JP2006100563A - Semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor device for a wafer level chip size package having a photosensitive resin composition which is excellent in low stress property, solvent resistance, low water absorption property, electrical property or the like, and a connection terminal which uses it and is excellent in high position accuracy and uniformity of a size and a height. <P>SOLUTION: The semiconductor device of a wafer level chip size is constituted of a chip 1 wherein a semiconductor circuit is formed, a device terminal 2 provided to a semiconductor circuit formation side surface of the chip, and a terminal 6 for external circuit substrate junction electrically coupled to the device terminal. The terminal for external circuit substrate junction consists of a projection part 7 formed of an insulator, and a metallic layer 9 provided to the insulator surface. The insulator 5 consists of a resin composition comprising an annular olefine resin (A) with an oxide group, a photooxidant generation agent (B), and a compound (C) having a reaction group which can be coupled to the oxide group of (A) at 130°C or higher. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a semiconductor device. More specifically, a photosensitive resin composition excellent in low stress, solvent resistance, low water absorption, electrical characteristics, adhesion and the like, and an external circuit board excellent in high positional accuracy, size and height uniformity using the same. The present invention relates to a semiconductor device for a wafer level package having a bonding terminal.

Technology related to mounting of semiconductor elements for high-density integrated circuits and the like has greatly changed. For example, in chip size package (CSP) technology, a semiconductor chip is mounted from a method of mounting a semiconductor chip on a ceramic material or a tape material, assembling it as a semiconductor package by resin sealing or the like, and bonding it to a mother board or daughter board. It is replacing the bare chip mounting method that joins motherboards and daughter boards without stopping. In the bare chip mounting method, a wiring board is attached to a semiconductor chip, and this is bonded to a board such as a mother board (hereinafter simply referred to as “external circuit board”) via a solder ball or the like, and cut into an IC chip. There is a so-called wafer level package method in which bump portions are directly formed on the wafer surface at the previous wafer stage, and then cut and bonded to a circuit board. Although there are technical difficulties from the viewpoint of miniaturization, the development focus is on the wafer level chip size packaging method. In the wafer level chip size package method, after forming a plurality of individual semiconductor circuits in a semiconductor circuit formation region of a wafer, an opening through which a device terminal provided for electrically connecting the semiconductor circuit and the outside of the circuit is exposed An insulating layer having a portion is provided. Then, a metal film is formed on the entire surface of the insulating layer using a sputtering apparatus or a vacuum evaporation apparatus. Next, a photosensitive resist is formed on the surface of the wiring part by a spin coater so as to have a thickness of 20 to 150 μm. Then, exposure is performed using a predetermined mask, development is performed, and an opening is provided at a position to be an external circuit board connection terminal (hereinafter also referred to simply as “connection terminal”), and the opening is formed by electrolytic plating. Fill with plating metal. The filling height in this case becomes the height of the connection terminal. At that time, the metal thin film provided on the insulating layer acts as a cathode during plating. Thereafter, the photosensitive resist is peeled off to obtain connection terminals made of metal protrusions. Further, the metal layer as a base is etched to form a wiring layer for connecting device terminals and connection terminals on the surface of the insulating layer, and divided into chips to obtain a wafer level package. In some cases, only the connection terminal is formed on the surface of the insulator layer, and this is connected to the device terminal with a fine wire or a conductive adhesive, and then the metal is raised on the terminal by a plating method. However, if an attempt is made to form a connection terminal by electroplating according to the above method, the height is as high as 20 to 100 μm, and thus it takes a long plating time of 1 to 5 hours and the semiconductor package manufacturing cost is high. . In addition, since the current density distribution is difficult to be uniform between the individual openings, it is inevitable that the height of the obtained bumps varies greatly, and as a result, unconnected portions are generated when connecting to the external circuit board. become. In addition, if there is dirt or oxide film on the base metal when forming the connection terminal, this effect weakens the adhesion of the wiring layer connecting the connection terminal and the device terminal to the insulating layer, resulting in mechanical reliability and electrical bondability. Cause problems. Specifically, there is a problem of poor bonding between a semiconductor chip and an external circuit board in semiconductor mounting.
In a wafer level chip size package, it is described in Patent Document 1 that a connection layer is formed by providing a metal layer on the surface of a protrusion formed of an insulating layer. Further, the insulator has low stress, solvent resistance, It has been an urgent task to provide low water absorption and electrical characteristics.
JP 2001-298120 A

  The present invention overcomes such drawbacks of the prior art and is a photosensitive resin composition excellent in low stress, solvent resistance, low water absorption, electrical properties, etc., and high positional accuracy, size and It is an object of the present invention to provide a semiconductor device for a wafer level chip size package having a connection terminal excellent in height uniformity and the like.

Such an object is achieved by the present invention described in the following [1] to [12].
[1] A wafer comprising a chip on which a semiconductor circuit is formed, device terminals provided on the surface of the chip on the semiconductor circuit forming side, and external circuit board bonding terminals electrically coupled to the device terminals In the level chip size semiconductor device, the external circuit board bonding terminal is composed of a protrusion made of an insulator and a metal layer provided on the surface of the insulator, and the insulator has a cyclic olefin resin (A) having an acidic group; A semiconductor device comprising a resin composition comprising 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.
[2] A protective film and an insulating layer are sequentially provided on the surface of the semiconductor circuit forming side excluding the device terminal portion provided on the surface of the semiconductor circuit forming side, and an external circuit board bonding terminal is provided on the insulating layer. And the device terminal and the metal layer of the external circuit board bonding terminal are electrically coupled to each other.
[3] A wiring layer for electrically coupling the device terminal and the metal layer of the external circuit board bonding terminal is provided on the insulating layer, and at least the metal layer of the external circuit board bonding terminal is exposed, The semiconductor device according to [1] or [2], wherein the wiring layer and the device terminal are covered with a sealing material layer.
[4] The semiconductor device according to [1], [2] or [3], wherein a solder ball is mounted on the surface of the metal layer of the external circuit board bonding terminal or a plating layer is provided.
[5] The semiconductor device according to any one of [1] to [4], wherein the cyclic olefin resin is a polynorbornene resin.
[6] The semiconductor device according to any one of [1] to [5], wherein the cyclic olefin resin (A) having an acidic group includes a repeating unit represented by the formula (1).

[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。]
［７］ 酸性基を有する環状オレフィン樹脂（Ａ）が式（２）で示される繰り返し単位を含むものである［１］〜［６］項のいずれか１項に記載の半導体装置。

[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 carboxyl group, 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. ]
[7] The semiconductor device according to any one of [1] to [6], wherein the cyclic olefin resin (A) having an acidic group includes a repeating unit represented by the formula (2).

[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。]

[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. ]

[8] The metal layer is composed of at least two layers, and the metal layer provided on the surface on the insulating layer side is formed of nickel, cobalt, chromium, titanium, vanadium, or an alloy containing these as a main component. The semiconductor device according to any one of [1] to [7].
[9] The semiconductor device according to any one of [2] to [8], wherein the insulating layer is made of a photosensitive resin.
[10] The semiconductor device according to item [9], wherein the photosensitive resin is composed of at least one of photosensitive polyimide, photosensitive polybenzoxazole, photosensitive epoxy, and photosensitive cyclic olefin resin.
[11] The semiconductor device according to any one of [3] to [10], wherein the sealant layer is made of a photosensitive resin.
[12] The semiconductor device according to [3] or [11], wherein the photosensitive resin is composed of at least one of photosensitive polyimide, photosensitive polybenzoxazole, photosensitive epoxy, and photosensitive cyclic olefin resin.

  According to the present invention, in the wafer level chip size package, since a connection terminal obtained by providing a metal layer on the surface of the protrusion formed by the insulating layer is employed, there is no need for manufacturing, and the positional accuracy and size of the terminal are reduced. Excellent variation and height uniformity. In addition, by using a resin composition with excellent low stress resistance, solvent resistance, low water absorption, electrical properties, etc. for the insulator, stress generated between the chip and the external circuit board can be relaxed, and A highly reliable semiconductor device can be provided.

    A semiconductor device of the present invention includes a chip on which a semiconductor circuit is formed, a device terminal provided on the surface of the chip on the semiconductor circuit forming side, a protrusion that is electrically coupled to the device terminal and is made of an insulator, and This is a wafer level chip size semiconductor device composed of external circuit board bonding terminals (connection terminals) made of a metal layer provided on the insulator surface. Next, the semiconductor device of the present invention having such a configuration will be described with reference to the accompanying drawings. 1 and 2 are cross-sectional views showing different configurations of the semiconductor device of the present invention. FIG. 1 is an example in which solder balls are mounted on the surface of the connection terminal, and FIG. This is an example in which a plating layer is provided. A protection having an opening 3 on a silicon chip 1 in which a semiconductor circuit is formed in a semiconductor circuit formation region, so that a device terminal 2 provided to electrically connect the semiconductor circuit and the external circuit is exposed. A membrane 4 is provided. An insulating layer 5 is provided on the protective film 4, and the insulating layer 5 is provided with an opening 8 through which the device terminal 2 is exposed. On the insulating layer 5, a projection 7 made of an insulator constituting the connection terminal 6 is provided at a position corresponding to an electrode (not shown) of the external circuit board. The surface of the projection 7 is covered with a metal layer 9 to form a connection terminal 6, and the connection terminal 6 and the device terminal 2 covered with the metal layer 9 are electrically coupled by the metal layer 9 constituting the wiring. ing. The material of the insulating layer 5 is not particularly limited as long as it stably supports the metal layer 9 and substantially secures electrical insulation and heat resistance, but a resin material that is inexpensive and excellent in workability can be used. Widely used. Such materials include polyester resins, epoxy resins, urethane resins, polystyrene resins, polyethylene resins, polyimide resins, polybenzoxazole resins, acrylonitrile-butadiene-styrene (ABS) copolymer resins, polycarbonate resins. Examples thereof include thermosetting resins and thermoplastic resins such as resins, silicone resins, fluorine resins, and cyclic olefin resins. Moreover, as a material which comprises the projection part 7, the cyclic olefin resin excellent in low stress property, electrical insulation, solvent resistance, and low water absorption is mentioned. In addition, although it is necessary to form the opening part 8 in the insulating layer 5, and the insulator on it, the projection part 7 is used, it is easy to use the photolithographic method as a processing method, and high position accuracy and high dimension. Since it is easy to obtain accuracy, it is desirable to use a photosensitive resin. Preferred examples of the resin include photosensitive polyimide, photosensitive polybenzoxazole, photosensitive epoxy resin, photosensitive cyclic olefin resin for the insulating layer 5, and photosensitive cyclic olefin resin for the protrusion 7. Further, a protrusion-shaped object may be separately prepared in advance and installed on the insulating layer 5 with an adhesive to form the protrusion 7. For example, the protrusion-shaped object may be fixed by heat fusion. However, this method may not always be sufficient when higher positional accuracy and higher dimensional accuracy are required. Moreover, after forming the insulating layer 5, the method of forming the projection part 7 in a desired position by printing methods, such as a screen printing method, may be used. The appropriate height of the protrusion and the thickness of the insulating layer are determined from the insulating effect, the effect of the sealing resin described later, the required height of the chip size package, etc., and it is preferable to increase the thickness unnecessarily. Absent. The shape of the protrusion 7 is not particularly limited, but the surface needs to have the solder ball 10 mounted stably, and it is desirable to have a flat portion or a spherical recess.

  Next, the metal layer 9 is basically formed using at least one kind of method such as sputtering, vacuum deposition, electroless plating, electrolytic plating, and the wiring layer is formed of the metal layer 9. It is produced by etching. In the present invention, the metal layer 9 is preferably composed of at least two layers. However, when copper or copper alloy having good conductivity is used, the adhesion strength with the insulating layer is relatively small, and a sufficient wiring layer cannot be obtained. In the example of FIG. 1, it has a three-layer structure, and includes an intermediate layer 11, a seed layer 12, and a base layer 13. Based on this example, the case where the metal layer 9 is composed of multiple layers will be described. First, the intermediate layer 11 is provided on the entire surface of the insulating layer 5. The intermediate layer 11 is made of a metal having a relatively strong adhesion to the insulating layer 5 such as chromium, nickel, titanium, vanadium, or an alloy containing these as a main component. This is because the seed layer 12 serving as a cathode or wiring when the base layer 13 is provided by electroplating is made of gold, silver, copper, aluminum, indium, or an alloy containing these as a main component. When it is directly formed on the insulating layer 5, the adhesion strength between the obtained metal layer 9 and the insulating layer 5 is relatively small, but by providing the intermediate layer 11, the metal layer 9 having a high adhesion strength is obtained. Because it will be possible.

  Since the intermediate layer 11 is provided directly on the surface of the insulating layer 5, it is provided by an electroless plating method, or a dry film forming method such as a sputtering method or a vapor deposition method, but the thickness is preferably 10 to 100 nm. If the film is too thin, a uniform film cannot be obtained. If the film is too thick, not only a long film formation time is required, but also a dense and uniform intermediate layer 11 cannot be obtained. For example, when an intermediate layer is obtained by a dry film formation method, the internal stress increases as the thickness of the obtained intermediate layer increases, and when the film is formed with chromium, the internal stress is usually increased when the film thickness exceeds 5 μm. The film peels off. Moreover, when a thick film is formed by electroless plating, the obtained film does not become dense. When the metal layer 9 has two layers, the base layer 13 is provided directly on the intermediate layer 11, but the base layer 13 has the electrical characteristics after the wiring is formed, the solder ball 10 and the plating layer for bonding. Copper or a copper alloy is preferably used because of its bondability with Fifteen. In the case of three layers, it is easy to form the seed layer 12 by a dry film forming method, but in this case, the thickness of the seed layer 12 is preferably 50 nm to 1 μm. For the reasons described above, even if the seed layer 12 is too thin or thick, a uniform film is not formed, and when the base layer is formed by electroplating, a sufficient function as a cathode is not exhibited. As described above, the base layer 13 may be composed of a conductive material such as copper or copper alloy. The thickness of the base layer 13 is such that the electrical characteristics of the finally obtained wiring are desired, and an electroplating method is used. It is efficient and preferable. The metal layer 9 thus obtained is etched by a photolithographic method to remove the metal layer 9 other than the wiring portion, the protrusion surface, and the device terminal surface portion. The protrusion 7 provided with the metal layer on the surface serves as the connection terminal 6 described above. Since the solder ball 10 is mounted on the surface of the terminal 6, it is preferable to have a planar shape or a concave shape. Next, the sealant layer 14 is provided so that the wiring layer and the surface portion of the device terminal 2 are not exposed and at least the surface of the connection terminal 6 is exposed. The semiconductor package of FIG. 1 has a solder ball 10 mounted on the surface of an external circuit board terminal, and FIG. 2 has a plating layer 15 provided. As the material of the plating layer 15, it is common to use at least one of gold, silver, palladium, nickel, solder and the like. As shown in FIG. 1, a solder ball 10 mounted is a BGA (Ball Grit Array) structure, and a plating layer 15 is provided as an LGA (Land Grit Array) structure as shown in FIG. Become.

  The material of the sealant layer 14 is not particularly limited as long as it can stably protect the wiring layer and the device terminal 2 and can substantially ensure electrical insulation and heat resistance. In actual production, polyester resin, epoxy resin, urethane resin, polystyrene resin, polyethylene resin, polyimide resin, polybenzoxazole resin, acrylonitrile-butadiene-styrene (ABS), which are inexpensive and excellent in workability ) Thermosetting resins or thermoplastic resins such as copolymer resins, polycarbonate resins, silicone resins, fluorine resins, and cyclic olefin resins can be used. In order to expose at least the surface of the connection terminal 6 neatly, the resin is photosensitive. For example, a sealant layer is provided on the entire surface on the wiring side so as to be buried in the connection terminal 6. Half etching is performed until the surface of the connection terminal 6 is exposed. Preferred resins are photosensitive polyimide, photosensitive polybenzoxazole, photosensitive epoxy resin, and photosensitive cyclic olefin resin. The effect of protecting with the sealing agent is not only to prevent damage to the wiring layer and the like, but also to prevent the semiconductor circuit formed on the silicon wafer 1 from being damaged by α rays, and to an external circuit board. In mounting, there is also an effect that the wiring layer is not contaminated and deteriorated by the flux attached to the solder. The thickness of the sealant layer may be a thickness sufficient to obtain these effects, and it is not preferable to increase the thickness unnecessarily. Specifically, an optimum value may be obtained as appropriate according to the composition and properties of the resin used. The electrical test / burn-in test of the semiconductor circuit formed on the silicon wafer 1 can be easily performed by directly applying a probe to the connection terminal 6. In the present invention, a wafer level chip size package of the present invention can be efficiently obtained by creating a plurality of packages at once using a wafer and dividing them.

  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.

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 alkynyl groups such as vinyl, allyl, butynyl, cyclohexyl groups, etc. include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl groups, etc., and specific examples of aryl groups include phenyl, 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 , —N (H) —S (O) ₂ —CF ₃ may be mentioned, respectively, but the present invention is not 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.

[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。]

[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 carboxyl group, 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 0.002 to 0.01 mol per gram of polymer. More preferably, it is 0.003-0.01 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- Nyl-2-norbornene and the like having an alkoxysilyl group include dimethylbis ((5-norbornen-2-yl) methoxy)) silane and the like having a silyl group such as 1,1,3,3, Examples of those having an aryl group such as 5,5-hexamethyl-1,5-dimethylbis ((2- (5-norbornen-2-yl) ethyl) trisiloxane) include 5-phenyl-2-norbornene, 5-naphthyl- Examples of those having an aralkyl group such as 2-norbornene and 5-pentafluorophenyl-2-norbornene include 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 5-pentafluorophenylmethane-2-norbornene, 5- (2-Pentafluorophenylethyl) -2-norbornene, 5- (3-Pentafluoro (Rhophenylpropyl) -2-norbornene and the like having an alkoxysilyl group include 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-trimethylsilyl Examples of those having a hydroxyl group, an ether group, an ester group, an acryloyl group or a methacryloyl group, such as methyl ether-2-norbornene, include 5-norbornene-2-methanol and this alkyl ether, acetic acid 5-norbornene-2-methyl ester , Propionic acid 5-norbornene 2-methyl ester, butyric acid 5-norbornene-2-methyl ester, valeric acid 5-norbornene-2-methyl ester, caproic acid 5-norbornene-2-methyl ester, caprylic acid 5-norbornene-2-methyl ester, caprin 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- Cylester, 5-norbornene-2-carboxylic 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 Nate, 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, (meth) 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) acrylic acid 5-norbornene-2-hexyl ester, (meth) acrylic acid 5-norbornene-2-octyl ester, (meth) acrylic acid 5-norbornene-2-decyl ester, etc. As those having an epoxy group, 5-[(2,3-epoxypropoxy) methyl] -2-norbornene and the like, and those comprising a tetracyclo ring as 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.

  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.

The present invention will be further described below using examples.
Example 1
<< 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 copolymer (A-1) is given.
All glass equipment was dried at 60 ° C. under 0.1 Torr for 18 hours. After that, the glass device was moved into a glove box in which the internal oxygen concentration and humidity were 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 73 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 = 50/50 copolymer Examples of the ring-opening metathesis copolymer (A-2) will be given.
All glass equipment was dried at 60 ° C. under 0.1 Torr for 18 hours. After that, the glass device was moved into a glove box in which the internal oxygen concentration and humidity were 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 norbornene Carboxylic acid trimethyl ester (99.1 g, 0.55 mol), 1-hexene (368 g, 2.2 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. 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
5 g of the obtained resin (A-1), 15 g of propylene glycol monoethyl ether, 0.8 g of bisphenol A type polyol type epoxy resin (YD-716, manufactured by Tohto Kasei Co., Ltd.)
And 0.5 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester of tris (4-hydroxyphenyl) methane was mixed to obtain a uniform photosensitive resin composition (1).
Insulating over the entire surface of a 6-inch diameter silicon wafer having 144 semiconductor circuits in the semiconductor circuit formation region, 54 device terminals for each semiconductor circuit, and a protective film provided on the circuit side surface other than these device terminals As a layer, positive photosensitive polybenzoxazole (product name CRC-8320: manufactured by Sumitomo Bakelite Co., Ltd.) was applied with a spin coater and pre-baked at 120 ° C. for 4 minutes with a hot plate to obtain a 7 μm thick coating film. Exposure (g-line stepper: NSR1505G3A 500mJ / cm ² ) from Nikon, development (developer: NMD-3: TMAH (tetramethylammonium hydroxy) manufactured by Tokyo Ohka Kogyo Co., Ltd.) D) 2.38% 20 sec paddle x 2), rinsed (pure water), and then cured in a nitrogen atmosphere at 150 ° C for 30 minutes + 320 ° C for 30 minutes. Further, in order to form projections for joining terminals thereon, the photosensitive resin composition (1) obtained above as an insulating layer was applied to the entire surface of a 6-inch diameter silicon wafer with a spin coater, and at 130 ° C. with a hot plate. Pre-baking was performed in 4 minutes to obtain a coating film having a thickness of 30 μm. Exposure (I-line stepper: Nikon NSR2244i 1000mJ / cm ² ), development (developer: 2.38% tetramethylammonium hydroxide aqueous solution), rinse (isopropyl alcohol) and insulation layer using the desired mask on the insulating layer surface Was etched to obtain a protrusion for a junction terminal required for each semiconductor circuit, and the insulator layer on the device terminal was also removed to expose the device terminal. Thereafter, it was cured at 160 ° C. for 30 minutes in a nitrogen atmosphere.

Next, a metal layer was formed on the surface of the insulating layer provided on the silicon wafer using an RF sputtering apparatus (manufactured by Shinko Seiki Co., Ltd.). In addition, the kind of metal used the chromium layer of thickness 300mm as an intermediate | middle layer, and used the copper layer 1000mm thick as a seed layer. As film forming conditions, an ultimate true pressure of 5 × 10 ⁻⁴ Pa, a sputtering pressure of 6.7 × 10 ⁻¹ Pa, and an Ar flow rate of 20 SCCM were employed by sputtering.
Next, a copper layer having a thickness of 15 μm was provided by an electrolytic copper plating method, and this was used as a base layer. At this time, the plating solution composition was 28 g / l copper, 200 g / l sulfuric acid, 70 mg / l chloride ion, and 25 ml / l additive (manufactured by Microfab Cu "B" EEJA (manufactured by Nippon Electroplating Engineers)). The plating conditions were a plating temperature of 28 ° C. and a current density of 3 A / dm ² .

Subsequently, a positive photoresist (manufactured by Tokyo Ohka Kogyo Co., Ltd., PMERP-LA900PM) was applied onto the wafer by spin coating so as to have a film thickness of 10 to 15 microns. This was cured in an oven at 110 ° C. for 6 minutes, and the resulting resist film was exposed using a wiring mask, and then developed using a developer (manufactured by Tokyo Ohka Kogyo Co., Ltd., P-7G).
Next, the seed layer and base layer of the metal layer exposed with the cupric chloride solution are etched, and then the resist is stripped with a stripping solution (PS made by Tokyo Ohka Kogyo Co., Ltd.), and then the intermediate layer is coated with a desmear solution (made by Magdamit) Then, a connection terminal and a wiring layer that electrically connects the connection terminal and the device terminal were obtained.

After that, photosensitive polybenzoxazole (trade name: CRC-8320, manufactured by Sumitomo Bakelite Co., Ltd.) is applied to the entire surface on the insulating layer side so that the thickness of the surface is uniform from the silicon wafer surface and the connection terminals are embedded. Then, a sealant layer is provided and then exposed and developed to half-etch the sealant layer using tetramethylammonium hydroxide (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to expose the tip of the connection terminal. It was. After curing in a nitrogen oven, flux was applied to the tip of the connection terminal, solder balls were mounted, reflowed, and the wafer was divided to obtain 144 wafer level chip size packages of the type shown in FIG.
Thereafter, these wafer level chip size packages were mounted on an external circuit board, subjected to a temperature cycle test, and then the conduction state and mechanical bonding were examined. As a result, it was found that there was no continuity failure and the fracture occurred on the base of the solder ball, and it was normally joined.

(Example 2)
5 g of the obtained resin (A-1), 15 g of propylene glycol monoethyl ether, 0.8 g of bisphenol A type polyol type epoxy resin (YD-716, manufactured by Tohto Kasei Co., Ltd.) and tris (4-hydroxyphenyl) methane 0.5 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester was mixed to obtain a uniform photosensitive resin composition (2).
By using this photosensitive resin composition (2), a wafer level chip size package was prepared in the same manner as in Example 1. And these were mounted in the external circuit board by the method similar to Example 1, and after conducting the temperature cycle test, the conduction | electrical_connection state and mechanical joining were investigated. As a result, no conduction failure was confirmed, and the fracture was also caused by the base of the solder ball, and it was confirmed that the soldering was normally performed.

(Comparative Example 1)
Insulating over the entire surface of a 6-inch diameter silicon wafer having 144 semiconductor circuits in the semiconductor circuit formation region, 54 device terminals for each semiconductor circuit, and a protective film provided on the circuit side surface other than these device terminals As a layer, negative photosensitive polyimide (product name: CRC-6087, manufactured by Sumitomo Bakelite Co., Ltd.) was applied with a spin coater and dried with a dryer at 80 ° C. for 1 hour to obtain a 40 μm coating film. Each semiconductor layer is half-etched by exposure (g-line stepper 1500mJ / cm ² ), development (developer: cyclopentanone), rinsing (propylene glycol monomethyl ether acetate) using the desired mask on the surface of the insulation layer A protrusion for a junction terminal required for the circuit was obtained.

Next, in order to remove the insulator layer on the device terminal, exposure and development were performed again through a mask, and the insulator on the device terminal was removed in the same manner as described above to expose the device terminal. Thereafter, it was cured in a nitrogen atmosphere at 150 ° C. for 30 minutes + 350 ° C. for 60 minutes.
Next, a metal layer was formed on the surface of the insulating layer provided on the silicon wafer using an RF sputtering apparatus. In addition, the kind of metal used the chromium layer of thickness 300mm as an intermediate | middle layer, and used the copper layer 1000mm thick as a seed layer. The base layer and the wiring layer were manufactured in the same manner as in Example 1.

After that, apply negative photosensitive polyimide (trade name CRC-6087, manufactured by Sumitomo Bakelite Co., Ltd.) over the entire surface of the insulating layer so that the thickness of the surface is uniform from the silicon wafer surface and the connection terminals are embedded. Then, a sealant layer was provided, and then the sealant layer was half-etched by exposure and development (developer: cyclopentanone) to expose the tip of the connection terminal. After curing in a nitrogen oven, flux was applied to the tip of the connection terminal, solder balls were mounted, reflowed, and the wafer was divided to obtain 144 wafer level chip size packages of the type shown in FIG.
Thereafter, these wafer level chip size packages were mounted on an external circuit board, subjected to a temperature cycle test, and then the conduction state was examined. As a result, conduction failure was observed. Above this, when a cross section of the level package was observed, cracks were found in the solder balls.

  The present invention has a photosensitive resin composition excellent in low stress, solvent resistance, low water absorption, electrical characteristics, and the like, and a connection terminal excellent in high positional accuracy, size and height uniformity using the same. It is suitably used for a semiconductor device for wafer level chip size package.

It is the example of this invention which mounted the solder ball on the surface of a connection terminal. It is the example of this invention which provided the plating layer in the connection terminal surface.

Explanation of symbols

1 −−− Silicon chip 2−− Device terminal 3−− Opening 4−− Protective film 5−− Insulating layer 6 −−− Connection terminal 7 −−− Projection 8 −−− Opening 9− --- Metal layer 10 --- Solder ball 11 --- Intermediate layer 12 --- Sheet layer 13 --- Base layer 14 --- Sealant layer 15 --- Plating layer

Claims (12)

Wafer level chip size comprising a chip on which a semiconductor circuit is formed, a device terminal provided on the semiconductor circuit forming side surface of the chip, and an external circuit board bonding terminal electrically coupled to the device terminal In this semiconductor device, the external circuit board bonding terminal is composed of a protrusion made of an insulator and a metal layer provided on the surface of the insulator, and the insulator has a cyclic olefin resin (A) having an acidic group and photoacid generation. A semiconductor device comprising a resin composition comprising an agent (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 protective film and an insulating layer are sequentially provided on the semiconductor circuit forming side surface excluding a device terminal portion provided on the semiconductor circuit forming side surface, and an external circuit board bonding terminal is provided on the insulating layer, and the device The semiconductor device according to claim 1, wherein the terminal and the metal layer of the external circuit board bonding terminal are electrically coupled. A wiring layer that electrically couples the device terminal and the metal layer of the external circuit board bonding terminal is provided on the insulating layer, and at least the metal layer of the external circuit board bonding terminal is exposed, and the wiring layer and The semiconductor device according to claim 1, wherein the device terminal is covered with a sealing material layer. 4. The semiconductor device according to claim 1, wherein solder balls are mounted on the surface of the metal layer of the external circuit board bonding terminal or a plating layer is provided. The semiconductor device according to claim 1, wherein the cyclic olefin resin is a polynorbornene resin. The semiconductor device according to claim 1, wherein the cyclic olefin resin (A) having an acidic group includes 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 carboxyl group, 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 semiconductor device according to any one of claims 1 to 6, 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 metal layer is composed of at least two layers, and the metal layer provided on the surface on the insulating layer side is formed of nickel, cobalt, chromium, titanium, vanadium, or an alloy containing these as a main component. The semiconductor device of any one of -7. The semiconductor device according to claim 2, wherein the insulating layer is made of a photosensitive resin. The semiconductor device according to claim 9, wherein the photosensitive resin is composed of at least one of photosensitive polyimide, photosensitive polybenzoxazole, photosensitive epoxy, and photosensitive cyclic olefin resin. The semiconductor device according to claim 3, wherein the sealant layer is made of a photosensitive resin. The semiconductor device according to claim 3 or 11, wherein the photosensitive resin is composed of at least one of photosensitive polyimide, photosensitive polybenzoxazole, photosensitive epoxy, and photosensitive cyclic olefin resin.

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