JP2006098762A - Photosensitive resin composition and semiconductor device using the same - Google Patents

Abstract

【Task】
The present invention is capable of development, can obtain a pattern with a high resolution and a high residual film ratio, can be cured at low temperature, and has excellent mechanical properties, adhesion, and water absorption as film properties after curing. It is an object of the present invention to provide a photosensitive resin composition having sensitivity and a semiconductor device using the same.
[Solution]
Cyclic olefin resin (A) having an acidic group, a photoacid generator (B), a compound (C) having a reactive group capable of binding to the acidic group (A) at a temperature of 130 ° C. or higher, and a filler A photosensitive resin composition comprising (D).

Description

  The present invention can obtain a pattern having a high resolution and a high residual film ratio, can be cured at low temperature, and can be developed with good mechanical properties, adhesive properties, and water absorption properties by blending a filler. The present invention relates to a high-sensitivity positive photosensitive resin and a semiconductor device using the same.

Conventionally, polyimide resin having excellent heat resistance and excellent electrical and mechanical properties has been used for the surface protection film and interlayer insulation film of semiconductor elements. There is a demand for significant improvement in heat cycle resistance, heat shock resistance, etc., due to thinning, downsizing of sealing resin packages, transition to surface mounting by solder reflow, etc. It seems that higher performance polyimide resin is required It has become.
On the other hand, a technique using a so-called photosensitive polyimide resin that imparts photosensitivity to the polyimide resin itself has recently attracted attention.
If this is used, a part of the pattern creation process can be simplified and the effect of shortening the process can be obtained. However, a solvent such as N-methyl-2-pyrrolidone is required for development, which causes a problem in safety and handling. . Recently, positive photosensitive resins that can be developed with an aqueous alkali solution have been developed. For example, Japanese Patent Publication No. 1-468662 discloses a positive photosensitive resin composed of a polybenzoxazole precursor and a diazoquinone compound. This has high heat resistance, excellent electrical properties, and fine processability, and has the potential not only for wafer coating but also as a resin for interlayer insulation. The development mechanism of this positive photosensitive resin is that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, and the diazoquinone compound undergoes a chemical change upon exposure to become soluble in the alkaline aqueous solution. By utilizing the difference in solubility between the exposed area and the unexposed area, it is possible to create a coating film pattern only on the unexposed area.

However, these photosensitive polyimides and photosensitive polybenzoxazoles require a high temperature of about 350 ° C. for dehydration ring closure, and this heat treatment also causes a problem that the characteristics of the semiconductor are remarkably deteriorated. For these reasons, it has been desired to develop a photosensitive resin that can be cured at a low temperature while satisfying the above characteristics.
Further, in recent years, the size of wafers has increased particularly, and 300 mm wafers have been used. In the case of a large wafer, since the linear expansion coefficients of the Si wafer and the photosensitive resin are different from each other, the wafer is warped, and there is a problem that the wafer is broken in the back grinding process in which the wafer is thinned. Therefore, it has been desired to develop a low-stress photosensitive resin in which the linear expansion coefficient of the photosensitive resin is close to that of a silicon wafer.

Japanese Patent Publication No. 61-21823

  The present invention is capable of development, can obtain a pattern with a high resolution and a high residual film ratio, can be cured at low temperature, and has excellent mechanical properties, adhesion, and water absorption as film properties after curing. It is an object of the present invention to provide a photosensitive resin composition having sensitivity and a semiconductor device using the same.

[式（１）中、ＸはO、CH₂、(CH₂)₂のいずれかであり、ｎは０〜５までの整数である。Ｒ¹〜Ｒ⁴は、それぞれ水素、アルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、又はエステル基を含有する官能基、ケトン基を含有する官能基、エーテル基を含有する官能基、カルボキシル基、フェノール性水酸基、−C(OH)−(CF₃)₂、−N(H)−S(O)₂−CF₃等の酸性基を含有する官能基のうちいずれであってもよい。Ｒ¹〜Ｒ⁴は、単量体の繰り返しの中で異なっていてもよいが、全繰り返し単位のＲ¹〜Ｒ⁴のうち、少なくとも一つは酸性基を有する。]
[４] 酸性基を有する環状オレフィン系樹脂（Ａ）が式（２）で示される繰り返し単位を含むものである[１]又は[２]記載の感光性樹脂組成物。

[式（２）中、YはO、CH₂、(CH₂)₂のいずれか、Zは-CH₂-CH₂-、-CH=CH-のいずれかであり、ｌは０〜５までの整数である。Ｒ⁵〜Ｒ⁸は、それぞれ水素、アルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、又はエステル基を含有する官能基、ケトン基を含有する官能基、エーテル基を含有する官能基、カルボキシル基、フェノール性水酸基、−C(OH)−(CF₃)₂、−N(H)−S(O)₂−CF₃等の酸性基を含有する官能基のうちいずれであってもよい。Ｒ⁵〜Ｒ⁸は単量体の繰り返しの中で異なっていてもよいが、全繰り返し単位のＲ⁵〜Ｒ⁸のうち、少なくとも一つは酸性基を有する。]
[５] 無機フィラー（Ｄ）が、シリカ、酸化アルミニウム、酸化ジルコニウムから選ばれる１種類以上であることを特徴とする[１]〜[４]記載の感光性樹脂組成物。
[６] 無機フィラー（Ｄ）の平均粒径が１ｎｍから１００ｎｍであることを特徴とする請求項[１]〜[５]記載の感光性樹脂組成物。
[７] [１]〜[６]記載の感光性樹脂組成物の樹脂層を半導体チップの回路素子形成面上に有することを特徴とする半導体装置。
[８] [１]〜[６]記載の樹脂組成物の樹脂層と、回路素子が形成された半導体チップと、リードフレームと、を有する半導体装置であって、該樹脂層の一方の面が半導体チップに直接接合し、かつ他方の面がリードフレームに直接接合していることを特徴とするリード・オン・チップ（Lead On Chip）構造の半導体装置。 [1] A cyclic olefin resin (A) having an acidic group, a photoacid generator (B), and a compound (C) having a reactive group capable of binding to the acidic group of (A) at a temperature of 130 ° C. or higher; A photosensitive resin composition comprising a filler (D).
[2] The photosensitive resin composition according to [1], wherein the cyclic olefin resin is a polynorbornene resin.
[3] The photosensitive resin composition according to [1] or [2], wherein the cyclic olefin resin (A) having an acidic group contains a repeating unit represented by the formula (1).

[In the formula (1), X is any one of O, CH ₂ and (CH ₂ ) ₂ , and n is an integer from 0 to 5. R ^{1 to} R ⁴ are each a functional group containing a hydrogen, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, or ester group, a functional group containing a ketone group, a functional group containing an ether group, Any of functional groups containing an acidic group such as a carboxyl group, a phenolic hydroxyl group, -C (OH)-(CF ₃ ) ₂ , -N (H) -S (O) ₂ -CF ₃ may be used. . R ^{1 to} R ⁴ may be different among the repeating monomers, but at least one of R ^{1 to} R ⁴ of all repeating units has an acidic group. ]
[4] The photosensitive resin composition according to [1] or [2], wherein the cyclic olefin resin (A) having an acidic group contains a repeating unit represented by the formula (2).

[In Formula (2), Y is any of O, CH ₂ , (CH ₂ ) ₂ , Z is any of —CH ₂ —CH ₂ —, —CH═CH—, and l is from 0 to 5 Is an integer. R ^{5 to} R ⁸ are each a functional group containing hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or an ester group, a functional group containing a ketone group, a functional group containing an ether group, Any of functional groups containing an acidic group such as a carboxyl group, a phenolic hydroxyl group, -C (OH)-(CF ₃ ) ₂ , -N (H) -S (O) ₂ -CF ₃ may be used. . R ^{5 to} R ⁸ may be different among the repeating monomers, but at least one of R ^{5 to} R ⁸ of all repeating units has an acidic group. ]
[5] The photosensitive resin composition according to [1] to [4], wherein the inorganic filler (D) is at least one selected from silica, aluminum oxide, and zirconium oxide.
[6] The photosensitive resin composition according to [1] to [5], wherein the inorganic filler (D) has an average particle size of 1 nm to 100 nm.
[7] A semiconductor device comprising a resin layer of the photosensitive resin composition according to any one of [1] to [6] on a circuit element forming surface of a semiconductor chip.
[8] A semiconductor device comprising a resin layer of the resin composition according to [1] to [6], a semiconductor chip on which circuit elements are formed, and a lead frame, wherein one surface of the resin layer is A semiconductor device having a lead-on-chip structure, wherein the semiconductor device is directly bonded to a semiconductor chip and the other surface is directly bonded to a lead frame.

  According to the present invention, according to the present invention, a pattern having a high resolution and a high residual film ratio can be formed, low temperature curing is possible, and excellent film properties after curing, low stress properties, low water absorption It has become possible to provide a highly sensitive positive photosensitive resin having

  The cyclic olefin monomer used in the present invention is generally a monocyclic compound such as cyclohexene or cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotriene. Examples include polycyclic compounds such as cyclopentadiene, tetracyclopentadiene, dihydrotetracyclopentadiene and the like. Substitutes in which a functional group is bonded to these monomers can also be used.

[式（３）中、ＸはO、CH₂、(CH₂)₂のいずれかであり、ｎは０〜５までの整数である。Ｒ¹〜Ｒ⁴は、それぞれ水素、アルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基、又はエステル基を含有する官能基、ケトン基を含有する官能基、エーテル基を含有する官能基、カルボキシル基、フェノール性水酸基、−C(OH)−(CF₃)₂、−N(H)−S(O)₂−CF₃等の酸性基を含有する官能基のうちいずれであってもよい。Ｒ¹〜Ｒ⁴は、単量体の繰り返しの中で異なっていてもよいが、全繰り返し単位のＲ¹〜Ｒ⁴のうち、少なくとも一つは酸性基を有する。] As the cyclic olefin monomer used for producing the cyclic olefin-based resin used in the present invention, a norbornene-type monomer represented by the general formula (3) is preferable.
Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, cyclopentyl, cyclohexyl, cyclooctyl groups, and the like. Specific examples of the alkenyl group include Specific examples of the alkynyl group include vinyl, allyl, butynyl, cyclohexenyl group, etc., and specific examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl group, and the like. , Naphthyl, anthracenyl group, etc., as specific examples of the aralkyl group, benzyl, phenethyl group, etc., as the functional group containing an acidic group, carboxyl group, phenolic hydroxyl group, -C (OH)-(CF ₃ ) ₂ Although -N (H) -S (O) 2 -CF 3 can be mentioned, the present invention is in no way limited thereto.
Regarding the functional group containing an ester group and the functional group containing a functional group containing a ketone group, the structure is not particularly limited as long as it is a functional group having these groups. The functional group containing an ether group includes a functional group containing a cyclic ether such as an epoxy group or an oxetane group.

[In the formula (3), X is any one of O, CH ₂ and (CH ₂ ) ₂ , and n is an integer from 0 to 5. R ^{1 to} R ⁴ are each a functional group containing a hydrogen, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, or ester group, a functional group containing a ketone group, a functional group containing an ether group, Any of functional groups containing an acidic group such as a carboxyl group, a phenolic hydroxyl group, -C (OH)-(CF ₃ ) ₂ , -N (H) -S (O) ₂ -CF ₃ may be used. . R ^{1 to} R ⁴ may be different among the repeating monomers, but at least one of R ^{1 to} R ⁴ of all repeating units has an acidic group. ]

  Examples of the cyclic olefin resin used in the present invention include polymers of the above cyclic olefin monomers. As the polymerization method, known methods such as random polymerization and block polymerization are used. Specific examples include (co) polymers of norbornene-type monomers, copolymers of norbornene-type monomers and other copolymerizable monomers such as α-olefins, and hydrogenation of these copolymers. A thing corresponds to a specific example. These cyclic olefin resins can be produced by a known polymerization method, and there are an addition polymerization method and a ring-opening polymerization method. Of these, polymers obtained by addition (co) polymerization of norbornene monomers, or polymers obtained by ring-opening polymerization of norbornene monomers and hydrogenated as necessary are preferred, but the present invention is not limited to these. It is not a thing.

  As addition polymers of cyclic olefin resins, (1) addition (co) polymers of norbornene monomers obtained by addition (co) polymerization of norbornene monomers, (2) norbornene monomers and ethylene, Addition copolymers with α-olefins, (3) addition copolymers of norbornene-type monomers and non-conjugated dienes, and other monomers as required. These resins can be obtained by all known polymerization methods. The type of cyclic olefin resin represented by the chemical formula (1) can be obtained by the above addition polymerization.

Examples of the ring-opening polymer of the cyclic olefin-based resin include (4) a ring-opening (co) polymer of a norbornene type monomer, and a resin obtained by hydrogenating the (co) polymer if necessary, (5) a norbornene type A ring-opening copolymer of a monomer and ethylene or α-olefins, and a resin obtained by hydrogenating the (co) polymer if necessary, (6) a norbornene-type monomer and a non-conjugated diene, or other monomers A ring-opening copolymer with-, and a resin obtained by hydrogenating the (co) polymer if necessary. These resins can be obtained by all known polymerization methods. A cyclic olefin resin of the type represented by the chemical formula (2) can be obtained by the ring-opening polymerization.
Among the above, (1) addition (co) polymer obtained by addition (co) polymerization of norbornene type monomer, (4) ring-opening (co) polymer of norbornene type monomer, and A resin obtained by hydrogenating a (co) polymer is preferred, but the present invention is not limited to these.

The addition polymer of the cyclic olefin resin is obtained by coordination polymerization using a metal catalyst or radical polymerization. Among them, in coordination polymerization, a polymer is obtained by polymerizing monomers in a solution in the presence of a transition metal catalyst (NiCOLE R. GROVE et al. Journal of Polymer Science: part B, Polymer Physics, Vol. 1). 37, 3003-3010 (1999)).
Representative nickel and platinum catalysts as metal catalysts for coordination polymerization are described in PCT WO 9733198 and PCT WO 00/20472. Examples of metal catalysts for coordination polymerization include (toluene) bis (perfluorophenyl) nickel, (mesylene) bis (perfluorophenyl) nickel, (benzene) bis (perfluorophenyl) nickel, bis (tetrahydro) bis ( Known metal catalysts such as perfluorophenyl) nickel, bis (ethyl acetate) bis (perfluorophenyl) nickel, and bis (dioxane) bis (perfluorophenyl) nickel may be mentioned.

The radical polymerization technique is described in Encyclopedia of Polymer Science, John Wiley & Sons, 13, 708 (1988).
Generally, in radical polymerization, the temperature is raised to 50 ° C. to 150 ° C. in the presence of a radical initiator, and the monomer is reacted in a solution. Examples of the radical initiator include azobisisobutyronitrile (AIBN), benzoyl peroxide, lauryl peroxide, azobisisocapronitrile, azobisisoleronitrile, and t-butyl hydrogen peroxide.

  A ring-opening polymer of a cyclic olefin resin is obtained by ring-opening (co) polymerization of at least one norbornene-type monomer by a known ring-opening polymerization method using titanium or a tungsten compound as a catalyst. Obtained by producing a thermoplastic saturated norbornene-based resin by hydrogenating the carbon-carbon double bond in the ring-opening (co) polymer by a conventional hydrogenation method, if necessary. .

  The cyclic olefin resin having an acidic group used in the present invention can be obtained by directly polymerizing a monomer having an acidic group by the above method. However, depending on the polymerization system, if the monomer contains an acidic group, the catalyst or the like may be deactivated and the polymerization may not proceed appropriately. In this case, the cyclic olefin-based resin having an acidic group of the present invention can be obtained by introducing a protective group into the acidic group, polymerizing, and deprotecting the polymer after production. Alternatively, a method may be adopted in which a functional group capable of chemically reacting with an acidic group is introduced into the monomer, and the functional group is converted into an acidic group by polymer reaction after polymer synthesis.

  As described above, the cyclic olefin-based resin having an acidic group uses a monomer obtained by substituting the ionizable hydrogen atom of the acidic group in the cyclic olefin monomer with another structure, polymerizes this, and then deprotects it. It can be obtained by introducing the original hydrogen atom. Specific examples of functional groups that can be substituted with hydrogen atoms at this time include tertiary butyl groups, tertiary butoxycarbonyl groups, tetrahydropyran-2-yl groups, trialkylsilyl groups such as trimethylsilyl groups, and methoxymethyl groups. And so on. Deprotection, that is, restoration of the acidic group by elimination of the protecting group from the monomer can be performed by a conventional method in the case of using the functional group as a protective group for the acidic functional group.

  A method for introducing an acidic group by polymerizing a cyclic olefin resin having no acidic group will be described. In the presence of a radical initiator, a cyclic olefin resin having no acidic group is converted into acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, endocis. Unsaturation such as -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid Mixed with polar group-containing compounds such as carboxylic acid compounds, or esters or amides thereof, or unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride, etc. Then, a cyclic olefin resin having an acidic group can be obtained by heating.

  The content of the unit having an acidic group in the copolymer can be determined optimally depending on whether or not alkali solubility can be exhibited after exposure. For example, the acidic group is preferably 0.2 to 0.1 mol per gram of polymer. More preferably, it is 0.03-0.1 mol. If the value is larger than the above range, the monomer selection range becomes extremely narrow, and it becomes difficult to align other characteristics. On the other hand, when the value is smaller than the above range, it becomes difficult to develop solubility in an alkaline aqueous solution, which is not preferable.

Among monomers for obtaining a cyclic olefin-based resin having an acidic group used in the present invention, a monomer having an acidic group or a monomer having a functional group that is deprotected to become an acidic group specifically includes bicyclo [ 2.2.1] hept-2-ene-5-carboxylic acid, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid, (bicyclo [2.2.1] hept-2-en-5-yl) acetic acid, 2- (bicyclo [2.2.1] hept- 2-ene-5-yl) propionic acid, 3- (bicyclo [2.2.1] hept-2-en-5-yl) butyric acid, 3- (bicyclo [2.2.1] hept-2-ene -5-yl) valeric acid, 3- (bicyclo [2.2.1] hept-2-en-5-yl) caproic acid, succinic acid mono- (2- (bicyclo [2.2.1] hept- 2-ene-5-yl) carbonyloxyethyl) ester, succinic acid mono- (2- (bicyclo [2.2.1] hept-2-en-5-yl) carbonyloxypropyl) ester, succinic acid mono- (2- (bicyclo [2.2.1] hept-2-en-5-yl) carbonyloxybutyl) ester, Mono- (2- (bicyclo [2.2.1] hept-2-en-5-yl) carbonyloxyethyl) ester, caproic acid mono- (2- (bicyclo [2.2.1] hept- 2-ene-5-yl) carbonyloxybutyl) ester, (bicyclo [2.2.1] hept-2-en-5-yl) carbonyloxyacetic acid, 2- (bicyclo [2.2.1] hept- 2-ene-5-yl) methylphenol, 3- (bicyclo [2.2.1] hept-2-en-5-yl) methylphenol, 4- (bicyclo [2.2.1] hept-2- En-5-yl) methylphenol, 4- (bicyclo [2.2.1] hept-2-en-5-yl) phenol, 4- (bicyclo [2.2.1] hept-2-ene-5 -Yl) methylcatechol, 3-methoxy-4- (bicyclo [2.2.1] Hept-2-en-5-yl) methylphenol, 3-methoxy-2- (bicyclo [2.2.1] hept-2-en-5-yl) methylphenol, 2- (bicyclo [2.2. 1] hept-2-en-5-yl) methylresorcin, 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl alcohol, 1,1 -Bistrifluoromethyl-3- (bicyclo [2.2.1] hept-2-en-5-yl) propyl alcohol, 1,1-bistrifluoromethyl-4- (bicyclo [2.2.1] hept- 2-ene-5-yl) butyl alcohol, 1,1-bistrifluoromethyl-5- (bicyclo [2.2.1] hept-2-en-5-yl) pentyl alcohol, 1,1-bistrifluoromethyl -6- (bicyclo [ 2.2.1] hept-2-en-5-yl) hexyl alcohol, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propylcarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-i-propylcarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-i-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (methoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (ethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (n-propoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (i-propoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (n-butoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (t-butoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (cyclohexyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (phenoxyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (tetrahydrofuranyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-di (tetrahydropyranyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene-8-carboxylic acid, and the like, but are not limited to these in the present invention.

Among the monomers for obtaining a cyclic olefin resin having an acidic group used in the present invention, specific examples of the monomers other than those described above include the following. As those having an alkyl group, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-butyl-2-norbornene, 5-pentyl-2-norbornene, 5-hexyl As those having an alkenyl group, such as 2-norbornene, 5-heptyl-2-norbornene, 5-octyl-2-norbornene, 5-nonyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl- 2-norbornene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2 -Norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pen Nyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2 -Norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexenyl) -2-norbornene, 5 Examples of those having an alkynyl group such as-(5-ethyl-5-hexenyl) -2-norbornene and 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene include 5- Examples of those having a silyl group such as nyl-2-norbornene include 1,1,3,3,5,5-hexamethyl-1,5-dimethylbis ((2- (5-norbornen-2-yl) ethyl) As those having an aryl group such as trisiloxane, those having an aralkyl group such as 5-phenyl-2-norbornene, 5-naphthyl-2-norbornene, and 5-pentafluorophenyl-2-norbornene are 5-benzyl- 2-norbornene, 5-phenethyl-2-norbornene, 5-pentafluorophenylmethane-2-norbornene, 5- (2-pentafluorophenylethyl) -2-norbornene, 5- (3-pentafluorophenylpropyl) -2 Examples of those having an alkoxysilyl group such as norbornene include dimethylbis ((5- Rubornen-2-yl) methoxy)) silane, 5-trimethoxysilyl-2-norbornene, 5-triethoxysilyl-2-norbornene, 5- (2-trimethoxysilylethyl) -2-norbornene, 5- (2 -Triethoxysilylethyl) -2-norbornene, 5- (3-trimethoxypropyl) -2-norbornene, 5- (4-trimethoxybutyl) -2-norbornene, 5-trimethylsilylmethyl ether-2-norbornene, etc. Examples of those having a hydroxyl group, an ether group, an ester group, an acryloyl group or a methacryloyl group include 5-norbornene-2-methanol and alkyl ethers thereof, acetic acid 5-norbornene-2-methyl ester, propionic acid 5-norbornene-2 -Methyl ester, 5-norbornene butyrate -2-methyl ester, valeric acid 5-norbornene-2-methyl ester, caproic acid 5-norbornene-2-methyl ester, caprylic acid 5-norbornene-2-methyl ester, capric acid 5-norbornene-2-methyl ester, Lauric acid 5-norbornene-2-methyl ester, stearic acid 5-norbornene-2-methyl ester, oleic acid 5-norbornene-2-methyl ester, linolenic acid 5-norbornene-2-methyl ester, 5-norbornene-2- Carboxylic acid, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid ethyl ester, 5-norbornene-2-carboxylic acid t-butyl ester, 5-norbornene-2-carboxylic acid i-butyl ester , 5-norbornene-2-carbo Acid trimethylsilyl ester, 5-norbornene-2-carboxylic acid triethylsilyl ester, 5-norbornene-2-carboxylic acid isobornyl ester, 5-norbornene-2-carboxylic acid 2-hydroxyethyl ester, 5-norbornene-2-methyl 2-carboxylic acid methyl ester, cinnamic acid 5-norbornene-2-methyl ester, 5-norbornene-2-methylethyl carbonate, 5-norbornene-2-methyl n-butyl carbonate, 5-norbornene-2- Methyl t-butyl carbonate, 5-methoxy-2-norbornene, (meth) acrylic acid 5-norbornene-2-methyl ester, (meth) acrylic acid 5-norbornene-2-ethyl ester, (meth) acrylic acid 5- Norbornene-2-n-butyl ester, ( T) Acrylic acid 5-norbornene-2-n-propyl ester, (meth) acrylic acid 5-norbornene-2-i-butyl ester, (meth) acrylic acid 5-norbornene-2-i-propyl ester, (meth) Examples of those having an epoxy group such as 5-norbornene-2-hexyl acrylate, (meth) acrylic acid 5-norbornene-2-octyl ester, (meth) acrylic acid 5-norbornene-2-decyl ester, [(2,3-Epoxypropoxy) methyl] -2-norbornene and the like, and those composed of a tetracyclo ring include 8,9-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 0 ^1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,12] Dodekku-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 0 ^1,6 ] Dodec-3-ene. However, the present invention is not limited to these.

  Suitable polymerization solvents for the above-described polymerization system include hydrocarbons and aromatic solvents. Examples of the hydrocarbon solvent include pentane, hexane, heptane, and cyclohexane, but are not limited thereto. Examples of the aromatic solvent include, but are not limited to, benzene, toluene, xylene and mesitylene. Diethyl ether, tetrahydrofuran, ethyl acetate, ester, lactone, ketone, amide can also be used. These solvents can be used alone or as a polymerization solvent.

  The molecular weight of the cyclic olefin resin of the present invention can be controlled by changing the ratio of the initiator and the monomer or changing the polymerization time. When the above-mentioned coordination polymerization is used, US Pat. As disclosed in US Pat. No. 6,136,499, the molecular weight can be controlled by using a chain transfer catalyst. In this invention, α-olefins such as ethylene, propylene, 1-hexane, 1-decene, 4-methyl-1-pentene are suitable for controlling the molecular weight.

  In the present invention, the weight average molecular weight is 5,000 to 500,000, preferably 7,000 to 200,000, more preferably 8,000 to 100,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using standard polynorbornene. (Conforms to ASTM D3536-91)

The photoacid generator (B) used in the present invention is a substance that generates Bronsted acid or Lewis acid upon irradiation with actinic rays, and includes, for example, onium salts, halogenated organic compounds, quinonediazide compounds, α, α-bis. Examples include (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds. In the present invention, it is preferable to use a quinonediazide compound.

  Preferable specific examples of the photoacid generator (B) used in the present invention include compounds having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure. These are known substances from U.S. Pat. Nos. 2,729,975, 2,797,213 and 3,669,658. Of these, 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid and phenol are used to obtain a high solubility contrast at a particularly small exposure amount. Ester compounds with compounds are preferred. These photoacid generators function as positive photoacid generators that generate a carboxyl group by a photoreaction during exposure by radiation irradiation and increase the solubility of an exposed portion in an alkaline developer.

  The content of the photoacid generator (B) used in the present invention is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble cyclic olefin resin (A). Part is desirable. If the blending amount is less than 1 part by weight, the exposure and development characteristics of the resin composition will be poor.

Specific examples of the compound (C) having a reactive group capable of binding to the acidic group of the cyclic olefin resin (A) having an acidic group at a temperature of 130 ° C. or higher used in the present invention are described. Specific examples of the reactive group capable of binding to an acidic group contained in the compound (C) include an epoxy group such as a glycidyl group and an epoxycyclohexyl group, an oxazoline group such as a 2-oxazolin-2-yl group, and N-hydroxymethylamino. Examples thereof include a methylol group such as a carbonyl group, and an alkoxymethyl group such as an N-methoxymethylaminocarbonyl group.
Examples of the compound (C) include phenyl glycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycidyloxypropyltrimethoxysilane, polymethyl (glycidyloxy) Epoxy group-containing silicone such as propyl) siloxane, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 1,3-bis (2-oxazolin-2-yl) benzene, 1,4-bis (2- Oxazolin-2-yl) benzene, 2,2′-bis (2-oxazoline), 2,6-bis (4-isopropyl-2-oxazolin-2-yl) pyridine, 2,6-bis (4-phenyl-) 2-Oxazolin-2-yl) pyridine, 2, 2'-isopropylidenebis (4-phenyl-2-oxazoline), (S, S)-(-)-2,2'-isopropylidenebis (4-tert-butyl-2-oxazoline), poly (2- Oxazoline ring-containing polymers such as propenyl-2-oxazoline), N-methylolacrylamide, N-methylolmethacrylamide, furfuryl alcohol, benzyl alcohol, salicyl alcohol, 1,2-benzenedimethanol, 1,3-benzenedimethanol, Examples include 1,4-benzenedimethanol and resol type phenol resin, but the present invention is not limited thereto. These may be used alone or in admixture of two or more.

  As for content of a compound (C), 1-100 weight part is preferable with respect to 100 weight part of cyclic olefin resin (A) which has the said acidic group, More preferably, it is 5-50 weight part. If the blending amount is less than 1 part by weight, the physical properties after curing of the resin composition will be poor.

  The resin solid content of the resin composition used in the present invention is 5 to 60% by weight. More preferably, it is 30-55 weight%, More preferably, it is 35-45 weight%. The solution viscosity is 10 to 25,000 cP, preferably 100 to 3,000 cP.

An organic filler, an inorganic filler, etc. can be used for the filler (D) used by this invention. Examples of the organic filler include epoxy resin, melamine resin, urea resin, acrylic resin, phenol resin, polyimide resin, polyamide resin, polyester resin, and Teflon (registered trademark) resin. As inorganic filler, metal oxide fine particles such as alumina, silica, magnesia, ferrite, aluminum oxide, zirconium oxide, titanium oxide, or silicates such as talc, mica, kaolin, zeolite, barium sulfate, calcium carbonate, fullerene, etc. Fine particles are used. The said filler is used 1 type or in mixture of 2 or more types. In particular, silica, aluminum oxide, and zirconium oxide are preferable because they do not exhibit thixotropy even after mixing and can be uniformly applied by a spinner.

The filler is fine particles having an average particle diameter of 1000 nm or less, preferably 1 to 100 nm or less. A more preferable range is 10 to 50 nm. Since UV exposure is performed during development, if a filler having an excessively large particle size is used, light is scattered and development cannot be performed appropriately. If the average particle diameter exceeds 1000 nm, the resolution and sensitivity are lowered, which is not preferable. The addition amount of the filler is 2 wt% or more and 70 wt% or less, preferably 50 wt% or less with respect to the solid content weight of the photosensitive resin composition. If it is 2 wt% or less, there is almost no effect of addition, and if it is 70 wt% or more, the development time becomes extremely long, or a film cannot be formed after curing.

  When mixing the filler and the resin, the photosensitive agent and the organic solvent, etc., it is preferable that the filler is uniformly dispersed in the resin composition. Dispersion can be carried out by a known method. For example, a photosensitive resin composition with good dispersion mixing can be obtained using a dispersing device having a strong shearing force such as a ball mill, a roll mill, or a diamond mill. Furthermore, in order to perform dispersion mixing well, it is possible to add a wetting agent, a dispersing agent, a silane coupling agent, a titanium coupling agent, an antifoaming agent, or the like, or to perform a hydrophobic treatment on the filler in advance.

As a method for producing the photosensitive resin composition in the present invention, in order to prevent secondary aggregation of the filler, the filler is uniformly dispersed in a solvent using a dispersing agent in advance, and then the resin, the photosensitive agent, etc. are dissolved. As a result, a uniform varnish can be obtained. Examples of the dispersing agent include an anionic active agent, a cationic active agent, a nonionic active agent, and an amphoteric active material. Among these, a cationic active agent and a nonionic active agent are preferable. Of these, phosphate ester type activators are preferred.

  In the resin composition of the present invention, additives such as a phenol resin, a leveling agent, an antioxidant, a flame retardant, a plasticizer, a silane coupling agent, and a curing accelerator are appropriately added for the purpose of improving characteristics such as sensitivity. Can be added.

In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl -3-methoxypropionate and the like, and these may be used alone or in combination. Good.
Among these, use of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, and cyclohexanone is preferable from the viewpoint of high solubility and easy removal during post-curing due to volatilization.

In order to use the resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, ceramic, aluminum substrate, glass substrate, film substrate and the like. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, spinless coating using a slit coater, and a combination of these coating methods. Next, after prebaking at 90 to 130 ° C. for about 1 to 30 minutes to dry the coating film, an active energy ray is irradiated to a desired pattern shape. The active energy ray is a general term for electromagnetic waves, radiation, or energy rays having an intermediate property thereof. For example, X-rays, electron beams, ultraviolet rays, visible rays, ionizing radiations and the like can be used, but those having a wavelength of 200 to 700 nm. Is preferred.
Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. The developer is not particularly limited, but includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and aqueous ammonia, aqueous solutions of organic alkalis such as tetramethylammonium hydroxide, ethylamine, triethylamine and triethanolamine, An aqueous solution to which an appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol and a surfactant are added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible. Next, the relief pattern formed by development is rinsed. As the rinsing liquid, for example, water or alcohol can be used. It is desirable to perform post-exposure on the entire resin pattern after rinsing. In the post-exposure, the entire surface of the resin layer after development can be exposed with an exposure machine, a UV conveyor, or the like used for pattern exposure. When the unreacted photosensitive group in the photoacid generator (B) is converted into a carboxyl group by this post-exposure step, light absorption can be suppressed and a resin layer excellent in transparency can be obtained.
The resin layer is completed by heat-curing after post-exposure. In other words, acidic groups that existed in the resin by heating and contributed to the expression of alkali solubility during photoprocessing, and carboxyl groups generated from the photoacid generator present in the resin layer by post-exposure can react with the acidic groups. It disappears by reacting with the functional group in a compound having a functional group, and prevents adverse effects derived from acidic groups from remaining in the reliability such as the dielectric constant and moisture resistance reliability of the processed resin layer, It is a feature of the present invention to form a strong cross-linked structure in the resin and improve the properties of the resin after thermosetting. Heat treatment is performed at a maximum temperature of 200 ° C. to 250 ° C. to remove the developer and the rinse solution, and the reaction is completed to obtain a final pattern rich in heat resistance.

Next, an application example to a semiconductor device having a lead-on-chip structure using the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of a resin-encapsulated semiconductor device having a LOC type structure of the present invention. A coating layer of the photosensitive resin composition of the present invention is provided on a chip 2, and this coating layer is bonded after patterning and curing. The chip 2 and the lead frame 3 are bonded and fixed as the agent 1, and the chip 2 and the lead frame 3 are connected with a gold wire, and then sealed with a resin seal 5. As a bonding method, the chip is heated to 50 to 300 ° C. and pressure-bonded for several seconds at a pressure of 0.1 to 10 kg / cm 2. FIG. 2 is a cross-sectional view of a conventional resin-encapsulated semiconductor device having a LOC structure, in which a chip 2 and a lead frame 3 are bonded and fixed via an insulating film 6 with an adhesive 1 ′ and then encapsulated with an encapsulating resin 5. It is a thing. Conventionally, since the insulating film 6 with the adhesive 1 ′ is bonded to the lead frame 3 and then the chip 2 and the lead frame 3 are bonded, the workability is not good. As an insulating film of the insulating film 6 with the adhesive 1 ′, a polyimide film having a large water absorption, linear expansion, and elastic modulus of about 20 μm is used. Therefore, generation of package cracks during solder immersion and stress from the sealing resin during mounting However, since the adhesive layer of the photosensitive resin of the present invention has a low water absorption rate and is a thin film, there is no generation of package cracks. A resin-encapsulated semiconductor device that can be relaxed and has a highly reliable LOC structure is obtained.

  The photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like.

Hereinafter, the present invention will be described specifically by way of examples.
<< Synthesis Example 1 >>
Synthesis of polymer 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl alcohol / 5-norbornene-2-carboxylic acid = 75/25 copolymer The example of a polymer (A-1) is given.
All glass equipment is dried at 60 ° C. under 0.1 torr for 18 hours. Thereafter, the glass device is moved into a glove box in which the internal oxygen concentration and humidity are kept within 1%, respectively, and installed in the glove box. Ethyl acetate (1000 g), cyclohexane (1000 g), 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl alcohol (65.9 g, 0.240 mol) ) And 5-norbornene-2-carboxylic acid trimethylsilyl ester (43.3 g, 0.240 mol) were added to the reaction flask. The reaction flask was removed from the glow box and dry nitrogen gas was introduced. The reaction intermediate was degassed by passing nitrogen gas through the solution for 30 minutes. Palladium catalyst, ie (allyl) palladium (tricyclohexylphosphine) trifluoroacetate 0.058 g (0.077 mmol) was dissolved in 16 ml of methylene chloride in a glove box, placed in a 25 ml syringe, removed from the glow box, and lithium tetrakis ( Pentafluorophenyl) borate (0.340 g) was added to the reaction flask along with a cocatalyst solution dissolved in 1000 g of toluene. Further, 1-hexene (25.9 g, 0.308 mol) was added and stirred at 20 ° C. for 5 hours to complete the reaction. Next, the polymer was put into methanol, and the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. After drying, 77.5 g (yield 71%) of polymer was recovered. The molecular weight of the obtained polymer was Mw = 52,200 Mn = 26,100 and monodispersity = 2.00 by GPC. Tg was 180 ° C. according to DMA. From ¹ H-NMR, the polymer composition was 72 mol% of 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl alcohol, 5-norbornene-2- The carboxylic acid was 27 mol%. Moreover, the acidic group of this resin was 0.0042 mol per 1 g of polymer.

<< Synthesis Example 2 >>
Synthesis of polymer 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl alcohol / 5-norbornene-2-carboxylic acid = opening of 50/50 copolymer Examples of the ring metathesis copolymer (A-2) will be given.
All glass equipment is dried at 60 ° C. under 0.1 torr for 18 hours. Thereafter, the glass device is moved into a glove box in which the internal oxygen concentration and humidity are kept within 1%, respectively, and installed in the glove box. Toluene (917 g), cyclohexane (917 g), 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl alcohol (151 g, 0.55 mol) and 5 -Norbornene-2-carboxylic acid trimethylsilyl ester (99.1 g, 0.55 mol), 1-hexene (368 g, 2.2 mol) was added to the reaction flask. The reaction flask was removed from the glow box and dry nitrogen gas was introduced. The reaction intermediate was degassed by passing nitrogen gas through the solution for 30 minutes. In a glove box, a solution of tungsten pentachloride in t-butyl alcohol / methanol (molar ratio 0.35 / 0.3) (0.05 mol / l) was prepared. Added to the reaction flask along with 0.634 g of cocatalyst solution dissolved in 25 g. The reaction was terminated by stirring at 20 ° C. for 5 hours.
Next, this solution is put in an autoclave, 40.02 g of RuHCl (CO) [P (C ₅ H ₅ ) ₃ ] ₃ is added, hydrogen is introduced until the internal pressure becomes 100 kg / cm ² , and the mixture is heated at 165 ° C. for 3 hours. Stirring was performed. After heating, the mixture was allowed to cool to room temperature, and the reaction product was added to methanol (975 mmol) and stirred for 18 hours. When the stirring was stopped, the aqueous layer and the solvent layer were separated. After separating the aqueous layer, 1 l of distilled water was added and stirred for 20 minutes. The aqueous layer separated and was removed. Washing was carried out 3 times with 1 l of distilled water. Thereafter, the polymer was put into methanol, and the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. After drying, 320 g (yield 85%) of polymer was recovered. The molecular weight of the obtained polymer was Mw = 16,000 Mn = 8,400 and monodispersity = 1.9 by GPC. Tg was 130 ° C. according to DMA. From ¹ H-NMR, the polymer composition was 48 mol% of 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl alcohol, 5-norbornene-2- The carboxylic acid was 52 mol%. Moreover, the acidic group of this resin was 0.0049 mol per 1 g of polymer.

Example 1
Preparation and characteristics evaluation of photosensitive resin composition 5 g of obtained resin (A-1), 15 g of propylene glycol monoethyl ether, bisphenol A type polyol type epoxy resin (YD-716, manufactured by Tohto Kasei Co., Ltd) 8 g and 0.5 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester of tris (4-hydroxyphenyl) methane were mixed. Thereafter, 0.5 g of silica (C-1: average particle size 100 nm, specific surface area 40 m ^{2 /} g) and phosphanol RE-610 (Toho Chemical Industry) were dispersed using a diamond mill, and then made of 1 μm fluororesin. It filtered with the filter and obtained the photosensitive resin composition (1).
The obtained photosensitive resin composition (1) was applied onto a silicon wafer with a spin coater and dried on a hot plate at 100 ° C. for 10 minutes to form a resin layer having a thickness of 10 μm. Using a parallel exposure machine (light source: high-pressure mercury lamp) through a mask, exposure was performed through a glass mask for 15 seconds at an exposure intensity of 25 mW / cm 2. Thereafter, the resin layer was immersed and developed in an aqueous 2.38% tetramethylammonium hydroxide solution for 60 seconds, whereby the resin layer in the exposed area was dissolved and a patterned resin layer could be obtained. Then, heat-curing was performed at 200 degreeC in the air for 1 hour using the hot air circulation type dryer. With respect to the obtained resin layer, the residual film ratio (film thickness after development / film thickness before development) was measured and found to be a very high value of 90.0%. Further, in the remaining pattern, no fine pattern peeling was observed, and it was confirmed that the adhesion during development was excellent. Thereafter, it was cured at 200 ° C. for 60 minutes to complete the crosslinking reaction.
Next, the silicon wafer was diced to 6 × 15 mm, and the resulting semiconductor chip was bonded to a 42 alloy lead frame at 200 ° C. for 1 second (1 Kg / cm 2). Thereafter, it was sealed in a 300 mil width SOJ having a LOC structure with an epoxy resin sealing material. Twenty sealed products were allowed to stand at 85 ° C./85% RH for 16 hours, and then subjected to IR flow (240 ° C. × 10 seconds) to examine the number of cracks generated in the package. Met. The measurement results showed good values for all items.
Separately, the photosensitive resin composition was similarly applied onto two silicon wafers and pre-baked, and then heated in an oven at 60 minutes / 200 ° C. to cure the resin. The cure shrinkage at this time was as low as 3%.
Thereafter, the cured film peeled off from the silicon wafer by being immersed in a 2% hydrogen fluoride aqueous solution was thoroughly washed with water and dried, and then the coefficient of linear expansion was measured by thermomechanical analysis (TMA) to be 8.5 × 10 ^−5. A low value of 1 / ° C. was obtained. The cured film was immersed in pure water for 24 hours and the water absorption was measured and found to be 0.2%.

Example 2
5 g of the obtained resin (A-2), 15 g of propylene glycol monoethyl ether, 0.8 g of bisphenol A type polyol type epoxy resin (YD-716), 1,2-naphthoquinone-2 of tris (4-hydroxyphenyl) methane -Diazide-5-sulfonic acid ester 0.5 g Silica (C-1) 0.5 g and Phosphanol RE-610 were mixed in the same manner as in Example 1 to obtain a uniform photosensitive resin composition (2). It was. The photosensitive resin composition (2) was processed and evaluated in the same manner as in Example 1. The residual film rate, water absorption rate, number of cracks generated, and linear expansion coefficient of the obtained resin layer were measured in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the resin components. The resin layer showed good values for all items.

Example 3
The silica (C-1) in Example 1 was evaluated using zircon oxide (C-2: average particle size 10 nm, specific surface area 50 m ² / g). The evaluation results are shown in Table 1 together with the resin component, and all items showed good values.

Example 4
The silica (C-1) in Example 1 was evaluated using aluminum oxide (C-3: average particle size 20 nm, specific surface area 40 m ² / g). The evaluation results are shown in Table 1 together with the resin component, and all items showed good values.

Example 5
Evaluation was performed with 30 parts by weight of silica in Example 3. The evaluation results are shown in Table 1 together with the resin component, and all items showed good values.

<< Example 6 >> Evaluation was performed by increasing the amount of silica added in Example 1 to 80 parts by weight. The evaluation results are shown in Table 1 together with the resin components. The cured film peeled from the silicon wafer was brittle, but the other characteristics were generally good.

Example 7
In Example 1, the evaluation was performed by adding 2 parts by weight of silica. The evaluation results are shown in Table 1 together with the resin component, and the cure shrinkage was 7%, which was slightly large.

《Comparative example》
In Example 1, the evaluation was performed without adding silica. The evaluation results are shown in Table 1 together with the resin component, and the cure shrinkage was as large as 13%.

  INDUSTRIAL APPLICABILITY The present invention is excellent in low stress, low water absorption, adhesion, workability and the like, and is a resin-encapsulated type having a surface protection film and interlayer insulating film of a semiconductor element, particularly a lead-on-chip structure. It is suitably used for a semiconductor device.

FIG. 1 is a cross-sectional view of a resin-encapsulated semiconductor device having a LOC structure of the present invention. FIG. 2 is a cross-sectional view of a resin-encapsulated semiconductor device having a LOC structure according to the prior art.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Insulating film which has adhesive function 2 Semiconductor chip 3 Lead frame 4 Gold wire 5 Sealing resin 6 Adhesive 7 Insulating film

Claims (8)

  Cyclic olefin resin (A) having an acidic group, a photoacid generator (B), a compound (C) having a reactive group capable of binding to the acidic group (A) at a temperature of 130 ° C. or higher, and a filler A photosensitive resin composition comprising (D).   The photosensitive resin composition according to claim 1, wherein the cyclic olefin resin is a polynorbornene resin. The photosensitive resin composition according to claim 1 or 2, wherein the cyclic olefin-based resin (A) having an acidic group contains a repeating unit represented by the formula (1).

[In the formula (1), X is any one of O, CH ₂ and (CH ₂ ) ₂ , and n is an integer from 0 to 5. R ^{1 to} R ⁴ are each a functional group containing a hydrogen, alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, or ester group, a functional group containing a ketone group, a functional group containing an ether group, Any of functional groups containing an acidic group such as a carboxyl group, a phenolic hydroxyl group, -C (OH)-(CF ₃ ) ₂ , -N (H) -S (O) ₂ -CF ₃ may be used. . R ^{1 to} R ⁴ may be different among the repeating monomers, but at least one of R ^{1 to} R ⁴ of all repeating units has an acidic group. ] The photosensitive resin composition according to claim 1 or 2, wherein the cyclic olefin resin (A) having an acidic group contains a repeating unit represented by the formula (2).

[In Formula (2), Y is any of O, CH ₂ , (CH ₂ ) ₂ , Z is any of —CH ₂ —CH ₂ —, —CH═CH—, and l is from 0 to 5 Is an integer. R ^{5 to} R ⁸ are each a functional group containing hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or an ester group, a functional group containing a ketone group, a functional group containing an ether group, Any of functional groups containing an acidic group such as a carboxyl group, a phenolic hydroxyl group, -C (OH)-(CF ₃ ) ₂ , -N (H) -S (O) ₂ -CF ₃ may be used. . R ^{5 to} R ⁸ may be different among the repeating monomers, but at least one of R ^{5 to} R ⁸ of all repeating units has an acidic group. ]   The photosensitive resin composition according to claim 1, wherein the inorganic filler (D) is at least one selected from silica, aluminum oxide, and zirconium oxide.   The photosensitive resin composition according to claim 1, wherein the inorganic filler (D) has an average particle size of 1 nm to 100 nm.   A semiconductor device comprising a resin layer of the photosensitive resin composition according to claim 1 on a circuit element forming surface of a semiconductor chip.   A semiconductor device comprising a resin layer of the resin composition according to claim 1, a semiconductor chip on which a circuit element is formed, and a lead frame, wherein one surface of the resin layer is directly bonded to the semiconductor chip. In addition, a semiconductor device having a lead-on-chip structure, wherein the other surface is directly bonded to the lead frame.

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