenyl) sulfo 2,2′-bis (3-amino-4-hydroxyphenyl) propane, 2,2′-bis (3-amino-4-aminophenyl) propane, 2,2′-bis (3-amino-4-) Examples of diamines that do not contain phenolic hydroxyl groups include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, diaminonaphthalene, piperazine, hexamethylenediamine. Tetramethylenediamine, m-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminobenzophenone, 2,2′-bis (4-aminophenyl) propane, 3,3′-diaminodiphenylsulfone, 3, , 3'-diaminodiphenyl and the like. As the diamine, 3,4'-diaminodiphenyl ether is particularly preferable, but is not limited thereto.

  X described in the above chemical formula 4 and the following chemical formulas 5 and 6 represents an average degree of polymerization and is an integer of 3 to 7, and y represents an average degree of polymerization and is an integer of 1 to 4.

  In the above chemical formula 5 and the following chemical formula 6, z, l (el), m and n are average degrees of polymerization, respectively, z is an integer of 5 to 15, n = 1 + m, and n is 2 to 2. It is an integer of 200, and l (el) and m satisfy the relationship m / (l + m) ≧ 0.04.

  Among the copolymers represented by the above chemical formula 5, a particularly preferred copolymer is a copolymer represented by the general formula represented by the following chemical formula 6.

  When the weight average molecular weight (Mw) of the copolymer is 100,000 or less, sufficient fluidity can be obtained in a temperature range of 160 to 180 ° C. In particular, when the weight average molecular weight (Mw) is 20,000 or less, good fluidity can be obtained even in a temperature range of 100 to 160 ° C. Therefore, the weight average molecular weight (Mw) of the copolymer is preferably 100,000 or less, and more preferably 20,000 or less.

  On the other hand, a resin (D) having a longer distance between functional groups than the phenol novolac resin contained in the epoxy resin curing agent (C) is represented by the following chemical formula 7.

R ⁴ described in Chemical Formula 7 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. a1 represents an integer of 1 to 4. a1 ′ represents an integer of 1 to 3. X represents a compound X ₁ represented by the following chemical formula 8 or a compound X ₂ represented by the following chemical formula 9. b represents an integer of 1 to 10, and c and d each represent 1.

R ⁵ described in Chemical Formula 8 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. e represents an integer of 1 to 4; f represents an integer of 0 to 9.

R ⁶ described in Chemical Formula 9 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. g represents an integer of 1 to 4. h represents an integer of 0 to 9.

  In addition, the resin (D) having a longer distance between functional groups than the phenol novolac resin contained in the epoxy resin curing agent (C) includes, for example, an ethylene oxide compound represented by the following chemical formula 10.

R ^{4 ′} described in Chemical Formula 10 above represents hydrogen or a monovalent substituent having 1 to 3 carbon atoms. a2 represents an integer of 1 to 4. a2 ′ represents an integer of 1 to 3. X ′ represents a compound X ₁ ′ represented by the following chemical formula 11 or a compound X ₂ ′ represented by the following chemical formula 12. b ′ represents an integer of 1 to 10, and c ′ and d ′ each represent 1.

R ^{5 ′} described in Chemical Formula 11 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. e ′ represents an integer of 1 to 4. f ′ represents an integer of 0 to 9.

R ^{6 ′} described in the chemical formula 12 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. g ′ represents an integer of 1 to 4. h ′ represents an integer of 0 to 9.

  In the resins represented by the chemical formulas 7 and 10, the distance between the functional groups is longer than that of the phenol novolac resin represented by the following chemical formula 13.

  Moreover, in this embodiment, although an epoxy resin (B) is not specifically limited, It is preferable that it is an epoxy resin in which the distance between functional groups is longer than a phenol novolak epoxy resin. This is because such an epoxy resin can efficiently form an IPN structure, and as a result, the elongation at break of the resin material according to the present embodiment can be further improved. Such epoxy resins having a longer distance between functional groups than phenol novolac epoxy resins include phenol biphenylene aralkyl type epoxy resins, phenol xylene aralkyl type epoxy resins, phenol diphenyl ether aralkyl type epoxy resins, and bifunctional biphenyl type epoxy resins. And anthracene-containing novolac epoxy resins, fluorene-containing novolac epoxy resins, bisphenolfluorene-containing novolac epoxy resins, phenol biphenylene triazine epoxy resins, and phenol xylene triazine epoxy resins. In addition, a phenoxy resin or the like having a bisphenol A type, a bisphenol F type, a bisphenol S type or a biphenyl skeleton-containing type and having both ends being epoxy groups can be used. This phenoxy resin has a polystyrene equivalent weight average molecular weight of about 20,000 to 100,000. As the epoxy resin (B), any one of these epoxy resins may be used alone, or a plurality of types may be mixed and used.

  In addition, among the epoxy resins included in the resin material according to the present embodiment, an epoxy resin other than the epoxy resin having a long distance between the functional groups is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene diol type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol F containing novolak type epoxy resin, bisphenol A containing novolak type epoxy Resin, phenol triazine type epoxy resin, cresol triazine type epoxy resin, tetraphenylol ethane type epoxy resin, trisphenylol ethane type epoxy resin, polyphenol type epoxy resin, aliphatic epoxy resin, aromatic ester type epoxy resin, cycloaliphatic Examples include ester type epoxy resins and ether ester type epoxy resins. In addition, glycidylated products of amine compounds such as diaminodiphenylmethane, diethylenetriamine and diaminodiphenylsulfone can also be used. These epoxy resins may be used alone or may be used in combination of a plurality of types.

  Furthermore, in the resin material according to the present embodiment, among the epoxy resin curing agent (C), components other than the resin (D) having a longer distance between functional groups than the above-described phenol novolac resin are particularly limited. It is not a thing. As this component, for example, bisphenol A type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, diphenyl ether of biphenyl isomer, naphthalene diol type resin, phenol novolac resin, cresol novolac resin, phenol diphenyl ether aralkyl type resin, Naphthalene-containing novolac resin, anthracene-containing novolac resin, fluorene-containing novolac resin, bisphenolfluorene-containing novolac resin, bisphenol F-containing novolac phenol resin, bisphenol A-containing novolac phenol resin, phenol biphenyl triazine resin, phenol xylene triazine Type resin, phenol triazine type resin, cresol novolac triazine type tree , Tetraphenylolethane type resin, trisphenylol ethane resin, polyphenol type resin, aromatic ester type phenol resin, alicyclic ester-containing phenol resin, and ester type phenol resin.

  Moreover, as a component of the curing agent for epoxy resin (C), amine compounds such as diaminodiphenylmethane, diethylenetriamine, and diaminodiphenylsulfone may be contained in addition to the above-described resins. Furthermore, a phenoxy resin which is a bisphenol A type, a bisphenol F type, a bisphenol S type or a biphenyl skeleton-containing type and one or both ends are hydroxyl groups can also be used. This phenoxy resin has a polystyrene-equivalent weight average molecular weight of, for example, about 20,000 to 100,000. These components may be contained alone in the epoxy resin curing agent (C), or may be contained in a mixture of a plurality of types.

  Furthermore, the resin material according to the present embodiment may contain an inorganic filler. However, when the inorganic filler is contained, the mass proportion of the inorganic filler in the total amount of the reactive elastomer (A), the epoxy resin (B), the epoxy resin curing agent (C) and the inorganic filler in the present invention is as follows. 30% by mass or less is preferable. When the mass ratio of the inorganic filler exceeds 30% by mass, the elongation at break decreases, the Young's modulus increases, and the stress relaxation properties may become insufficient.

  As this inorganic filler, known fillers can be used. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, beryllia, talc (talc) ), Powders such as mica (mica), titanium oxide, zirconia, or beads made by spheroidizing these materials, single crystal fibers such as calcium titanate, silicon carbide, silicon nitride, boron nitride, alumina, aluminum hydroxide, Metal hydrates such as magnesium hydroxide and zinc borate, surface treated with various organic substances such as epoxy resin and phenol resin, the above metal hydrate, the metal was solidified to improve acid resistance Examples include various metal hydrates such as magnesium hydroxide. These fillers may be used individually by 1 type, and may mix 2 or more types.

  Further, the resin material according to the present embodiment may contain a curing accelerating catalyst. As a hardening acceleration catalyst, what is generally used for hardening of an epoxy resin and a hardening | curing agent can be used, and it does not specifically limit. Examples include imidazoles, diazabicycloalkenes and derivatives thereof, and tertiary amines. These curing accelerating catalysts may be used alone or in combination of two or more.

  Furthermore, the high toughness resin material according to the present embodiment may be added with other flexibility additives such as silicone rubber, silicone powder, acrylonitrile butadiene rubber (NBR), and indene, as necessary. Furthermore, a coupling agent such as an organic silane compound, an organic titanate compound, or an organic aluminate compound may be appropriately blended. In particular, among the silane coupling agents, an organic silane compound, that is, an alkoxysilane having a reactive functional group is effective in improving the adhesion and soldering heat resistance of the resin material according to this embodiment. Specific examples of the alkoxysilane include aminosilane compounds such as γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples include epoxysilane compounds such as diethoxysilane, mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane, and ureidosilane compounds such as γ-ureidopropyltriethoxysilane.

  Furthermore, the resin material of the present embodiment includes, as an adhesion improver between the resin material and the copper foil surface, components used for a rust preventive agent that can be bonded to the copper surface, that is, a triazole compound, a mercapto. Mercapto compounds other than silane compounds and copper complexes of imidazoles may be added. Examples of triazole compounds include 1,2,3-benzotriazole and tolyltriazole. Examples of mercapto compounds include 2,4,6-trimercapto-s-triazine, 2-di-n-butylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine. Etc. Examples of the copper complex of imidazole include 2-methylimidazole copper (2) complex. Of these, one component may be used alone, or two or more components may be mixed and used.

  Furthermore, you may add a flame retardant to the resin material of this embodiment as needed. Examples of these flame retardants include halogen flame retardants, nitrogen flame retardants, phosphorus flame retardants, and inorganic flame retardants. Examples of halogen-based flame retardants include brominated bisphenol A resins and epoxidized products thereof. Among nitrogen-based flame retardants, examples of the additive compound include melamine and isocyanuric acid compounds. Among nitrogen-based flame retardants, examples of the reactive compound include a phenol triazine type curing agent and an epoxy resin. Examples of phosphorus flame retardants include red phosphorus, phosphoric acid compounds, and organic phosphorus compounds. Examples of the inorganic flame retardant include compounds obtained by coating the surface of talc or silica with the metal hydrate, zinc molybdate, zinc stannate, zinc molybdate or zinc stannate. In addition, when a halogen flame retardant is used, extremely excellent flame retardancy can be obtained by using antimony oxide in combination.

  Furthermore, the resin material according to the present embodiment may contain known substances other than those described above as long as the reliability of the semiconductor device using the resin material is not lowered. For example, you may contain a pigment, antioxidant, an organic solvent, etc.

  Next, the effect of the first embodiment will be described. In view of the above-mentioned problems, the present inventors have conducted extensive experimental research to develop a high toughness resin material having high elongation at break and excellent stress relaxation and flexibility, and obtained the following knowledge. That is, the epoxy resin curing agent (C) contains, in addition to the phenolic curing agent, a resin (D) having a longer distance between functional groups than the phenol novolac resin, thereby curing the epoxy resin curing agent (C). ), The network of the crosslinked structure when the epoxy resin (B) is thermally cured can be enlarged. Thereby, the reactive elastomer (A) and the epoxy resin (B) can be efficiently reacted to form an interpenetrating network (IPN) structure positively. As a result, the stress relaxation property of the resin material can be improved.

The inventors of the present invention, for example, used an ethylene oxide compound (E), that is, a phenolic hydroxyl group (—OH) as ethylene oxide (—OCH) as the resin (D) having a longer distance between functional groups than the phenol novolac resin. ₂ CH ₂ OH) was found to be usable. Thereby, since the distance between the cross-linking points of the epoxy resin (B) and the curing agent (C) can be increased, the reactive elastomer (A) and the epoxy resin (B) efficiently react to form an IPN structure. It can be formed efficiently, and the molecular chain entanglement effect is enhanced. As a result, the elongation at break of the resin material is increased, and a so-called high toughness resin material can be obtained.

  Thus, the resin material according to the first embodiment contains a reactive elastomer (A) capable of reacting with an epoxy resin, an epoxy resin (B), and a curing agent for epoxy resin (C), Resin (D) in which the content of the reactive elastomer (A) is 60% by mass or more and less than 100% by mass with respect to the total amount, and the epoxy resin curing agent (C) has a longer distance between functional groups than the phenol novolac resin (D ), For example, since it contains an ethylene oxide compound (E), the elongation at break is high.

  Next, a second embodiment of the present invention will be described. The resin material according to this embodiment has an elongation at break of 50% or more and a Young's modulus in a temperature range of 10 to 30 ° C. of 1 GPa or less. Moreover, this resin material contains the reactive elastomer (A) which can react with an epoxy resin, and an epoxy resin (B) as an essential component. Further, this resin material may contain an epoxy resin curing agent (C). When the content of the reactive elastomer (A) is A, the content of the epoxy resin (B) is B, and the content of the curing agent for epoxy resin (C) is C, (A × 100) / (A + B + C ) Is 60% by mass or more and less than 100% by mass. Note that the value of C may be 0. Furthermore, the epoxy resin (B) contains an epoxy resin having a longer distance between functional groups than the phenol novolac resin, for example, an epoxidized product (F) of an ethylene oxide compound.

  When the value of (A × 100) / (A + B + C) is less than 60% by mass, the reactive elastomer (A) that ensures the toughness of the resin material is insufficient, and sufficient elongation at break cannot be obtained. Therefore, the value is set to 60% by mass or more.

  In the resin material according to the present embodiment, the composition of the reactive elastomer (A) is the same as that in the first embodiment. In addition, the resin material according to the present embodiment may or may not contain the epoxy resin curing agent (C). What is necessary is just to use, for example, what is necessary is just to use a phenol type hardening | curing agent. Components other than the above in the resin material of the present embodiment are the same as those in the first embodiment.

  As described above, in the present embodiment, the epoxy resin (B) contains an epoxidized product (F) of an ethylene oxide compound. The epoxidized product (F) of this ethylene oxide compound is represented by the following chemical formula 14.

R ⁷ described in the chemical formula 14 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. i represents an integer of 1 to 4. i ′ represents an integer of 1 to 3. Y represents a compound Y ₁ represented by the following chemical formula 15 or a compound Y ₂ represented by the following chemical formula 16. j represents an integer of 1 to 10, and k and o (o) each represent 1.

R ⁸ described in the chemical formula 15 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. p represents an integer of 1 to 4. q represents an integer of 0 to 9.

R ⁹ described in Chemical Formula 16 represents a monovalent substituent having 1 to 3 carbon atoms or hydrogen. r represents an integer of 1 to 4. s represents an integer of 0 to 9.

  Next, the effect of the second embodiment will be described. When the present inventors use a resin having a longer distance between functional groups (in this case, an epoxy group) than a phenol novolac epoxy resin as the epoxy resin (B), the IPN structure is more efficiently formed. It has been found that a high-toughness resin material can be obtained because of easy formation.

  In addition, the present inventors, for example, as a compound (F) obtained by epoxidizing the above ethylene oxide compound so as to easily form an IPN structure as an epoxy resin having a longer distance between functional groups than a phenol novolac resin. It has been found that a resin that can increase the distance between various crosslinking points can be used. Thereby, even when the resin material does not contain an epoxy resin curing agent, or when a conventional epoxy resin curing agent, for example, the above-described phenolic curing agent is used as the epoxy resin curing agent (C). , The distance between the crosslinking points of the epoxidized product (F) and the curing agent can be increased, the reactive elastomer (A) efficiently penetrates into the crosslinked structure, and the entanglement effect of the molecular chain is increased. That is, an IPN structure can be formed efficiently, and a resin material having a low Young's modulus and a high elongation at break, that is, a high toughness resin material can be obtained.

  Thus, in the resin material according to the present embodiment, since the epoxy resin (B) contains the epoxidized product (F) of the ethylene oxide compound, the IPN structure can be efficiently formed, and the Young The rate is low and the elongation at break is high.

  Next, a third embodiment of the present invention will be described. The resin material according to the present embodiment contains a reactive elastomer (A) that can react with an epoxy resin, an epoxy resin (B), and a curing agent for epoxy resin (C). When the content of the reactive elastomer (A) is A, the content of the epoxy resin (B) is B, and the content of the curing agent for epoxy resin (C) is C, (A × 100) / (A + B + C ) Is 60% by mass or more and less than 100% by mass. The epoxy resin (B) contains an epoxidized product (F) of an ethylene oxide compound, and the curing agent for epoxy resin (C) contains an ethylene oxide compound (E).

  The resin material according to the present embodiment has a breaking elongation of 50% or more and a Young's modulus in a temperature range of 10 to 30 ° C. of 1 GPa or less.

  When the value of (A × 100) / (A + B + C) is less than 60% by mass, the reactive elastomer (A) that ensures the toughness of the resin material is insufficient, and sufficient elongation at break cannot be obtained. Therefore, the value is set to 60% by mass or more.

  In the resin material according to the present embodiment, the compositions of the reactive elastomer (A) and the ethylene oxide (E) are the same as those in the first embodiment. The composition of the epoxidized product (F) of the ethylene oxide compound is the same as that in the second embodiment. Furthermore, the components other than those described above in the resin material of the present embodiment are the same as those in the first embodiment.

  In this embodiment, the resin material contains a reactive elastomer (A) that can react with an epoxy resin, an epoxy resin (B), and a curing agent for epoxy resin (C), and a reactive type for these total amounts. The elastomer (A) content is 60% by mass or more and less than 100% by mass, the epoxy resin curing agent (C) contains the ethylene oxide compound (E), and the epoxy resin (B) is an epoxidized product of the ethylene oxide compound. Since (F) is contained, the elongation at break is high.

  Next, a fourth embodiment of the present invention will be described. The resin material according to the present invention contains a reactive elastomer (A) capable of reacting with an epoxy resin and an epoxy resin (B) as essential components. Moreover, this resin material may contain the hardening | curing agent (C) for epoxy resins. When the content of the reactive elastomer (A) is A, the content of the epoxy resin (B) is B, and the content of the curing agent for epoxy resin (C) is C, (A × 100) / (A + B + C ) Is 70% by mass or more and less than 100% by mass. Note that the value of C may be 0.

  When the value of (A × 100) / (A + B + C) is less than 70% by mass, the reactive elastomer (A) that ensures the toughness of the resin material is insufficient, and sufficient elongation at break cannot be obtained. Therefore, the said value shall be 70 mass% or more.

  In the resin material according to the present embodiment, the compositions of the reactive elastomer (A) and the epoxy resin (B) are the same as those in the first embodiment. In addition, when the epoxy resin curing agent (C) is used, a conventional epoxy resin curing agent may be used as in the second embodiment described above. Components other than the above in the resin material of the present embodiment are the same as those in the first embodiment.

  In the resin material having the reactive elastomer (A) and the epoxy resin (B) as essential components, the present inventors, for example, between the crosslinking points such as the ethylene oxide compound (E) or the epoxidized product (F) described above. Even without using a resin that can increase the distance, the mass ratio {(A × 100) / (A + B + C)} of the reactive elastomer (A) is limited to a range of 70% by mass or more and less than 100% by mass. It was found that the elongation at break shows a specific increase at room temperature, for example, 25 ° C., and exhibits extremely excellent stress relaxation properties.

  On the other hand, in the above-mentioned Patent Document 1, only an example in which the mass ratio of the reactive polyamide elastomer is 50% by mass or less is shown with respect to the total amount of the epoxy resin, the curing agent, and the reactive polyamide elastomer. When the mass ratio is 70% by mass or more, it is not disclosed or suggested that the elongation at break of the resin material increases specifically. Thus, in this embodiment, the special performance improvement of the resin material which is not disclosed or suggested in the above-mentioned Patent Document 1 is realized.

  Next, a fifth embodiment of the present invention will be described. This embodiment is an embodiment of a varnish solution for forming the resin material according to the first embodiment described above. The varnish solution according to this embodiment is obtained by uniformly dissolving or dispersing a resin material having the same components as those of the resin material according to the first embodiment described above in an organic solvent.

  The type and amount of the organic solvent are not particularly limited as long as the varnish solution according to the present embodiment has a viscosity and volatility suitable for producing a cured product. . For example, in order to sufficiently disperse the reactive elastomer, N-methylpyrrolidone (NMP), dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), cyclohexanone or cyclopentanone is used as the organic solvent. It is preferable. Although methyl ethyl ketone (MEK) may be used in combination with these organic solvents, the mass ratio of MEK in the total amount of the organic solvent is preferably 50% or less so that the reactive elastomer (A) does not precipitate.

  In the present embodiment, the varnish solution for forming the resin material according to the first embodiment has been described. However, the resin material for forming the resin material according to the second to fourth embodiments described above has been described. The varnish solution is the same as in this embodiment. That is, a resin material having the same components as the resin materials according to the second to fourth embodiments is uniformly dissolved or dispersed in an organic solvent.

  Next, a sixth embodiment of the present invention will be described. This embodiment is an embodiment of a B stage material for forming the resin material according to the first embodiment described above. The B stage material according to the present embodiment is obtained by applying the varnish solution according to the fifth embodiment described above to a copper foil and then heating the resin material contained in the varnish solution by a general method of heating. It is a single-sided copper-clad B-stage resin material in a cured state. And the resin material which concerns on the above-mentioned 1st Embodiment is producible by hardening the B stage material which concerns on this embodiment.

  In the present embodiment, the B-stage material for forming the resin material according to the first embodiment has been described. However, in order to form the resin material according to the second to fourth embodiments described above. This B stage material is also the same as in the present embodiment. Moreover, you may use the foil which consists of metals or alloys other than copper instead of copper foil.

  Next, a seventh embodiment of the present invention will be described. This embodiment is an embodiment of a laminate including the resin material according to the first embodiment described above. The laminate according to the present embodiment is a single-sided copper-clad resin material (two-layer FCCL) provided with a copper foil and a resin layer formed on the copper foil. The resin layer is formed of the resin material according to the first embodiment described above. That is, it is produced by curing the B-stage material according to the aforementioned sixth embodiment.

  Further, another resin layer made of polyimide or PEN may be formed on this resin layer. Thereby, a three-layer FCCL can be manufactured. Further, two copper foils may be arranged via a resin layer and bonded by heating and pressing to produce a double-sided copper-clad sheet having a three-layer structure consisting of copper foil-resin layer-copper foil. . Furthermore, you may produce the double-layered copper clad sheet of the 5 layer structure which consists of another resin layer-resin layer-copper foil which consists of copper foil-resin layer-polyimide or PEN.

  In addition, the varnish solution according to the fifth embodiment described above is applied to a glass substrate such as a glass woven fabric (glass cloth) or a glass nonwoven fabric (glass paper), or an aramid substrate such as an aramid woven fabric or an aramid nonwoven fabric. Alternatively, after impregnation, a prepreg is produced by heating, and a plurality of the prepregs are superposed, and a copper foil is superposed on one or both sides of the laminated structure, and then pressurized while heating to contain the base material. A copper-clad laminate can be produced. At this time, if a copper foil is not used, a laminate can be obtained.

  In this embodiment, the resin layer is formed of the resin material according to the first embodiment described above. However, the present invention is not limited to this, and the resin layer may be any one of the second to fourth described above. You may form with the resin material which concerns on this embodiment. Moreover, you may use the foil which consists of metals or alloys other than copper instead of copper foil.

  Next, an eighth embodiment of the present invention will be described. This embodiment is an embodiment of a wiring board provided with the resin material according to the first embodiment described above. The wiring board according to the present embodiment is obtained by patterning a copper foil and forming a wiring in the laminated body according to the seventh embodiment described above.

  Next, a ninth embodiment of the present invention will be described. This embodiment is an embodiment of a semiconductor device provided with the wiring board according to the above-described eighth embodiment. FIG. 1 is a cross-sectional view showing a semiconductor device according to this embodiment. As shown in FIG. 1, the semiconductor device 1 according to the present embodiment is an FCBGA type semiconductor device. The semiconductor device 1 is provided with a package substrate 2. The package substrate 2 is formed by laminating a plurality of wiring layers. In each wiring layer, a wiring 3 made of, for example, copper and a via 4 connected to the wiring 3 are formed. A plurality of mounting pads 5 are formed on the uppermost wiring layer of the package substrate 2. The wiring 3, the via 4, and the mounting pad 5 are collectively referred to as wiring. On the other hand, a plurality of ball pads 6 are formed on the lower surface of the package substrate 2. The mounting pads 5 and the ball pads 6 viewed from a direction perpendicular to the upper surface of the package substrate 2 (hereinafter referred to as a plan view) are arranged in a matrix.

  The ball pads 6 are larger than the mounting pads 5 in plan view, and the arrangement intervals of the ball pads 6 are larger than the arrangement intervals of the mounting pads 5. Each mounting pad 5 is connected to the ball pad 6 through the wiring 3 and the via 4. A solder bump 7 is connected to the mounting pad 5, and a BGA ball 8 is connected to the ball pad 6. The BGA ball 8 is larger than the solder bump 7.

  A semiconductor chip 9 is mounted on the package substrate 2. The semiconductor chip 9 is, for example, provided with a multilayer wiring layer (not shown) on a silicon substrate (not shown), and an integrated circuit is formed on the surface of the silicon substrate and the multilayer wiring layer. Input / output pads (not shown) are provided on the surface of the multilayer wiring layer in the semiconductor chip 9, that is, the surface facing the package substrate 2, and each input / output pad is connected to each solder bump 7. . Thereby, the input / output pads of the semiconductor chip 9 are connected to the mounting pads 5 via the solder bumps 7 and further connected to the BGA balls 8 via the wiring 3, the vias 4 and the ball pads 6. An underfill resin 10 is filled around the solder bump 7 between the package substrate 2 and the semiconductor chip 9. Thereby, the semiconductor chip 9 is connected and fixed to the package substrate 2.

  A stiffener 11 made of, for example, stainless steel or copper is provided in a region surrounding the semiconductor chip 9 on the package substrate 2. The stiffener 11 is bonded to the package substrate 2 by an adhesive layer 15. The stiffener 11 has a frame shape in plan view, and the semiconductor chip 9 is accommodated in the opening thereof. The upper surface of the stiffener 11 is substantially flush with the upper surface of the semiconductor chip 9.

  Furthermore, a lid 12 made of, for example, ceramics is provided on the semiconductor chip 9 and the stiffener 11. The lid 12 is bonded to the semiconductor chip 9 by the adhesive layer 13 and is bonded to the stiffener 11 by the adhesive layer 14. The shape of the lid 12 is a shape that substantially overlaps the package substrate 2 in plan view. The lid 12 functions as a heat sink for the semiconductor chip 9. Furthermore, the semiconductor device 1 is mounted on a mother board (not shown) or the like via the BGA balls 8.

  The wiring layer (not shown) on the uppermost wiring layer of the package substrate 2, that is, the surface facing the semiconductor chip 9 and on which the mounting pads 5 are formed, has a temperature of 10 to 30 ° C. It is formed of a resin material having a Young's modulus of 1 GPa or less and a breaking elongation of 50% or more. This uppermost wiring layer is formed of the resin material according to the first embodiment described above.

  Next, the operation of the present embodiment configured as described above will be described. As shown in FIG. 1, the semiconductor device 1 is mounted on a mother board (not shown) via BGA balls 8. The motherboard is, for example, an FR-4 substrate or an FR-5 substrate, for example, a glass epoxy substrate in which a glass cloth is immersed in an epoxy resin.

  A power supply potential and a signal are input to the semiconductor device 1 via the motherboard. At this time, the power supply potential and the signal are input to the semiconductor chip 9 through a current path including the BGA ball 8 → the ball pad 6 → the via 4 and the wiring 3 → the mounting pad 5 → the solder bump 10. The semiconductor chip 9 performs information processing such as signal storage and calculation based on the input power supply potential and signal, and outputs the result. The output signal is output to the mother board through a current path including the solder bump 10 → the mounting pad 5 → the via 4 and the wiring 3 → the ball pad 6 → the BGA ball 8, and is output to the outside through the mother board. .

  At this time, heat is generated by the operation of the semiconductor chip 9. Although a part of this heat is absorbed by the lid 12, the heat capacity of the lid 12 is limited. Therefore, the other part of the heat is conducted to the package substrate 2 through the solder bump 7, and the rest is transferred to the semiconductor chip 9. Accumulated. As a result, the temperatures of the semiconductor chip 9, the solder bump 7 and the package substrate 2 inevitably rise. Thereby, although the semiconductor chip 9 and the package substrate 2 are thermally expanded, the thermal expansion coefficient of silicon forming the substrate of the semiconductor chip 9 and the thermal expansion coefficient of the resin material mainly forming the package substrate 2 are Since they are different from each other, the respective thermal expansion amounts are also different from each other. As a result, a shearing force is applied between the semiconductor chip 9 and the package substrate 2 via the solder bumps 7.

  At this time, in this embodiment, since the uppermost wiring layer of the package substrate 2 is formed of a relatively soft resin material having a Young's modulus of 1 GPa or less, this wiring layer is used for thermal expansion of the semiconductor chip 9. It can follow and deform. As a result, the force acting between the semiconductor chip 9 and the package substrate 2 is relieved, and a large force is not applied to the solder bump 7. Similarly, when the semiconductor device 1 is heated or cooled due to an external temperature change, the thermal stress acting between the semiconductor chip 9 and the package substrate 2 is relieved by the deformation of the wiring layer, and the solder bumps 7 are excessive. Force is not applied. As a result, the semiconductor device 1 does not warp and the solder bump 7 is not destroyed.

  As described above, in the present embodiment, the uppermost layer of the package substrate 2, that is, the wiring layer on the semiconductor chip 9 side, is formed of a material having a Young's modulus of 1 GPa or less when the temperature is 10 to 30 ° C. Even if a temperature cycle is applied to the semiconductor device 1 due to the operation of the semiconductor chip 9 or a change in the external temperature, it is possible to prevent the solder bump 7 from being damaged by applying an excessive force to the solder bump 7. Further, it is possible to prevent the solder bump 7 from being fatigued and destroyed due to repeated application of thermal stress to the solder bump 7. For this reason, the semiconductor device 1 has high connection reliability with respect to the temperature cycle.

  Further, since the breaking elongation amount of the material forming the uppermost wiring layer of the package substrate 2 is 50% or more, even if the wiring layer is deformed following the thermal expansion of the semiconductor chip 9, the wiring layer Defects such as cracks do not occur or break, and the reliability of the semiconductor device 1 is high.

  In the ninth embodiment, the uppermost wiring layer of the package substrate 2 is formed from the resin material according to the first embodiment. You may form with the resin material which concerns on that embodiment. Further, not only the uppermost wiring layer of the package substrate 2 but also two or more wiring layers including the uppermost layer may be formed of the resin material according to any one of the first to fourth embodiments. You may form all the wiring layers of 2 with these resin materials. As a result, the entire package substrate 2 can be deformed, and the effect of relieving thermal stress is further increased.

  In particular, in addition to the uppermost layer of the package substrate 2, the lowermost wiring layer of the package substrate 2, that is, the wiring layer facing the mother board (not shown) in the package substrate 2 is any one of the first to fourth It is preferable to form with the resin material which concerns on embodiment. Accordingly, the lowermost wiring layer of the package substrate 2 can be deformed following the thermal expansion of the mother board, and the thermal stress applied to the BGA ball 8 can be relaxed. As a result, warpage of the semiconductor device 1 and fatigue failure of the BGA ball 8 can be prevented, and connection reliability with respect to a temperature cycle can be improved. Further, an interlayer insulating film disposed in the semiconductor chip 9 may be formed of the resin material.

Test example 1

  Hereinafter, the effect of the embodiment of the present invention will be specifically described in comparison with a comparative example that deviates from the scope of the claims. First, Test Example 1 will be described. In this test example, the resin material described in each of the above-described embodiments is actually produced, and a laminate film, a double-sided copper-clad sheet, and an FCBGA type semiconductor device are produced using this resin material, and these characteristics are evaluated. did. First, each component which forms the resin material which concerns on an Example and a comparative example is demonstrated. Table 1 shows each of these components, namely, a reactive elastomer (A), an epoxy resin (B), a curing agent for epoxy resin (C), a resin (D) having a longer distance between functional groups than a phenol novolac resin, ethylene An epoxidized product (F) of an oxide compound (E) and an ethylene oxide compound is shown.

  As the reactive elastomer (A), the reactive polyamide elastomer (A1) or (A2) shown in Table 1 was used. The structures of the reactive polyamide elastomers (A1) and (A2) can be represented by the following chemical formula 17. In the following chemical formula 17, x, y, z, l (el), m and n are average polymerization degrees, x is an integer of 3 to 7, y is an integer of 1 to 4, and z is 5 to 15 N = l + m, n represents an integer of 2 to 200, and m / (l + m) ≧ 0.04.

  Moreover, the phenol biphenylene aroxy epoxy resin (B1), the phenol xylylene epoxy resin (B2), or the phenol novolac epoxy resin (B3) shown in Table 1 was used for the epoxy resin (B). The structure of the phenol biphenylene aroxy epoxy resin (B1) can be represented by the following chemical formula 18, the structure of the phenol xylylene epoxy resin (B2) can be represented by the following chemical formula 19, and the structure of the phenol novolac epoxy resin (B3) can be represented by the following chemical formula 20. be able to. In the following chemical formulas 18 to 20, n represents an integer of 0 to 75.

  Furthermore, p-cresol novolak resin (C1) or phenol novolac resin (C2) shown in Table 1 was used as the curing agent for epoxy resin (C). The structure of the p-cresol novolac resin (C1) can be represented by the following chemical formula 21, and the structure of the phenol novolak resin (C2) can be represented by the following chemical formula 22. In the following chemical formulas 21 and 22, n represents an integer of 0 to 75.

  Furthermore, the phenol biphenylene aralkyl resin (D1) or the phenol xylylene resin (D2) shown in Table 1 was used for the resin (D) having a longer distance between the functional groups than the phenol novolac resin. The structure of the phenol biphenylene aralkyl resin (D1) can be represented by the following chemical formula 23, and the structure of the phenol xylylene resin (D2) can be represented by the following chemical formula 24. In the following chemical formulas 23 and 24, n represents an integer of 0 to 75.

  Furthermore, the phenol biphenylene aralkyl type ethylene oxide resin (E1), the phenol xylylene type ethylene oxide resin (E2), or the phenol novolac type ethylene oxide resin (E3) shown in Table 1 is used for the ethylene oxide compound (E). did. Hereinafter, the ethylene oxide resin is also referred to as EO resin. The structure of the phenol biphenylene aralkyl type EO resin (E1) can be represented by the following chemical formula 25, the structure of the phenol xylylene type EO resin (E2) can be represented by the following chemical formula 26, and the structure of the phenol novolac type EO resin (E3) can be represented by the following chemical formula 27. Can be expressed as In the following chemical formulas 25 to 27, n represents an integer of 0 to 75.

  Furthermore, the epoxidized product of ethylene oxide compound (F) includes the epoxidized product of phenol biphenylene aralkyl type ethylene oxide compound (F1), the epoxidized product of phenol xylylene type ethylene oxide compound (F2) shown in Table 3, or the phenol novolak. Type ethylene oxide compound epoxidized product (F3) was used. The structure of the epoxidized product (F1) can be represented by the following chemical formula 29, the structure of the epoxidized product (F2) can be represented by the following chemical formula 29, and the structure of the epoxidized product (F3) can be represented by the following chemical formula 30. In the following chemical formulas 28 to 30, n represents an integer of 0 to 75, and G represents a glycidyl group represented by the following chemical formula 31.

  The resin material containing each of the components described above was dissolved and dispersed in an organic solvent together with a curing accelerating catalyst to prepare a varnish solution. Table 2 shows the curing acceleration catalyst and organic solvent used, and the types of copper foil used in the steps described below.

  And using this varnish solution, the laminate film, the single-sided copper clad prepreg material, and the double-sided copper clad sheet were produced. Moreover, the FCBGA type semiconductor device was produced using the single-sided copper clad prepreg material. Hereinafter, a method for manufacturing these samples will be described.

(1) Production of Laminate Film The above varnish solution was uniformly coated on a polyethylene terephthalate (PET) film coated with a release agent with a coating machine so as to obtain a desired thickness. Thereafter, the solvent is evaporated at a temperature of 100 ° C. for 5 minutes to volatilize the solvent, and then the resin surface is covered with a PET film with a release agent, that is, a three-layer laminate film, that is, (Release PET layer— A laminate film having a structure of (resin layer-release PET layer) was produced. In addition, the resin layer (including residual solvent) in this laminate film is in an uncured state.

(2) Production of single-sided copper-clad prepreg material The varnish solution was uniformly applied to the roughened surface (also referred to as a matte surface) of the copper foil shown in Table 2 with a coating machine so as to obtain the desired thickness. . Then, it is dried at a temperature of 100 ° C. for 5 minutes to volatilize a certain amount of solvent, and then the resin surface is covered with a PET film with a release agent, and a one-layer copper-clad prepreg material having a three-layer structure (release PET-resin Minute-copper foil). The resin layer (including the residual solvent) in the prepreg material is in an uncured state.

(3) Preparation of double-sided copper-clad sheet The varnish solution was uniformly applied to the roughened surface (matte surface) of the copper foil shown in Table 2 with a coating machine so as to obtain the desired thickness. Then, it dried for 5 minutes at the temperature of 100 degreeC, and the solvent was volatilized a fixed quantity. Next, another copper foil shown in Table 2 was prepared, and this other copper foil was applied to the resin surface of a sample (copper foil-resin layer) obtained by applying a varnish solution to the copper foil and drying it. The layers were stacked so that their roughened surfaces were in contact. Then, a pressure of 3 MPa was applied to the laminate at a temperature of 160 ° C. for 1 hour, and the laminate was press-molded by leaving it to stand at a temperature of 180 ° C. for 2 hours. Thereby, a double-sided copper-clad sheet (copper foil-resin layer-copper foil) was produced. The resin layer (including the residual solvent) in the double-sided copper-clad sheet is in a cured state.

(4) Fabrication of FCBGA type semiconductor device The FCBGA type semiconductor device shown in FIG. 1 was fabricated using the resin materials according to the examples and comparative examples described above. That is, wiring was formed on the copper foil of the single-sided copper-clad prepreg material described in the above (2), and this single-sided copper-clad prepreg material was laminated by a build-up method to produce a package substrate. Then, a semiconductor chip was mounted on the package substrate, a frame-shaped stiffener was provided around the semiconductor chip, and a lid (heat sink) was bonded onto the semiconductor chip and the reinforcing plate.

  Using the laminated film, single-sided copper-clad prepreg material, double-sided copper-clad sheet, and FCBGA type semiconductor device prepared as described above as samples, the amount of elongation at break, Young's modulus, flexibility, circuit embedding and temperature cycle reliability Evaluated. Hereinafter, these evaluation methods will be described.

(5) Evaluation of toughness After applying a pressure of 3 MPa at a temperature of 160 ° C. for 1 hour, the laminate film was left for 2 hours without applying a pressure at a temperature of 180 ° C. A cured film for a tensile test of 50 μm was prepared. The cured film was cut into a strip shape having a width of 10 mm and a length of 80 mm, and a tensile test was performed. The tensile test conditions were set such that the distance between the supports for supporting the cured film was 60 mm, and the tensile speed was 5 mm / min. By this tensile test, the amount of elongation at break and Young's modulus were calculated.

(6) Refractive evaluation The above double-sided copper-clad sheet, that is, the copper foil “USLP” or “HLP” shown in Table 2 is used, and the double-sided copper-clad sheet having a resin part thickness of 25 μm is 1 ° at 180 °. The material in which cracks did not occur was determined to be acceptable, and the material in which cracks were generated was determined to be unacceptable.

(7) Evaluation of circuit embedding property The release PET on one side was peeled off from the laminate film (release PET layer-resin layer-release PET layer) of the above (1) to expose the resin layer. On the other hand, a conventional three-layer CCL, ie, a conventional three-layer CCL having a three-layer structure of (PEN layer-resin layer (ABF-GX (trade name) manufactured by Ajinomoto Fine Techno))-copper foil) is prepared. A line and space pattern simulating a copper wiring circuit was formed on the surface. The width of the line and space of this pattern was 100 μm. And the copper foil surface of 3 layer CCL was accumulated on the resin layer of the laminate film, and the mirror wafer was further mounted on 3 layer CCL.

  This produced the sample laminated | stacked in order of (release PET layer-resin layer (resin layer of an Example or a comparative example) -copper foil-conventional resin layer-PEN layer-mirror wafer). This sample was applied with a pressure of 1 MPa at a temperature of 180 ° C. for 30 minutes using a vacuum laminator to bond the resin layer of the laminate film and the patterned copper foil. Next, this sample was observed with a microscope, and the degree to which the copper foil pattern was embedded in the resin layer was observed to determine whether the circuit embedding property was good or bad. The case where the circuit embedding property was particularly excellent was marked with ◎, and the case where the circuit embedding property was good enough for practical use was marked with ○.

(8) Evaluation of temperature cycle resistance reliability 38 FCBGA type semiconductor devices prepared in the above (4) were prepared for each resin material, and a temperature cycle test was performed on these semiconductor devices. The temperature cycle test started from room temperature, cooled to −40 ° C., held at −40 ° C. for 15 minutes, then heated to 125 ° C. and held at 125 ° C. for 15 minutes as one cycle. The heating and cooling time was fixed at 15 minutes. When 1000 cycles of the temperature cycle test were conducted, a crack occurred at the joint (solder bump) between the semiconductor chip constituting the FCBGA type semiconductor device and the package substrate. The number of occurrences was used as an index of connection reliability. It can be said that the FCBGA type semiconductor device having a smaller number of defects is superior in temperature cycle reliability.

  Tables 3 to 8 show the compositions of the resin materials and the evaluation results according to the examples and comparative examples. For example, as shown in Table 3. 1, the reactive elastomer (A) is a polyamide elastomer (A1) 60 mass%, an epoxy resin (B), an epoxy resin (B1) 23.86 mass%, and an epoxy resin curing agent (C). A mixture obtained by adding 0.05% by mass of an imidazole as a curing accelerating catalyst to a resin material containing 16.14% by mass of the epoxy resin curing agent (D1) is added to an organic solvent (78% by mass of cyclopentanone). It was dissolved and dispersed in 22% by mass of methyl ethyl ketone (MEK) to prepare a varnish solution having a nonvolatile content (total amount of the above components other than the organic solvent) of 30% by mass. Then, using the varnish solution thus obtained, various evaluation samples shown in the above (1) to (4) were prepared, and each evaluation method shown in the above (5) to (8) was used. Sample performance was evaluated. No. Samples other than 1 were also No. 1 except that the resin materials having the formulations shown in Tables 3 to 8 were used. A sample was prepared by the same method as in Example 1 and evaluated.

  In each table, “phr” is an abbreviation of “per hundred resin” and represents the mass ratio (% by mass) of the curing accelerating catalyst when the mass of the resin is 100. Further, the “connection reliability” column shows the number of semiconductor devices in which defects occurred among the 38 FCBGA type semiconductor devices for each sample after the temperature cycle test shown in (8) above. Furthermore, in Tables 3 to 8, the blank components are not contained in the resin material.

  No. shown in Tables 3 to 8 1 to No. 4, no. 8 and no. 10 to No. No. 25 is an example of the present invention. 5 to No. 7, no. 9 and no. 26 is a comparative example. Example No. 1 to No. 4, Example No. 8 and Example No. 10 to No. The resin material according to No. 25 contains the reactive elastomer (A) and the epoxy resin (B), the elongation at break is 50% or more, and the Young's modulus is 1 Gpa or less. It was excellent. In addition, the semiconductor device in which the wiring layer of the package substrate is formed of these resin materials has no more than two semiconductor devices in which defects occur after the above-described temperature cycle test among the 38 semiconductor devices, and the connection reliability is high. It was excellent. The temperature cycle test described above is set to a condition that is considerably stricter than the actual use conditions. Therefore, even if 2 out of 38 defective products occur in this test, there is no problem in actual use.

  In contrast, Comparative Example No. 5 to No. 7, Comparative Example No. 9 and Comparative Example No. The resin material according to No. 26 had an elongation at break of less than 50%, so that at least one of flexibility and connection reliability of the semiconductor device was inferior. In particular, Comparative Example No. In the semiconductor device according to No. 26, since the wiring layer was formed of a resin material having a Young's modulus of 1.70 GPa at room temperature, as a result of the above-described temperature cycle test, 10 out of 38 semiconductor devices were defective. Connection reliability was inferior to other comparative examples.

  In addition, Example No. 1 to No. 2, Example No. 8, Example No. 10 to 17, Example No. 20 and Example No. No. 23 was particularly excellent in circuit embedding. Example No. shown in Table 7 18 and Example No. As is clear from comparison with No. 20, when the polyamide elastomer A2 having a lower molecular weight is used as the reactive elastomer (A) than when the polyamide elastomer A1 is used (Example No. 18) (Example) No. 20) was superior in circuit embedding.

Test example 2

  Next, Test Example 2 will be described. In Test Example 2, a commercially available resin material was used as the material for the package substrate, and a semiconductor device was manufactured by the same method as in Test Example 1 described above, and a temperature cycle test was performed. The results are shown in Table 9.

  As shown in Table 9, Comparative Example No. 31 and no. Compared with the Example of this invention shown in the above-mentioned Test Example 1, No. 32 was remarkably inferior in connection reliability.

  The present invention can be applied to a resin material used for an insulating layer of a semiconductor device, and particularly suitable for a resin material for forming a wiring board of a semiconductor device in which a semiconductor chip is directly mounted on a wiring board such as FCBGA. Can be used for

It is sectional drawing which shows the semiconductor device which concerns on the 9th Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Semiconductor device 2; Package board 3; Wiring 4; Via 5; Mount pad 6; Ball pad 7; Solder bump 8; BGA ball 9; Adhesive layer

Claims (20)

A resin material for forming an insulating layer of a semiconductor device contains an epoxy resin and a reactive elastomer capable of reacting with the epoxy resin, has an elongation at break of 50% or more, and is a Young in a temperature range of 10 to 30 ° C. A resin material having a rate of 1 GPa or less. It contains a curing agent for epoxy resin, the curing agent for epoxy resin contains a resin having a longer distance between functional groups than phenol novolac resin, the content of the reactive elastomer is A, and the content of the epoxy resin is The value of (A × 100) / (A + B + C) is 60% by mass or more and less than 100% by mass, where B and the content of the epoxy resin curing agent are C. 2. Resin material. The resin material according to claim 2, wherein the resin having a longer distance between functional groups than the phenol novolac resin is an ethylene oxide compound. When the epoxy resin contains an epoxy resin having a longer distance between functional groups than the phenol novolak resin, the content of the reactive elastomer is A, and the content of the epoxy resin is B, (A × 100) / The resin material according to claim 1, wherein the value of (A + B) is 60% by mass or more and less than 100% by mass. It contains a curing agent for epoxy resin, the epoxy resin contains an epoxy resin having a longer distance between functional groups than the phenol novolac resin, the content of the reactive elastomer is A, the content of the epoxy resin is B, 2. The resin material according to claim 1, wherein when the content of the curing agent for epoxy resin is C, the value of (A × 100) / (A + B + C) is 60% by mass or more and less than 100% by mass. . 6. The resin material according to claim 4, wherein the epoxy resin having a longer distance between functional groups than the phenol novolac resin is an epoxidized product of an ethylene oxide compound. It contains a curing agent for epoxy resin, the epoxy resin contains an epoxidized product of an ethylene oxide compound, the curing agent for epoxy resin contains an ethylene oxide compound, the content of the reactive elastomer is A, and the epoxy resin The value of (A × 100) / (A + B + C) is 60% by mass or more and less than 100% by mass, where B is the content of C and the content of the curing agent for epoxy resin is C. 1. The resin material according to 1. When the content of the reactive elastomer is A and the content of the epoxy resin is B, the value of (A × 100) / (A + B) is 70% by mass or more and less than 100% by mass. Item 4. The resin material according to Item 1. When the content of the reactive elastomer is A, the content of the epoxy resin is B, and the content of the curing agent for the epoxy resin is C, it contains (A × 100) / ( The resin material according to claim 1, wherein the value of (A + B + C) is 70% by mass or more and less than 100% by mass. The resin material according to any one of claims 1 to 9, wherein the reactive elastomer is a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer. A varnish solution, wherein the resin material according to any one of claims 1 to 10 is dissolved or dispersed in a solvent. A B stage material obtained by heating the varnish solution according to claim 11. The B stage material according to claim 12, wherein the B stage material is applied on a foil made of a metal or an alloy. It has the foil which consists of a metal or an alloy, and the resin layer provided on this foil, The said resin layer is formed with the resin material of any one of Claims 1 thru | or 10. Laminated body. It has another resin layer formed on the said resin layer, The laminated body of Claim 14 characterized by the above-mentioned. It has the foil which consists of another metal or alloy formed on the said resin layer, The laminated body of Claim 14 characterized by the above-mentioned. A wiring board comprising one or a plurality of wiring layers, wherein the wiring layer includes a wiring and the resin material according to any one of claims 1 to 10. The wiring board according to claim 17, further comprising a cover layer made of an insulating material and covering the wiring. A semiconductor device comprising an insulating layer formed of the resin material according to claim 1. 20. The semiconductor device according to claim 19, further comprising a wiring board and a semiconductor chip mounted on the wiring board, wherein the insulating layer is provided in the wiring board.

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