TWI486704B - Photosensitive resin composition and semiconductor device - Google Patents

Description

Photosensitive resin composition and semiconductor device

The present invention relates to a photosensitive resin composition using a cyclic olefin resin and a semiconductor device produced using the same.

Conventionally, in recent years, due to factors such as high integration and enlargement of semiconductor components, thinning and miniaturization of sealing resin packages, and shifting to surface mounting by reflow, the requirements for heat cycle resistance and thermal shock resistance are required. Significant improvement. The surface protective film and the interlayer insulating film of such a semiconductor element are made of a polyimide resin having excellent heat resistance and excellent electrical properties, mechanical properties, and the like.

On the other hand, the protective film and the insulating film on the semiconductor element are easy to perform fine processing such as opening of a via hole for wiring the semiconductor element, and the like. The technique in which the polyimide resin itself imparts photosensitivity. For example, the photosensitive polyimide resin has the following formula (4) and the like.

[Chemical 1]

Further, recently, a positive photosensitive resin composition which can be developed by using an aqueous alkali solution has been developed, for example, it is revealed that polybenzoic acid is derived from polybenzobenzene. A positive photosensitive resin composition comprising an azole precursor and a diazonium compound (see, for example, Patent Document 1). This has high heat resistance, excellent electrical properties, and fine workability, and can be used not only as a wafer coating but also as a resin for interlayer insulation. The development mechanism of the positive photosensitive resin composition is that the diazonium compound in the unexposed portion is insoluble in the alkaline aqueous solution because the diazonium compound is chemically changed by exposure, and thus the positive photosensitive resin composition is The unexposed portion is kept in a state of being insoluble in the alkaline aqueous solution, and the exposed portion is soluble in the alkaline aqueous solution, so that the solubility between the exposed portion and the unexposed portion is poor, and the coating film pattern having only the unexposed portion can be produced. .

However, in recent years, the speed of high-speed semiconductors has evolved, and wiring has evolved to use copper. Therefore, a photosensitive resin composition having excellent adhesion to copper has been developed. For example, a photosensitive resin composition comprising a cyclic olefin resin and an organic ruthenium compound containing a sulfur atom is disclosed (for example, see Patent Document 2). Although this material has excellent adhesion to copper, on the other hand, during the storage at normal temperature, there is a problem that the adhesion of the development step is lowered. In this case, it is desired to develop a photosensitive resin composition which is excellent in adhesion and maintains stability at room temperature.

[Advanced technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Special Fair No. 1-468686

Patent Document 2: Japanese Patent No. 4170277

An object of the present invention is to provide a photosensitive resin composition which is excellent in storage stability at room temperature and has excellent adhesion properties after curing.

Such an object is achieved by the present invention described in the following [1] to [18].

[1]

A photosensitive resin composition comprising a cyclic olefin resin (A), an organic ruthenium compound (B1) represented by the following general formula (1), and a sulfur-containing organic ruthenium compound (B2):

[Chemical 2]

(R ² O) ₃ ─Si─R ¹ ─Si─(OR ² ) ₃ (1)

(In the formula (1), R ¹ is an alkylene group having 5 to 30 carbon atoms or an organic group having at least one aromatic ring; and R ² is an alkyl group having 1 to 10 carbon atoms.).

[2]

The photosensitive resin composition according to the above [1], wherein the sulfur-containing organic ruthenium compound (B2) is an organic ruthenium compound represented by the following general formula (2) and a general formula (3): One or more selected from the group consisting of organic hydrazine compounds;

[Chemical 3]

(In the formula (2), R ³ and R ⁴ are an alkyl group having 1 to 10 carbon atoms; and R ⁵ and R ⁶ are linear or branched alkyl groups, and have a carbon number of 1 to 10; k And l is 0 or 1; m is an integer from 1 to 10; n is 0, 1 or 2.).

[Chemical 4]

(In the formula (3), R ⁷ and R ⁸ are an alkyl group having 1 to 10 carbon atoms; p is an integer of 0 to 10; q is 0, 1 or 2.)

[3]

The photosensitive resin composition as described in [1] or [2], wherein the ratio of the amount of (B2) to the organic cerium compound (B1) is [1 (B1) by weight / (B2) by weight). 10 or less.

[4]

The photosensitive resin composition according to any one of the above aspects, wherein the compounding amount of the organic cerium compound (B1) is 1 part by weight based on 100 parts by weight of the cyclic olefin resin (A). More than 10 parts by weight or less.

[5]

The photosensitive resin composition as described in any one of the above-mentioned [1], wherein the R ¹ of the above organic sulfonium compound (B1) is an alkylene group having 6 to 8 carbon atoms.

[6]

The photosensitive resin composition of any one of the above-mentioned cyclic olefin resin (A) is a cyclic olefin resin having a structural unit represented by the following general formula (6). :

[Chemical 5]

(In the formula (6), X is an oxygen atom (-O-) or a methylene group (-CH ₂ -). r is an integer of 0 to 5. R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group The R ¹¹ to R ¹⁴ systems may be the same or different.).

[7]

The photosensitive resin composition of the above-mentioned cyclic olefin resin (A), wherein the structural unit represented by the above general formula (6) is present in an amount of 10 to 100 mol% based on the total structural unit.

[8]

The photosensitive resin composition of any one of [1] to [7], wherein the cyclic olefin resin (A) is a cyclic olefin resin (A-1) having an acid polymerizable functional group, and Further, it contains a photoacid generator (C).

[9]

The photosensitive resin composition according to the above [8], wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is one of the structural units represented by the following general formula (6). Or a cyclic olefin resin having two or more kinds, and at least one of R ¹¹ to R ¹⁴ is a structural unit of a functional group having an epoxy group, and is a total structural unit of 5 to 95 mol %;

[Chemical 6]

(In the formula (6), X is an oxygen atom (-O-) or a methylene group (-CH ₂ -). r is an integer of 0 to 5. R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group The R ¹¹ to R ¹⁴ systems may be the same or different.).

[10]

The photosensitive resin composition according to the above [8], wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is a structural unit represented by the following general formula (7-1). The structural unit configuration shown in the following general formula (7-2);

[Chemistry 7]

[化8]

(In the formulae (7-1) and (7-2), R ²¹ to R ²⁷ are hydrogen, alkyl, alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, having an ester Any of a functional group having a ketone group, a functional group having a ketone group, or a functional group having an ether group.

[11]

The photosensitive resin composition according to the above [8], wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is a structural unit represented by the following general formula (8-1), and the following a structural unit represented by the general formula (8-2) and a structural unit represented by the following general formula (8-3);

[Chemistry 9]

[化10]

[11]

(In the formulae (8-1), (8-2) and (8-3), R ³¹ to R ⁴⁰ are hydrogen, alkyl, alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, Any one of an alkoxyalkyl group, a functional group having an ester group, a functional group having a keto group, or a functional group having an ether group. s is an integer of 0 to 5.).

[12]

The photosensitive resin composition according to the above [11], wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is a structural unit represented by the following formula (9-1), and the following formula (9) -2) the structural unit shown and the structural unit shown in the following formula (9-3);

[化12]

[Chemistry 13]

[Chemistry 14]

[13]

The photosensitive resin composition according to the above [10], wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group has a ratio of the structural unit represented by the general formula (7-1). It is 20~80 mol% of the total structural unit.

[14]

The photosensitive resin composition according to the above [11], wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group has a ratio of the structural unit represented by the general formula (8-1). It is 20~80 mol% of the total structural unit.

[15]

The photosensitive resin composition according to the above [12], wherein the ratio of the structural unit represented by the general formula (9-1) in the cyclic olefin resin (A-1) having the acid polymerizable functional group is It is 20~80 mol% of the total structural unit.

[16]

The photosensitive resin composition according to any one of the above aspects, wherein the cyclic olefin resin (A) is reduced by the following general formula (5). a cyclic olefin resin obtained by polymerizing one or more of the ethylenic cyclic olefin monomers;

[化15]

(In the formula (5), any one of an X-based oxygen atom (-O-) or a methylene group (-CH ₂ -). r is an integer of 0 to 5. R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group The R ¹¹ to R ¹⁴ systems may be the same or different.).

[17]

The photosensitive resin composition as described in any one of [1] to [7], wherein the cyclic olefin resin (A) is a cyclic olefin resin (A-2) having a photopolymerizable functional group.

[18]

The photosensitive resin composition according to the above [17], wherein the cyclic olefin resin (A-2) having a photopolymerizable functional group is one of the structural units represented by the following general formula (6) or cyclic olefin resin composed of two or more, and R ¹¹ ~ R ¹⁴ in the presence of at least one structural unit to those of the alkenyl or alkynyl group ratio, lines 20 to 60 mole% of the total of the structural unit;

[Chemistry 16]

(In the formula (6), X is an oxygen atom (-O-) or a methylene group (-CH ₂ -). r is an integer of 0 to 5. R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group The R ¹¹ to R ¹⁴ systems may be the same or different.).

[19]

The photosensitive resin composition as described in any one of [1] to [18] further containing an antioxidant (D).

[20]

A semiconductor device produced by using the photosensitive resin composition according to any one of [1] to [19].

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in storage stability at room temperature and has excellent adhesion properties after curing.

The photosensitive resin composition of the present invention contains a cyclic olefin resin (A), an organic cerium compound (B1) represented by the general formula (1), and a photosensitive resin composition of the sulfur-containing organic cerium compound (B2). .

[化17]

(R ² O) ₃ -Si-R ¹ -Si-(OR ² ) ₃ (1)

Therefore, the photosensitive resin composition of the present invention provides a photosensitive resin composition which is excellent in storage stability at room temperature and has excellent adhesion properties after curing.

In the photosensitive resin composition of the present invention, for example, a place (exposed portion) irradiated with actinic rays is insolubilized or insoluble, and only a portion (unexposed portion) that is not irradiated with actinic rays is selectively selected. When the developer is dissolved and removed, the negative photosensitive property of the patterned resin film can be formed, or the place where the actinic radiation is irradiated (exposed portion) can be easily dissolved, and only the portion can be selectively used. Any mechanism such as positive photosensitive property in which a patterned resin film can be formed by dissolving and removing can be applied. Among them, the negative sensitization mechanism can be applied to the cross-linking reaction form as follows. The crosslinking reaction or the polymerization reaction of the exposed portion is performed by irradiation with actinic rays, irradiation with actinic rays, and subsequent heat curing. The exposed portion where the crosslinking reaction or the polymerization reaction has been carried out is not easily dissolved in the developing solution, and on the other hand, only the unexposed portion in which the crosslinking reaction or the polymerization reaction is not carried out can be easily dissolved in the developing solution, and thus development can be performed. A relief pattern of the exposed portion is obtained. Therefore, examples of the form of the photosensitive resin composition of the present invention include the following examples.

(I) contains a cyclic olefin resin (hereinafter also referred to as "cyclic olefin resin (A-1)"), an organic ruthenium compound (B1) represented by the above general formula (1), and a sulfur-containing organic ruthenium compound (B2). And a photosensitive resin composition of the photo-acid generator (C) having a functional group which promotes a polymerization reaction by generating a photo-acid generator during irradiation with actinic rays (hereinafter also referred to as " Acid polymerizable functional group").

(II) contains a cyclic olefin resin (hereinafter also referred to as "cyclic olefin resin (A-2)"), an organic ruthenium compound (B1) represented by the above general formula (1), and a sulfur-containing organic ruthenium compound (B2) And a photosensitive resin composition of the photopolymerization initiator (E) which is required to generate a radical by the functional group itself by irradiation with actinic rays or to be irradiated with actinic rays. In the case of a radical generated by the photopolymerization initiator (E), a functional group for photopolymerization (hereinafter also referred to as "photopolymerizable functional group") is used.

(III) contains a cyclic olefin resin (hereinafter referred to as "cyclic olefin resin (A-3)") having no acid polymerizable functional group and photopolymerizable functional group, and organic compound represented by the above general formula (1) A photosensitive resin composition of the hydrazine compound (B1), the sulfur-containing organic hydrazine compound (B2), the acid-polymerizable functional group-containing compound (F), and the photoacid generator (C).

(IV) contains a cyclic olefin resin (A-3) not containing an acid polymerizable functional group and a photopolymerizable functional group, an organic ruthenium compound (B1) represented by the above general formula (1), and a sulfur-containing organic ruthenium A photosensitive resin composition of the compound (B2), the photopolymerizable functional group-containing compound (G), and optionally the photopolymerization initiator (E).

The "acid-polymerizable functional group" is a functional group which promotes polymerization by the presence of an acid, and examples thereof include an epoxy group, an oxetanyl group, and a vinyl ether group, and an epoxy group is preferred. On the other hand, the acid produced by the photoacid generator (C) upon irradiation with actinic rays is subjected to heat hardening after irradiation with actinic rays, and is applied to the cyclic olefin resin (A-1) of (I). The acid-polymerizable functional group to be bonded, the acid-polymerizable functional group bonded to the other cyclic olefin resin (A-1), or the compound (F) having an acid-polymerizable functional group in (III) The acid-polymerizable functional group bonded thereto reacts with the acid-polymerizable functional group bonded to the other compound (F) having an acid-polymerizable functional group to promote the formation of a crosslinked structure.

The term "photopolymerizable functional group" means a radical generated by a functional group itself by irradiation with actinic rays or a radical generated by photopolymerization initiator (E) when irradiated with actinic rays, and The functional group for polymerizing the other functional group may, for example, be a vinyl group, a vinylphenyl group, a propenyl group or a methacryl group, and is preferably a propenyl group or a methacryl group. Further, the radical generated by the functional group itself by irradiation with actinic rays or the radical generated by the photopolymerization initiator (E) during irradiation with actinic radiation is used in the cyclic olefin resin (A). -2) The photopolymerizable functional group bonded to the upper surface reacts with the photopolymerizable functional group bonded to the other cyclic olefin resin (A-2) to initiate a crosslinking reaction.

The "acid-polymerizable functional group-containing compound (F)" refers to a compound which is polymerized by the presence of an acid generated by a photo-acid generator by irradiation with actinic rays, and has, for example, an epoxy group or an oxa group. A compound such as a cyclobutane group or a vinyl ether group. Further, the compound (F) having an acid polymerizable functional group may be a low molecular weight compound or a high molecular weight compound, except for the cyclic olefin resin (A-1). Therefore, when the acid generated by the photoacid generator (C) is irradiated with actinic rays, the compound (F) having an acid polymerizable functional group is polymerized to initiate polymerization.

The "photopolymerizable functional group-containing compound (G)" means a radical generated by a functional group itself by irradiation with actinic rays or a photopolymerization initiator (E) when irradiated with actinic rays. A compound which is polymerized by generating a radical, for example, a compound having a vinyl group, a propenyl group, a methacryl group or the like. Further, the compound (G) having a photopolymerizable functional group may be a low molecular weight compound or a high molecular weight compound, except for the cyclic olefin resin (A-2). However, a radical generated by a functional group itself by irradiation with actinic rays or a radical generated by a photopolymerization initiator (E) upon irradiation with actinic rays causes a photopolymerizable functional group. The compound (G) is polymerized to initiate polymerization.

The photosensitive resin composition (I) of the present invention will be described in more detail. The photosensitive resin composition of the present invention contains a cyclic olefin resin (A-1) having an acid polymerizable functional group, an organic cerium compound (B1) represented by the formula (1), and a sulfur-containing organic cerium compound (B2). And a photosensitive resin composition of the photoacid generator (C).

The cyclic olefin resin (A-1) having an acid polymerizable functional group contained in the photosensitive resin composition (I) of the present invention is composed of a polymer of a cyclic olefin and having a bond on the main chain. A resin having an acid polymerizable functional group. Further, among the cyclic olefin resins (A-1) having an acid polymerizable functional group, a cyclic olefin resin having an epoxy group is preferred.

The cyclic olefin resin (A-1) having an acid polymerizable functional group is a cyclic olefin monomer having an acid polymerizable functional group in the molecule (hereinafter also referred to as "a cyclic olefin monomer having an acid polymerizable functional group" The body (H-1)") is obtained by a method of polymerization. Further, the cyclic olefin resin (A-1) having an acid polymerizable functional group may be a cyclic olefin monomer having no acid polymerizable functional group (hereinafter also referred to as "a ring having no acid polymerizable functional group" The olefin monomer (H-2)" is polymerized to obtain a cyclic olefin resin having no acid polymerizable functional group (hereinafter also referred to as "cyclic olefin resin (J) having no acid polymerizable functional group" Then, it is obtained by a method of introducing an acid-polymerizable functional group such as an epoxy group into a side chain by a modification reaction in which an acid polymerizable functional group is introduced into the obtained polymer. The method of performing the reforming reaction is a method of graft-reacting an unsaturated monomer having an acid polymerizable functional group such as an epoxy group onto a cyclic olefin resin (J) having no acid polymerizable functional group. a method of reacting a compound having an acid polymerizable functional group such as an epoxy group with a reactive functional group moiety of a cyclic olefin resin (J) having no acid polymerizable functional group; and in the case of an epoxy group, A method for epoxidizing a carbon-carbon double bond by using an epoxidizing agent such as peroxygen or hydrogen peroxide as a cyclic olefin resin (J) having a carbon-carbon double bond in the molecule and having no acid-polymerizable functional group. method.

The cyclic olefin monomer (H-2) having no acid polymerizable functional group may, for example, be a monocyclic ring such as cyclohexene or cyclooctene; Alkene Diene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclopentadiene, tetracyclopentadiene, dihydrotetracyclopentadiene The polycyclic monomer, the cyclic olefin monomer (H-2) having no acid polymerizable functional group may have various functional groups.

The cyclic olefin monomer (H-1) having an acid polymerizable functional group may be a part of a cyclic olefin monomer (H-2) having no acid polymerizable functional group, and may be substituted by an acid polymerizable functional group. Compound. Examples of the cyclic olefin monomer (H-1) having an acid polymerizable functional group include a monocyclic ring such as cyclohexene or cyclooctene having an acid polymerizable functional group such as an epoxy group; Reduction of acid polymerizable functional groups Alkene Diene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclopentadiene, tetracyclopentadiene, dihydrotetracyclopentadiene Wait for a multi-ring.

Further, the cyclic olefin monomer (H-1) having an acid polymerizable functional group and the cyclic olefin monomer (H-2) having no acid polymerizable functional group are collectively referred to as "cyclic olefin monomer" hereinafter. (H)" is described.

The cyclic olefin resin (A-1) having an acid polymerizable functional group and the cyclic olefin resin (J) having no acid polymerizable functional group may be a polymerization polymerization of one cyclic olefin monomer (H). The body may be a copolymer of two or more kinds of cyclic olefin monomers (H), or may be copolymerizable with one or more kinds of cyclic olefin monomers (H) and such as α-olefins. a copolymer of other monomers, and may also be a hydride of the (co)polymers.

The cyclic olefin resin (A-1) having an acid polymerizable functional group and the cyclic olefin resin (J) having no acid polymerizable functional group are carried out by a known polymerization method using a cyclic olefin monomer (H). Obtained by polymerization. The polymerization method of the cyclic olefin monomer (H) is an addition polymerization method and a ring opening polymerization method. Further, in the polymerization of the cyclic olefin monomer (H), a known polymerization method such as random polymerization or block polymerization can be employed. The cyclic olefin resin (A-1) having an acid polymerizable functional group and the cyclic olefin resin (J) having no acid polymerizable functional group are preferably reduced by The cyclic olefin monomer having an ethylenic skeleton is a resin obtained by addition (co)polymerization, but the present invention is not limited thereto.

The cyclic olefin resin (A-1) having an acid polymerizable functional group obtained by an addition polymerization method and the cyclic olefin resin (J) having no acid polymerizable functional group are exemplified by (1) Addition (co)polymerization of the cyclic olefin monomer (H) to obtain an addition (co)polymer of the cyclic olefin monomer (H); (2) a cyclic olefin monomer (H), and ethylene or An addition copolymer of an α-olefin; (3) an addition copolymer of a cyclic olefin monomer and a non-conjugated diene, and optionally other monomers. These resins can be obtained in accordance with all known polymerization methods.

When the cyclic olefin monomer (H) system has a drop In the case of the cyclic olefin monomer (H) having an ethylenic skeleton, a cyclic olefin resin (A-1) having an acid polymerizable functional group and a cyclic olefin resin having no acid polymerizable functional group are obtained by an addition polymerization method. (J), can be cited: (1a) make the fall The cyclic olefin monomer of the olefinic skeleton is subjected to addition (co)polymerization to obtain a reduced Addition (co)polymer of cyclic olefin monomer of olefinic skeleton; (2a) with a drop a cyclic olefin monomer having an olefinic skeleton, an addition copolymerization with ethylene or an α-olefin; (3a) having a lowering An addition copolymer of a cyclic olefin monomer having an ethylenic skeleton, a non-conjugated diene, and optionally other monomers. These resins can be obtained in accordance with all known polymerization methods. In addition, in the present invention, the so-called "drop The olefinic skeleton refers to the 3-position and the 6-position of the cyclohexene skeleton, and the crosslinking is carried out by using one carbon atom. Alkene skeleton; the 3-position and the 6-position of the cyclohexene skeleton, a 7-side oxy group which is crosslinked by one oxygen atom Alkene skeleton.

The cyclic olefin resin (A-1) having an acid polymerizable functional group and the cyclic olefin resin (J) having no acid polymerizable functional group obtained by a ring opening polymerization method include (4) a cyclic ring. A ring-opening (co)polymer of an olefin monomer (H) or a resin which is hydrogenated. These resins are obtained, for example, by a method known by displacement polymerization.

When the cyclic olefin monomer (H) system has a drop In the case of the cyclic olefin monomer (H) having an ethylenic skeleton, a cyclic olefin resin (A-1) having an acid polymerizable functional group and a cyclic olefin having no acid polymerizable functional group are obtained by a ring-opening polymerization method. Resin (J), can be cited as: (4a) with a drop a ring-opening (co)polymer of a cyclic olefin monomer (H) having an ethylenic skeleton or a resin which is hydrogenated; (5a) having a lowering Cyclic olefin monomer (H) of the olefinic skeleton A ring-opening copolymer of a cyclic olefin monomer having an ethylenic skeleton or a resin obtained by hydrogenating the same. These resins are obtained by all known polymerization methods.

The addition polymerization method of the cyclic olefin monomer (H) includes coordination polymerization using a metal catalyst or radical polymerization. In the coordination polymerization, a cyclic olefin monomer (H) is obtained by polymerizing in a solution in the presence of a transition metal catalyst to obtain a resin (for example, NiCOLER. GROVE et al. Journal of Polymer Science: Part B, Polymer Physics, Vol. 37, 3003-3010 (1999)). Representative nickel and platinum catalysts for the metal catalyst used in the coordination polymerization are as described in PCT WO9733198 and PCTWO00/20472. Examples of the metal catalyst for coordination polymerization include bis(toluene)bis(perfluorophenyl)nickel, bis(symmetric trimethyl)bis(perfluorophenyl)nickel, and bis(phenyl)bis(perfluoro). Phenyl) nickel, bis(tetrahydro)bis(perfluorophenyl)nickel, bis(ethyl acetate)bis(perfluorophenyl)nickel, double (two A known metal catalyst such as alkane) bis(perfluorophenyl)nickel. Other useful catalysts include the nickel and palladium compounds disclosed in PCT WO97/33198 and PCTWO00/20472.

Regarding the free radical polymerization technique, it is described in Encyclopedia of Polymer Science, John Wiley & Sons, 13, 708 (1988). In general, the radical polymerization is carried out by raising the temperature to 50 to 150 ° C in the presence of a radical initiator, and then reacting the cyclic olefin monomer (H) in a solution. The radical initiator may be exemplified by azobisisobutyronitrile (AIBN), benzammonium peroxide, lauryl peroxide, azobisisohexonitrile, azobisisovaleronitrile, and tert-butyl peroxidation. Hydrogen, etc.

With a drop The ring-opening polymerization method of the cyclic olefin monomer (H) having an ethylenic skeleton may, for example, be a known ring-opening polymerization method, for example, using titanium or a tungsten compound as a catalyst, and lowering at least one or more A method of ring-opening (co)polymerization of a cyclic olefin monomer (H) having an ethylenic skeleton to obtain a ring-opened (co)polymer. The carbon-carbon double bond in the ring-opening (co)polymer may also be hydrogenated after ring-opening polymerization, if necessary, by a usual hydrogenation method.

In the addition polymerization method or the ring-opening polymerization method of the cyclic olefin monomer (H), a suitable solvent used may be a saturated hydrocarbon solvent or an aromatic solvent. Examples of the saturated hydrocarbon solvent include pentane, hexane, heptane, cyclohexane, and the like, but are not limited thereto. Examples of the aromatic solvent include benzene, toluene, xylene, and symmetrical trimethylbenzene, but are not limited thereto. Other solvents include diethyl ether, tetrahydrofuran, ethyl acetate, esters, lactones, ketones, and decylamines. These solvents may be used alone or in combination of two or more.

The molecular weight of the cyclic olefin resin (A-1) having an acid polymerizable functional group and the molecular weight of the cyclic olefin resin (J) having no acid polymerizable functional group are carried out by performing addition polymerization or ring opening. In the polymerization method, the ratio of the polymerization initiator to the monomer is changed, or the polymerization time or temperature is changed to control. The weight average molecular weight of the cyclic olefin resin (A-1) having an acid polymerizable functional group is preferably 10,000 to 500,000, more preferably 30,000 to 100,000, still more preferably 50,000 to 80,000. Further, the weight average molecular weight was measured using a gel permeation chromatography (GPC) using standard polystyrene (according to ASTM Ds 3536-91). When a metal catalyst for coordination polymerization is used, the molecular weight can also be controlled by the use of a chain transfer catalyst as disclosed in U.S. Patent No. 6,136,499. The use of chain transfer catalysts is particularly useful for molecular weight control of alpha-olefins such as ethylene, propylene, 1-hexene, 1-decene, 4-methyl-1-pentene, and the like.

The cyclic olefin monomer (H) is preferably a lower one represented by the general formula (5). Alkenyl cyclic olefin monomer.

[化18]

In the formula (5), X is an oxygen atom (-O-) or a methylene group (-CH ₂ -). r is an integer of 0 to 5, preferably an integer of 0 to 2. R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, an alkenyl group, an alkynyl group, a decyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a functional group having an ester group, a functional group having a keto group, and an ether group. A functional group or a functional group having an epoxy group. The R ¹¹ to R ¹⁴ systems may be the same or different.

The alkyl group of R ¹¹ to R ¹⁴ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a dodecyl group. , cyclopentyl, cyclohexyl, cyclooctyl and the like.

Further, examples of the alkenyl group of R ¹¹ to R ^{14 include} a vinyl group, an allyl group, a butynyl group, and a cyclohexenyl group.

Further, examples of the alkynyl group of R ¹¹ to R ¹⁴ include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, and a 2-butynyl group.

Further, examples of the aromatic group of R ¹¹ to R ¹⁴ include a phenyl group, a naphthyl group, an anthracenyl group and the like.

Further, examples of the aralkyl group of R ¹¹ to R ¹⁴ include a benzyl group and a phenethyl group. Further, the present invention is not limited to the above.

The functional group having an ester group of R ¹¹ to R ¹⁴ is taken up before the functional group having an ester group, and the rest of the structure is not particularly limited.

Further, the functional group having a ketone group of R ¹¹ to R ¹⁴ is taken up before the functional group having a ketone group, and the rest of the structure is not particularly limited.

Further, the functional group having an ether group of R ¹¹ to R ¹⁴ is taken up before the functional group having an ether group, and the rest of the structure is not particularly limited.

Further, the functional group having an epoxy group of R ¹¹ to R ¹⁴ is taken up before the functional group having an epoxy group, and the rest is not particularly limited in structure, and is preferably a function having a glycidyl ether group. base.

As the cyclic olefin monomer (H), for example, those having an alkyl group are exemplified by 5-methyl-2-nor Alkene, 5-ethyl-2-nor Alkene, 5-propyl-2-lower Alkene, 5-butyl-2-lower Alkene, 5-pentyl-2-nor Alkene, 5-hexyl-2-nor Alkene, 5-heptyl-2-nor Alkene, 5-octyl-2-nor Alkene, 5-mercapto-2-lower Alkene, 5-mercapto-2-lower Alkene, etc.; in addition, if there is an alkenyl group, it can be cited as: 5-allyl-2-lower Alkene, 5-methylene-2-nor Alkene, 5-ethylidene-2-nor Alkene, 5-isopropylidene-2-lower Alkene, 5-(2-propenyl)-2-lower Alkene, 5-(3-butenyl)-2-nor Alkene, 5-(1-methyl-2-propenyl)-2-nor Alkene, 5-(4-pentenyl)-2-lower Alkene, 5-(1-methyl-3-butenyl)-2-nor Alkene, 5-(5-hexenyl)-2-nor Alkene, 5-(1-methyl-4-pentenyl)-2-lower Alkene, 5-(2,3-dimethyl-3-butenyl)-2-lower Alkene, 5-(2-ethyl-3-butenyl)-2-nor Alkene, 5-(3,4-dimethyl-4-pentenyl)-2-lower Alkene, 5-(7-octenyl)-2-nor Alkene, 5-(2-methyl-6-heptenyl)-2-nor Alkene, 5-(1,2-dimethyl-5-hexenyl)-2-lower Alkene, 5-(5-ethyl-5-hexenyl)-2-nor Alkene, 5-(1,2,3-trimethyl-4-pentenyl)-2-lower Alkene, etc.; further, in the case of an alkynyl group, 5-ethynyl-2-norr Alkene, etc.; further, in the case of an alkyl group, 1,1,3,3,5,5-hexamethyl-1,5-dimethylbis(2-(5-lower) Alken-2-yl)ethyl)trioxane, etc.; in addition, if it has an aromatic group, it can be cited as: 5-phenyl-2-lower Alkene, 5-naphthyl-2-nor Alkene, 5-pentafluorophenyl-2-lower Alkene, etc.; further, those having an aralkyl group may be exemplified by 5-benzyl-2-nor Alkene, 5-phenylethyl-2-nor Alkene, 5-pentafluorophenylmethyl-2-nor Alkene, 5-(2-pentafluorophenethyl)-2-nor Alkene, 5-(3-pentafluorophenylpropyl)-2-nor Alkene, etc.; further, in the case of an alkoxyalkylene group, a dimethyl bis ((5-lower) Alken-2-yl)methoxy)decane, 5-trimethoxydecane-2-lower Alkene, 5-triethoxynonane-2-lower Alkene, 5-(2-trimethoxydecaneethyl)-2-lower Alkene, 5-(2-triethoxydecaneethyl)-2-lower Alkene, 5-(3-trimethoxydecanepropyl)-2-lower Alkene, 5-(4-trimethoxydecanebutyl)-2-lower Alkene, 5-trimethyldecane methyl ether-2-lower Alkene and the like.

As the cyclic olefin monomer (H), those having a hydroxyl group, an ether group, a carboxyl group, an ester group, an acryloyl group, or a methacrylium group can be exemplified by 5-nor Alkene-2-methanol and its alkyl ether, acetic acid 5-nor Alkene-2-methyl ester, propionic acid 5-nor Alkene-2-methyl ester, butyric acid 5-nor Alkene-2-methyl ester, valeric acid 5-nor Alkene-2-methyl ester, hexanoic acid 5-drop Alkene-2-methyl ester, octanoic acid 5-nor Alkene-2-methyl ester, decanoic acid 5-nor Alkene-2-methyl ester, lauric acid 5-drop Alkene-2-methyl ester, stearic acid 5-dower Alkene-2-methyl ester, oleic acid 5-nor Alkene-2-methyl ester, sublinoleic acid 5-dower Alkene-2-methyl ester, 5-nor Alkene-2-carboxylic acid, 5-nor Methyl 2-carboxylate, 5-nor Ethyl 2-carboxylic acid ethyl ester, 5-nor Tert-butyl carboxylic acid, 5-butane Iso-2-carboxylic acid isobutyl ester, 5-nor Alkene-2-carboxylic acid trimethyldecane ester, 5-nor Ethyl-2-carboxylic acid triethyl decyl ester, 5-nor Alkene-2-carboxylic acid Ester, 5-drop 2-hydroxyethyl 2-carboxylate, 5-nor Methyl 2-ethyl-2-carboxylate, 5-decanoic acid Alkene-2-methyl ester, 5-nor Alkene-2-methylethyl carbonate, 5-nor Alkene-2-methyl-n-butyl carbonate, 5-nor Alkene-2-methyl tert-butyl carbonate, 5-methoxy-2-lower Alkene, (meth)acrylic acid 5-nor Alkene-2-methyl ester, (meth)acrylic acid 5-nor Alkene-2-ethyl ester, (meth)acrylic acid 5-nor Alkenyl-2-n-butyl ester, 5-(meth)acrylic acid Alkenyl-2-n-propyl ester, 5-(meth)acrylic acid Alkenyl-2-isobutyl ester, 5-(meth)acrylic acid Alkenyl-2-isopropyl ester, 5-(meth)acrylic acid Alkenyl-2-hexyl ester, 5-(meth)acrylic acid Alkenyl-2-octyl ester, 5-(meth)acrylic acid Further, it is exemplified by a tetracyclic ring, and is exemplified by 8-methoxycarbonyltetracyclo [4. 4. 0. 1 ^{2, 5.} 1 ^{7, 10} ] ^dodeca- 3-ene, 8-ethoxycarbonyltetracyclo[4. 4. 0. 1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-n-propoxycarbonyltetracyclo[4. 4. 0 . 1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-isopropyloxycarbonyltetracyclo [4. 4. 0. 1 ^2,5 . 1 ^7,10 ] dodeca-3- Alkene, 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-tributoxycarbonyltetracyclo[4. 4. 0. 1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-ring Hexyloxytetracyclo[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 ]12 carbon 3-ene, 8-tetrahydrofuranoxycarbonyltetracyclo[4. 4. 0. 1 ^2,5 . 1 ^7,10 ]-3-dodecene, 8-tetrahydropyranyloxycarbonyltetracyclo [4. 4. 0. 1 ^2,5 . 1 ^7,10 ] ^Dodeca -3-ene, 8-methyl-8-methoxy Carbonyltetracyclo[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]} dodeca-3-ene, 8-methyl-n-propoxycarbonyl tetracyclo [4.4.3 .1 ^2,5 1 ^7,10] -3 dodecene - alkene, 8-methyl-8-isopropyloxycarbonyltetracyclo[4. 4. 0. 1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-methyl-8-n-butyl Oxycarbonyl tetracyclo[4. 4. 0. 1 ^2,5 . 1 ^7,10 ] dodeca-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 ]12 Carbon-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-phenylcyanocarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyl-8-tetrahydrofuranoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, methyl-8-tetrahydropyranyloxy carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8 Acetyl-8-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8,9-bis (methoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8,9-bis(ethoxycarbonyl)tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8,9 - bis(n-propoxycarbonyl)tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8,9-di(isopropoxycarbonyl)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-bis(phenoxycarbonyl)tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene , 8,9-bis(tetrahydrofuranoxycarbonyl)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, 8,9-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, tetracyclo[ 4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-en-8-carboxylic acid, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^dodecan -3- 8-carboxylic acid, 8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8- Yl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 .0 ^1,6] dodeca-3-ene , 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,12 ]dodec-3-ene, 8-ethylenetetracycline [4.4.0.1 ^2,5 .1 ^7,10 0 ^{1 , 6} ] dodeca-3-ene and the like.

The cyclic olefin resin (A-1) having an acid polymerizable functional group is preferably a cyclic olefin resin having a structural unit represented by the general formula (6).

[Chemistry 19]

In the formula (6), X is an oxygen atom (-O-) or a methylene group (-CH ₂ -). r is an integer from 0 to 5, preferably an integer from 0 to 3. R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, an alkenyl group, an alkynyl group, a decyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a functional group having an ester group, a functional group having a keto group, and an ether group. A functional group or a functional group having an epoxy group. The R ¹¹ to R ¹⁴ systems may be the same or different.

The cyclic olefin resin (A-1) having a structural unit represented by the general formula (6) is one or two or more kinds of structural units represented by the general formula (6), and is a structural unit constituting the resin main chain, for example: (i) a cyclic olefin resin (A-1) having a structural unit represented by the general formula (6) having at least one of R ¹¹ to R ¹⁴ and having a functional group having an epoxy group, or (ii) R ¹¹ to R ^{14 which} are generally a structural unit represented by the formula (6) are not a functional group having an epoxy group, and have a ring of an acid polymerizable functional group having a structural unit other than the structural unit represented by the formula (6). Olefin resin (A-1).

In the cyclic olefin resin (A-1) having a structural unit represented by the general formula (6), the molar % of the structural unit represented by the general formula (6) is 10 to 100 mol%, preferably 50 to 100 mol. Ear %, especially good 100% by mole. In the cyclic olefin resin (A-1) having a structural unit represented by the general formula (6), the cyclic olefin resin (A-1) having a structural unit of 100 mol% as shown by the general formula (6) is generally used. The cyclic olefin resin (A-1) having one or more of the structural units represented by the formula (6) and the structural unit represented by the general formula (6) in the cyclic olefin resin (A-1) The total count is preferably 10 to 10,000. In addition, when the cyclic olefin resin (A-1) having the structural unit represented by the general formula (6) has two or more structural units represented by the general formula (6), the structural unit represented by the general formula (6) The molar % is the total mole % of the two or more structural units. Further, the molar % of these structural units is the same as the % of each monomer before polymerization.

In the cyclic olefin resin (A-1) having a structural unit represented by the general formula (6), when the molar percentage of the structural unit represented by the general formula (6) is 100 mol%, the cyclic olefin resin (A-1) A structural unit having at least one of R ¹¹ to R ¹⁴ as a functional group having an epoxy group, and preferably at least one of R ¹¹ to R ¹⁴ is a structural unit having a functional group having an epoxy group The ratio of existence is 5 to 95 mol%, particularly preferably 20 to 80 mol%, and more preferably 30 to 70 mol%. In addition, the cyclic olefin resin (A-1) having a structural unit represented by the general formula (6) has a general formula (6) in which at least one of two or more R ¹¹ to R ¹⁴ is a functional group having an epoxy group. In the structural unit shown, at least one of R ¹¹ to R ¹⁴ is a molar % of a structural unit represented by the general formula (6) having a functional group of an epoxy group, and is a total of two or more structural units. %. Further, the molar % of these structural units is the same as the % of each monomer before polymerization.

The cyclic olefin resin (A-1) having an acid polymerizable functional group is preferably a general formula from the viewpoint of excellent resin properties (low elastic modulus, high elongation, low water absorption, etc.) after curing. The cyclic olefin resin (A-1) having a structural unit (7-1) and a structural unit represented by the general formula (7-2) is more preferably a structural unit represented by the general formula (8-1). A cyclic olefin resin (A-1) composed of a structural unit represented by the general formula (8-2) and a structural unit represented by the general formula (8-3). A cyclic olefin resin (A-1) composed of a structural unit represented by the general formula (8-1), a structural unit represented by the general formula (8-2), and a structural unit represented by the general formula (8-3) By deriving from the aralkyl group When the skeleton of the olefin monomer is introduced into the resin, the solubility in a polar solvent such as cyclopentanone or heptanone which is a solvent for the negative developer can be improved, and the workability is excellent.

[Chemistry 20]

[Chem. 21]

In the formulae (7-1) and (7-2), R ²¹ to R ²⁷ are hydrogen, an alkyl group, an alkenyl group, an alkynyl group, a decyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, or an ester group. Any of a functional group, a functional group having a ketone group, or a functional group having an ether group.

The cyclic olefin resin (A-1) composed of the structural unit represented by the general formula (7-1) and the structural unit represented by the general formula (7-2) is a structural unit represented by the general formula (7-1). In the structural unit represented by the general formula (7-2), a polymer chain of a resin is formed, and in the resin, the structural unit represented by the general formula (7-1) may be one type or two or more types. Further, the structural unit represented by the general formula (7-2) may be one type or two or more types. In other words, in the cyclic olefin resin (A-1) composed of the structural unit represented by the general formula (7-1) and the structural unit represented by the general formula (7-2), R ²¹ to R ²⁷ may be the same. Can also be different.

In the cyclic olefin resin (A-1) composed of the structural unit represented by the general formula (7-1) and the structural unit represented by the general formula (7-2), the structural unit represented by the general formula (7-1) Molar%, preferably 20 to 80 mol%, particularly good 30 to 70 mol%, and the molar percentage of the structural unit represented by the general formula (7-2), preferably 20 to 80 mol% , especially good 30~70 mol%. In addition, the cyclic olefin resin (A-1) composed of the structural unit represented by the general formula (7-1) and the structural unit represented by the general formula (7-2) has two or more general formulas (7- 1) In the case of the structural unit shown or two or more structural units represented by the general formula (7-2), the structural unit of the structural unit represented by the general formula (7-1) is two or more general formulas (7). -1) The total number of structural units shown in the general formula (7-2), and the total number of structural units shown in the general formula (7-2). Moer%. Further, the molar % of these structural units is the same as the % of each monomer before polymerization.

[化22]

[化23]

[Chem. 24]

In the formula (8-1), the formula (8-2) and the formula (8-3), R ³¹ to R ⁴⁰ are hydrogen, alkyl, alkenyl, alkynyl, nonanealkyl, aryl, aralkyl, alkane. Any of a oxonyl group, a functional group having an ester group, a functional group having a keto group, or a functional group having an ether group. s is an integer from 0 to 5. Further, R ³¹ to R ³³ in the preferred formula (8-1) are all hydrogen, and s in the formula (8-2) is an integer of 1 to 3, and R ³⁷ in the formula (8-3) Any of ~R ⁴⁰ is an alkyl group having 4 to 12 carbon atoms.

a cyclic olefin resin (A-1) composed of a structural unit represented by the general formula (8-1), a structural unit represented by the general formula (8-2), and a structural unit represented by the general formula (8-3), A polymer chain of a resin is formed in a resin by using a structural unit represented by the general formula (8-1), a structural unit represented by the general formula (8-2), and a structural unit represented by the general formula (8-3). The structural unit represented by the general formula (8-1) may be one type or two or more types, and the structural unit represented by the general formula (8-2) may be one type or two or more types. Further, the structural unit represented by the general formula (8-3) may be one type or two or more types. In other words, a cyclic olefin resin (A-1) composed of a structural unit represented by the general formula (8-1), a structural unit represented by the general formula (8-2), and a structural unit represented by the general formula (8-3). In the case, the R ³¹ to R ⁴⁰ systems may be the same or different.

The cyclic olefin resin (A-1) consisting of a structural unit represented by the general formula (8-1), a structural unit represented by the general formula (8-2), and a structural unit represented by the general formula (8-3) The molar % of the structural unit represented by the general formula (8-1) is preferably 10 to 80 mol%, particularly preferably 20 to 60 mol%, and further, the structural unit represented by the general formula (8-2) The molar % is preferably 10 to 80 mol %, and the extra fine is 20 to 60 mol %, and the molar percentage of the structural unit represented by the general formula (8-3) is preferably 10 to 80 mol %. The special best is 20~60%. Further, a cyclic olefin resin composed of a structural unit represented by the general formula (8-1), a structural unit represented by the general formula (8-2), and a structural unit represented by the general formula (8-3) (A- 1) has two or more structural units represented by the general formula (8-1), two or more structural units represented by the general formula (8-2), or two or more structural units represented by the general formula (8-3) In the case of the structural unit of the general formula (8-1), the total number of structural units of the structural unit shown by the general formula (8-1) is two or more, and the general formula (8-2) is similar. The structural unit of the structural unit shown is a total of two or more structural units represented by the general formula (8-2), and the structural unit of the structural unit represented by the general formula (8-3) is a Moh% system. The total mole % of the structural unit represented by two or more general formulas (8-3). Further, the molar % of these structural units is the same as the % of each monomer before polymerization.

The cyclic olefin resin (A-1) having an acid-polymerizable functional group is more preferably from the viewpoint of excellent resin properties (low modulus of elasticity, high elongation, low water absorption, etc.) after curing. 9-1) a structural unit, a cyclic olefin resin (A-1) composed of a structural unit represented by the formula (9-2) and a structural unit represented by the formula (9-3). By coming down from the base The skeleton of the olefin monomer is introduced into the resin to obtain a low elastic film, and is derived from the phenylethyl group. When the skeleton of the olefin monomer is introduced into the resin, a film excellent in low water absorbability, chemical resistance, and polar solvent solubility can be obtained.

[化25]

[Chem. 26]

[化27]

The cyclic olefin resin (A-1) composed of the structural unit represented by the formula (9-1), the structural unit represented by the formula (9-2), and the structural unit represented by the formula (9-3) is used. The structural unit shown in (9-1), the structural unit represented by the formula (9-2), and the structural unit represented by the formula (9-3) form a polymer chain of a resin. In the cyclic olefin resin (A-1) composed of the structural unit represented by the formula (9-1), the structural unit represented by the formula (9-2), and the structural unit represented by the formula (9-3), 9-1) The moie % of the structural unit shown is preferably 10 to 80 mol%, particularly preferably 20 to 60 mol%, and the molar % of the structural unit represented by the formula (9-2) is preferably 10~80 mol%, especially good 20~60 mol%, and the molar % of the structural unit shown by formula (9-3) is preferably 10~80 mol%, especially good 20~60 Moer%. Further, the molar % of these structural units is the same as the % of each monomer before polymerization.

In the cyclic olefin resin (A-1) having an acid polymerizable functional group, the resin having an acid polymerizable functional group is an epoxy group (that is, a cyclic olefin resin (A-1) having an epoxy group), having a ring In the cyclic olefin resin (A-1) of the oxy group, the structural unit derived from the cyclic olefin monomer (H-2) having an epoxy group is mol% (that is, in the total polymerization monomer before polymerization, having a ring The molar % of the cyclic olefin monomer (H-2) of the oxy group is appropriately selected by the method of crosslinking by exposure, and the oxime which can withstand the crosslinking density of the developer is appropriately selected, preferably 5~95 mole%, especially good 20~80 mole%, and better 30~70 mole%. The structural unit mol% derived from the cyclic olefin monomer (H-2) having an epoxy group in the cyclic olefin resin (A-1) having an epoxy group (in the total polymerization monomer before polymerization, When the molar percentage of the cyclic olefin monomer (H-2) having an epoxy group is within the above range, a low value of a resin water absorption of less than 0.3% by weight and a low dielectric constant of less than 2.6 can be exhibited. The dielectric loss is less than 0.001, and the glass transition point is excellent physical properties such as 170 to 400 °C.

The photosensitive resin composition (I) of the present invention contains the organic hydrazine compound (B1) represented by the general formula (1). The organic ruthenium compound (B1) represented by the general formula (1) improves the adhesion between the cured product of the photosensitive resin composition and the substrate, and particularly the cured product of the photosensitive resin composition, ruthenium, ruthenium oxide, The adhesion between inorganic ruthenium compounds such as ruthenium nitride.

[化28]

(R ² O) ₃ ─Si─R ¹ ─Si─(OR ² ) ₃ (1)

In the formula (1), R ¹ is an alkylene group having 5 to 30 carbon atoms or an organic group having at least one aromatic ring. R ² is an alkyl group having 1 to 10 carbon atoms, which may be the same or different. Further, from the viewpoint of enhancing the affinity with the cyclic olefin resin (A), the organic ruthenium compound (B1) represented by the general formula (1) wherein R ¹ is an alkylene group having 6 to 8 carbon atoms is preferred. . The organic ruthenium compound (B1) represented by the general formula (1) wherein R ¹ is an alkylene group having 6 to 8 carbon atoms may, for example, be bis(trimethoxydecyl)hexane or bis(triethoxydecane). Hexane, bis(trimethoxydecyl)heptane, bis(triethoxydecyl)heptane, bis(trimethoxydecyl)octane, bis(triethoxydecyl)octane Wait.

The photosensitive resin composition (I) of the present invention contains a sulfur-containing organic cerium compound (B2). Further, in the present invention, the term "sulfur-containing" in the sulfur-containing organic antimony compound (B2) means a sulfur atom in the molecule. On the other hand, the sulfur-containing organic bismuth compound (B2) is derived from a photosensitive resin composition and a metal (metal, copper, aluminum, titanium, tungsten, chromium, or the like, a metal monomer film or an alloy film, etc., particularly gold and copper. From the viewpoint of the adhesion between the resin and the phenolic antioxidant, the thermal oxidizing property of the cured resin film is improved, and the organic bismuth compound represented by the general formula (2) and the general formula are preferred. (3) One or two or more selected from the group consisting of the organic hydrazine compounds shown.

[化29]

In the formula (2), R ³ and R ⁴ are an alkyl group having 1 to 10 carbon atoms. R ⁵ and R ⁶ are linear or branched alkyl groups and have a carbon number of 1 to 10. k and l are 0 or 1. The m is an integer of 1 to 10, preferably an integer of 2 to 4. n is 0, 1 or 2. When there are two or more R ³ in the molecule, the R ³ system may be the same or different. Further, when there are two or more R ⁴ in the molecule, the R ⁴ groups may be the same or different.

[化30]

In the general formula (3), R ⁷ and R ⁸ are an alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 10, and q is 0, 1 or 2. When there are two or more R ⁷ in the molecule, the R ⁷ system may be the same or different. When there are two or more R ⁸ in the molecule, the R ⁸ groups may be the same or different.

The sulfur-containing organic hydrazine compound represented by the general formula (2), specifically, bis(3-triethoxydecanepropyl)disulfane, bis(3-triethoxydecanepropyl) Tetrasulfane, bis(3-triethoxydecanepropyl)hexasulfane, bis(3-triethoxydecanepropyl)octaneane, and the like. Further, specific examples of the sulfur-containing organic hydrazine compound represented by the formula (3) include γ-thiolpropyltrimethoxydecane and γ-thiolpropyltriethoxydecane.

(B2) The compounding amount ratio [(B1) weight / (B2) weight] of the organic hydrazine compound (B1) represented by the general formula (1) is preferably 1 or more and 20 or less, particularly preferably 1 or more and 10 Hereinafter, it is more preferably 1 or more and 8 or less, and still more preferably 1.2 or more and 6 or less. When the compounding amount of the organic hydrazine compound (B1) represented by the general formula (1) is within the above range, the storage stability of the photosensitive resin composition at normal temperature can be improved.

The compounding amount of the organic hydrazine compound (B1) represented by the general formula (1) is preferably 1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the cyclic olefin resin (A-1). 2 parts by weight or more and 18 parts by weight or less. When the amount of the organic ruthenium compound (B1) represented by the general formula (1) is within the above range, it is possible to form a photosensitive resin composition excellent in adhesion to a substrate or a metal film and excellent in damage at normal temperature. .

The photosensitive resin composition (I) of the present invention is not limited to the range of not impairing properties, except for the organic cerium compound (B1) represented by the general formula (1) and the sulfur-containing organic cerium compound (B2). An organic ruthenium compound other than (B1) and (B2) (hereinafter also referred to as "organo ruthenium compound (B3)") is contained. Specific examples of the organic hydrazine compound (B3) include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-aminopropyltriethyl The oxoxane and the organic hydrazine compound represented by the general formula (10) are not limited thereto.

[化31]

In the formula (10), t is 0, 1, or 2. R ⁴¹ is a methylene group, a linear alkyl group having 2 to 20 carbon atoms, a branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 2 to 20 carbon atoms, and 2~ An alkylene oxide having 6 carbon atoms and a linking group selected from a poly(alkylene oxide) group. R ⁴² is an alkyl group having 1 to 4 carbon atoms. When there are two or more R ⁴² in the molecule, R ⁴² may be the same or different. R ⁴³ is hydrogen and an alkyl group having 1 to 4 carbon atoms. When there are two or more R ⁴³ in the molecule, the R ⁴³ system may be the same or different.

The photosensitive resin composition (I) of the present invention contains a photoacid generator (C). The photoacid generator (C) is a compound which generates an acid by irradiation with actinic rays, and all known compounds can be used. Further, the photoacid generator (C) is crosslinked by an acid polymerizable functional group (particularly an epoxy group), and is cured by subsequent hardening to improve the adhesion to the substrate.

The photoacid generator (C) is a phosphonium salt, a quinone imine compound, a halogen compound, or a sulfonate, or a combination thereof. The onium salt which is a photoacid generator (C) may, for example, be a diazonium salt, an ammonium salt, a phosphonium salt, a phosphonium salt, a phosphate salt, a phosphonium salt or a hydronium hydrogen salt. The relative anion of the onium salt which is a photoacid generator (C) is removed before it becomes a relative anion of the onium salt, and the rest is not limited. The relative anion of the phosphonium salt of the photoacid generator (C) is not particularly limited, and is preferably an anion having a small nucleophilicity, for example, a conjugate base such as a perfluoroalkanesulfonate or a hexafluorophosphoric acid. Salt, hexafluoroantimonate, tetrafluoroborate, hydrazine (pentafluorophenyl) borate, and the like.

The phosphonium salt which is a photoacid generator (C) may, for example, be triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroarsenate or triphenylsulfonium tetrafluoride. Phosphate, triphenylsulfonium tetrafluorosulfate, 4-thiophenoxydiphenylphosphonium tetrafluoroborate, 4-thiophenoxydiphenylphosphonium tetrafluoroantimonate, 4-thiobenzene Oxydiphenylphosphonium tetrafluoroarsenate, 4-thiophenoxydiphenylphosphonium tetrafluorophosphate, 4-thiophenoxydiphenylphosphonium tetrafluorosulfonate, 4-third Phenylphenyldiphenylphosphonium tetrafluoroborate, 4-tert-butylphenyldiphenylphosphonium tetrafluorosulfonate, 4-tert-butylphenyldiphenylphosphonium tetrafluoroantimonate, 4- Tert-butylphenyldiphenylphosphonium trifluorophosphonate, 4-tert-butylphenyldiphenylphosphonium trifluorosulfonate, ginseng (4-methylphenyl)phosphonium trifluoroborate, ginseng (4-methylphenyl)phosphonium tetrafluoroborate, ginseng (4-methylphenyl)phosphonium hexafluoroarsenate, ginseng (4-methylphenyl)phosphonium hexafluorophosphate, ginseng (4-A) Phenyl phenyl) hexafluorosulfonate, ginseng (4-methoxyphenyl) fluorene tetrafluoroborate, ginseng (4-methoxyphenyl) hexafluoroantimonate, ginseng (4-methoxy Phenyl) Fluorophosphate, ginseng (4-methoxyphenyl)phosphonium trifluorosulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate Acid salt, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluorosulfonate, 3,3-dinitrodiphenylphosphonium tetrafluoroborate, 3,3-dinitrodiphenyl Base hexafluoroantimonate, 3,3-dinitrodiphenylphosphonium hexafluoroarsenate, 3,3-dinitrodiphenylphosphonium trifluorosulfonate, 4,4-di Nitrodiphenylphosphonium tetrafluoroborate, 4,4-dinitrodiphenylphosphonium hexafluoroantimonate, 4,4-dinitrodiphenylphosphonium hexafluoroarsenate, 4, The 4-dinitrodiphenylsulfonium trifluorosulfonate may be used alone or in combination of two or more.

The halogen compound which belongs to the photoacid generator (C) is exemplified by 2,4,6-para(trichloromethyl)tri 2-allyl-4,6-bis(trichloromethyl)tri , α,β,α-tribromomethylphenylhydrazine, α,α-2,3,5,6-hexachloroxylene, 2,2-bis(3,5-dibromo-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoroxylene, 1,1,1-cis (3,5-dibromo-4-hydroxyphenyl)ethane, one of which can be used alone Two or more types may be used in combination.

The sulfonic acid esters belonging to the photoacid generator (C) include 2-nitrobenzyl tosylate, 2,6-dinitrobenzyl toluenesulfonate, and 2,4-dinitrobenzyl toluenesulfonate. Ester, 2-nitrobenzyl methanesulfonate, 2-nitrobenzyl ethanesulfonate, 9,10-dimethoxyindole-2-sulfonate, 1,2,3-cis (methanesulfonate) Oxy)benzene, 1,2,3-sodium (ethionyloxy)benzene, 1,2,3-paraxyl (propanesulfonyloxy)benzene, etc., these may be used alone or in combination 2 or more types.

The photoacid generator (C) is preferably 4,4'-di-t-butylphenylphosphonium trifluoromethanesulfonate, 4,4',4"-parade (t-butylphenyl)pyrene Fluoromethanesulfonate, diphenylphosphonium (pentafluorophenyl) borate, triphenylsulfonium diphenylphosphonium (pentafluorophenyl) borate, 4,4'-di-t-butyl Phenylhydrazine (pentafluorophenyl)borate, ginseng (t-butylphenyl)phosphonium (pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl Phenylhydrazine (pentafluorophenyl) borate, or a combination of these.

The amount of the photoacid generator (C) is preferably 0.1 part by weight or more and 100 parts by weight or less, particularly preferably 0.1 part by weight or more and 10 parts by weight based on 100 parts by weight of the cyclic olefin resin (A-1). the following.

The photosensitive resin composition (I) of the present invention may contain a sensitizer for improving the photosensitive characteristics as necessary. The sensitizer can broaden the wavelength range in which the photoacid generator (C) can be activated, and is added in a range that does not directly affect the resin crosslinking reaction. The most preferred sensitizer is a compound which has a maximum absorption coefficient in the vicinity of the light source used and which can efficiently transfer the absorbed energy to the photoacid generator. The sensitizer of the photoacid generator (C) is a cyclic aromatic compound such as ruthenium, osmium or iridium. The sensitizer of the photoacid generator (C) may, for example, be 2-isopropyl-9H-thioxanthene-9-ene, 4-isopropyl-9H-thioxanthene-9-one, 1-chloro- 4-propoxy thioxanthenol , or a combination of these. The amount of the sensitizer is preferably 0.1 parts by weight or more and 10 parts by weight or less, particularly preferably 0.2 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the cyclic olefin resin (A-1). When the light source is a long wavelength such as g line (435 nm) and i line (365 nm), the sensitizer is effective for activating the photoacid generator (C).

The photosensitive resin composition (I) of the present invention may further contain a small amount of an acid scavenger as necessary. The photosensitive resin composition (I) of the present invention contains an acid scavenger to improve the resolution. The acid trapping agent captures the acid generated by the photoacid generator (C) by irradiation with actinic rays, thereby preventing the acid from diffusing into the unexposed portion. Examples of the acid scavenger include pyridine, lutidine, and phenothiazine. Second- and third-grade amines such as tri-n-propylamine and triethylamine are not limited to this. The amount of the acid-trapping agent is preferably 0.01 parts by weight or more and 0.2 parts by weight or less based on 100 parts by weight of the cyclic olefin resin (A-1).

The photosensitive resin composition (I) of the present invention may further contain an antioxidant (D) as necessary. The antioxidant (D) is one or more selected from the group consisting of a phenolic antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. The antioxidant (D) suppresses oxidation at the time of hardening and oxidation of the resin film in a subsequent process or reliability test.

Examples of the phenolic antioxidant of the antioxidant (D) include pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and 3,9-double {2-[ 3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl}2,4,8,10-tetra Spiro[5,5]undecane, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, 1,6-hexanediol-bis[3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4 -hydroxybenzyl)benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-de Octadecyloxyphenol, (3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, (3,5-di-t-butyl-4-hydroxybenzyl)phosphonic acid Aliphatic ester, thiodiethylene glycol bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl-inter Cresol), 2-octylthio-4,6-bis(3,5-di-t-butyl-4-hydroxyphenoxy)-s-three , 2,2'-methylenebis(4-methyl-6-tert-butyl-6-butylphenol), 2,2'-methylenebis(4-ethyl-6-tributyl) Phenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butanoate]diol, 4,4'-butylene bis(6-tert-butyl-intermediate Phenol), 2,2'-ethylenebis(4,6-di-t-butylphenol), 2,2'-ethylenebis(4-secondbutyl-6-tert-butylphenol) 1,1,3-glycol(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxyl) 3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-gin (2,6-dimethyl-3-hydroxy-4-tributyl) Benzyl)isomeric cyanurate, 1,3,5-gin (3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3 , 5-paran [(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxyethyl]isocyanate, hydrazine [methylene-3-(3,5-di) Third butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-propenyloxy-3-tert-butyl-5-methyl Benzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetra Spiro[5,5]undecane-bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[β-(3- Tributyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl -6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(6-(1- Methylcyclohexyl)-4-methylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis(2-(3-third) 4-hydroxy-5-methylphenylpropenyloxy) 1,1-dimethylethyl)-2,4,8,10-tetra Spiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-bis(3,5-di-t-butyl- 4-hydroxybenzyl) sulfide, 4,4'-thiobis(6-tert-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di Triamylhydroquinone, 2-t-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl -6-(1-methylcyclohexyl, styrene phenol, 2,4-bis((octylthio)methyl)-5-methylphenol, etc. among these, preferably hindered phenolic resistant Oxidizer.

Examples of the phosphorus-based antioxidant of the antioxidant (D) include bis-(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite and ginseng (2,4-second third). Butyl phenyl phosphite), hydrazine (2,4-di-tert-butyl-5-methylphenyl)-4,4'-phenylphenyl diphosphonate, 3,5-di-third 4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6-diisopropylphenylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di Tert-butylphenyl)octyl phosphite, ginseng (mixed mono- and dinonylphenyl phosphite), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, double (2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-octadecyloxycarbonylethyl- Phenyl) pentaerythritol diphosphite, etc. Among these, a phosphite and a phosphate are preferable.

The sulfur-based antioxidant of the antioxidant (D) may, for example, be 3,3'-dithiogallate diacetate or bis(2-methyl-4-(3-n-dodecyl)thiopropionate Oxy)-5-t-butylphenyl) sulfide, distearyl-3,3'-thiodipropionate, pentaerythritol lanthanum (3-lauryl) thiopropionate, and the like.

The amount of the antioxidant (D) is preferably 0.1 parts by weight or more and 100 parts by weight or less, particularly preferably 0.1 parts by weight or more and 15 parts by weight or less based on 100 parts by weight of the cyclic olefin resin (A-1).

The photosensitive resin composition (I) of the present invention may further contain an additive such as a compound (F) having an acid polymerizable functional group, a leveling agent, a flame retardant, and a plasticizer, as necessary.

In the photosensitive resin composition (I) of the present invention, the cyclic olefin resin (A-1), the organic ruthenium compound (B1) represented by the general formula (1), the sulfur-containing organic ruthenium compound (B2), and The photoacid generator (C) and other components added as needed are dissolved in a solvent and used after forming a varnish. The solvent is a non-reactive solvent and a reactive solvent, and the non-reactive solvent has a carrier action of a resin or an additive, and is removed during coating or hardening. The reactive solvent contains a reactive group which is compatible with the hardener added to the resin composition. The non-reactive solvent may be a hydrocarbon solvent or an aromatic solvent, and examples thereof include a hydrocarbon such as pentane, hexane, heptane, cyclohexane or decalin, and a hydrocarbon solvent of a cycloalkane; benzene, toluene, xylene, and symmetry. An aromatic solvent such as trimethylbenzene. As the non-reactive solvent, for example, diethyl ether, tetrahydrofuran, anisole, acetate, ester, lactone, ketone, decylamine can also be used. Examples of the reactive solvent include a cyclic ether compound such as cyclohexene oxide and α-pinene oxide; and an aromatic ring such as [methylenebis(4,1-exphenoxymethylene)]diethylene oxide. a cycloaliphatic vinyl ether compound such as 1,4-cyclohexanedimethanol divinyl ether; or an aromatic compound such as bis(4-vinylphenyl)methane; these may be used alone or in combination of two or more. . The solvent is preferably symmetrical trimethylbenzene or decalin, and these are preferably used for resin coating on a substrate such as ruthenium, ruthenium dioxide, ruthenium nitride or ruthenium oxynitride.

The amount of the solid matter when the photosensitive resin composition (I) of the present invention is dissolved in a solvent (in other words, the amount of the component other than the solvent in the solution in which the photosensitive resin composition (I) of the present invention is dissolved in a solvent) It is 5 parts by weight or more and 60 parts by weight or less, preferably 30 parts by weight or more and 55 parts by weight or less, and particularly preferably 35 parts by weight or more and 45 parts by weight or less. Further, when the photosensitive resin composition (I) of the present invention is dissolved in a solvent, the solution viscosity is 10 cP or more and 25,000 cP or less, preferably 100 cP or more and 3,000 cP or less.

In the present invention, the cyclic olefin resin (A-1), the organic ruthenium compound (B1) represented by the formula (1), the sulfur-containing organic ruthenium compound (B2), and the photoacid generator (C), And an organic hydrazine compound (B3), an antioxidant (D), a sensitizer, an acid scavenger, a leveling agent, an antioxidant, a flame retardant, a plasticizer, a decane coupling agent, etc., which are added to the solvent, as needed By mixing, a solution of the photosensitive resin composition (I) of the present invention can be obtained.

Next, the photosensitive resin composition (II) of the present invention will be described. The photosensitive resin composition (II) of the present invention is substituted with a cyclic olefin resin (A-1) having an acid polymerizable functional group of the photosensitive resin composition (I) of the present invention, and is substituted with a photopolymerizable functional group. The cyclic olefin resin (A-2) is substituted with a photopolymerizable functional group as a photopolymerizable functional group, and the photoacid generator (C) is substituted with a photopolymerization initiator (E). The photosensitive resin composition (I) of the invention is similar. In addition, the cyclic olefin resin (A-2) having a photopolymerizable functional group is substituted by (acid group) in the acid polymerizable functional group in the cyclic olefin resin (A-1) having an acid polymerizable functional group. Other than the photopolymerizable functional group such as an acrylonitrile group, the same applies to the cyclic olefin resin (A-1) having an acid polymerizable functional group, and the production method thereof is to change the acid polymerizable functional group to photopolymerization. The rest of the functional group is the same as the method for producing the cyclic olefin resin (A-1) having an acid polymerizable functional group.

The cyclic olefin resin (A-2) having a photopolymerizable functional group is preferably a cyclic olefin resin composed of one or more of the structural units represented by the general formula (6), and R ¹¹ to R ¹⁴ At least one of them is a cyclic olefin resin (A-2) having a structural unit ratio of an alkenyl group or an alkynyl group of 20 to 60 mol% based on the total structural unit.

The photopolymerization initiator (E) is removed before being irradiated with actinic rays to generate a radical, and the rest is not particularly limited, and examples thereof include diphenyl ketone, acetophenone, and benzoin. Benzoin isobutyl ether, benzoin methyl benzoate, benzoin benzoic acid, benzoin methyl ether, benzyl sulfinyl sulfide, benzyl, dibenzyl, diethylidene and the like. In addition, the photopolymerization initiator (E) is contained in the photosensitive resin composition (II) of the present invention, and optionally contains a photopolymerization initiator (E). Further, the photosensitive resin composition (II) of the present invention may further contain a compound (G) having a photopolymerizable functional group as needed.

The photosensitive resin composition (III) of the present invention will be described. In the photosensitive resin composition (III) of the present invention, the cyclic olefin resin (A-1) having an acid polymerizable functional group of the photosensitive resin composition (I) of the present invention is substituted with an acid polymerizable functional group. The same is true for the photosensitive resin composition (I) of the present invention, except that the cyclic olefin resin (A-3) having a photopolymerizable functional group and the compound (F) having an acid polymerizable functional group are further contained. . The cyclic olefin resin (A-3) is a cyclic olefin resin (A-1) having an acid polymerizable functional group by using a monomer having no acid polymerizable functional group and a photopolymerizable functional group. The monomer having an acid polymerizable functional group and a photopolymerizable functional group is polymerized, and a reforming reaction after polymerization can be carried out to carry out the production. In the photosensitive resin composition (III) of the present invention, the cyclic olefin resin (A-3) having no acid polymerizable functional group and photopolymerizable functional group preferably has a polar functional group such as a carboxyl group.

The compound (F) having an acid polymerizable functional group may be a low molecular weight compound or a high molecular weight compound as long as it has an acid polymerizable functional group, and is not particularly limited, and examples thereof include a double Polyfunctional epoxy resin such as phenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether; polymethyl ( A polyoxyl group containing an epoxy group, etc., such as a glycidoxypropyl) siloxane. Further, a reactive solvent such as the above cycloaliphatic vinyl ether compound can be used as the compound (F) having an acid polymerizable functional group. Further, the photoacid generator (C) used in the photosensitive resin composition (III) of the present invention is the same as the photoacid generator (C) described in the photosensitive resin composition (I) of the present invention.

The photosensitive resin composition (IV) of the present invention will be described. The photosensitive resin composition (IV) of the present invention is a compound (F) having a photopolymerizable functional group in place of the compound (F) having an acid polymerizable functional group of the photosensitive resin composition (III) of the present invention. And the acid polymerizable functional group is substituted with a photopolymerizable functional group, and the photoacid generator (C) is substituted with the photopolymerization initiator (E), and the rest is combined with the photosensitive resin composition (III) of the present invention. same. In addition, the photopolymerization initiator (E) used in the photosensitive resin composition (IV) of the present invention is the same as the photopolymerization initiator (E) described in the photosensitive resin composition (II) of the present invention. In addition, the photopolymerization initiator (E) contained in the photosensitive resin composition (IV) of the present invention is optional, and a photopolymerization initiator (E) is optionally contained.

The compound (G) having a photopolymerizable functional group may be a low molecular weight compound or a high molecular weight compound as long as it has a photopolymerizable functional group, and is not particularly limited, and for example, Ethylene glycol acrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, glyceryl diacrylate, glyceryl dimethacrylate , a difunctional acrylate such as 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate; trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triacrylic acid Polyfunctional acrylates such as pentaerythritol, pentaerythritol trimethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

The photosensitive resin composition of the present invention contains both the organic antimony compound (B1) represented by the general formula (1) and the sulfur-containing organic antimony compound (B2), and thus the compound and the cyclic olefin resin (A) The interaction between the cyclic olefin resin (A) and the substrate and the metal can reduce the adverse effect of the sulfur-containing organic cerium compound (B2) on the preservation stability.

Next, a method of producing the semiconductor device of the present invention will be described using the photosensitive resin composition of the present invention. First, the photosensitive resin composition of the present invention is applied onto a support (for example, a germanium wafer, a ceramic, an aluminum substrate, or the like). Examples of the coating method include spin coating using a spin coater, spray coating using a spray coater, dipping, printing, roll coating, and the like.

Next, prebaking is carried out at 90 ° C to 140 ° C, and after the coating film is dried, actinic radiation is applied to the desired pattern shape. The actinic ray system may use X-rays, electron beams, ultraviolet rays, visible rays, or the like, and is preferably light having a wavelength of from 200 nm to 700 nm.

Next, after irradiation with actinic rays, in order to further accelerate the crosslinking reaction by the acid generated by irradiation with actinic rays, it is preferred to heat the system. The curing conditions are from 50 ° C to 200 ° C, preferably from 80 ° C to 150 ° C, and particularly from 90 ° C to 130 ° C.

Next, a relief pattern is obtained by dissolving and removing the unirradiated portion by the developer. Examples of the developing solution include hydrocarbons such as pentane, hexane, heptane, and cyclohexane such as alkane or cycloalkane; and aromatic solvents such as toluene, symmetrical trimethylbenzene, xylene, and symmetrical trimethylbenzene. Further, for example, decenes such as limonene, dipentene, decene, and kumarin; and ketones such as cyclopentanone, cyclohexanone, and 2-heptanone may be used, and it is preferred to use an appropriate amount in the above. The organic solvent of the surfactant. The developing method may take the form of, for example, spraying, paddle method, dipping, ultrasonication or the like. Next, the embossing pattern formed by the development is used for cleaning. The cleaning solution uses alcohol. Next, after the developer and the cleaning solution are removed, heat treatment is performed at 50 ° C to 200 ° C to terminate the crosslinking of the epoxy group, whereby a higher degree of characteristics can be exhibited.

Next, the germanium wafer formed by the existing pattern is diced and diced, and the obtained semiconductor wafer and the lead frame are heated and then fixed, and then electrically connected by a gold wire bonding wire. Then, a semiconductor device is sealed by using an epoxy-based sealing resin composition to obtain a semiconductor device. The sealing method can take the form of, for example, transfer molding, compression molding, injection molding, and the like.

Examples of the apparatus produced by using the photosensitive resin composition of the present invention include a general semiconductor device such as a memory element and a logic element, an image sensor, a display device using a liquid crystal or an organic EL, and a microelectromechanical system. (MEMS) devices, etc.

In the case of a general semiconductor device, characteristics such as photosensitivity, heat resistance, and even desired low-temperature processability and low internal stress are required for the photosensitive resin composition and the cured product thereof. The photosensitive resin composition of the present invention has excellent photosensitivity and heat resistance, and can impart low-temperature workability and low internal stress, and can be effectively used as a protective film, an insulating film, a photoresist, or the like of a semiconductor device.

In the case of the image sensor device, the photosensitive resin composition and the cured product thereof are required to have characteristics such as photosensitivity, pattern formation ability in particular thick film, and heat resistance. The photosensitive resin composition of the present invention not only has good heat resistance, but since the main chain belongs to an olefin structure, it is highly transparent in nature, and has a good pattern forming ability at the time of thick film, and thus can be effectively used as a compartment of an image sensor device. Wall (barrier material), protective film, etc.

In the case of the display device, characteristics such as photosensitivity, heat resistance, and transparency are required for the photosensitive resin composition and the cured product thereof. As described above, the photosensitive resin composition of the present invention is excellent in these properties, and thus can be effectively used as a protective film, an insulating film, a planarizing film, and the like of a display device.

In the case of a microelectromechanical system device, the photosensitive resin composition and the cured product thereof are required to have photosensitivity, particularly in the form of a thick film, and heat resistance. As described above, the photosensitive resin composition of the present invention is excellent in heat resistance and pattern forming ability in a thick film, and thus can be effectively used as a structure, an overcoat material, or the like of a microelectromechanical system device.

(Example)

Hereinafter, the present invention will be specifically described by way of examples, but is not limited thereto.

(Example 1)

Lifting Alkene/phenethyl reduction Alkene/glycidyl ether An example of a copolymer (A-1-1) having an ene = 50/20/30.

Drying at 110 ° C for 18 hours, then moving into a reaction vessel in a nitrogen-treated hand-held work box, adding ethyl acetate (230 g), cyclohexane (230 g), phenethyl Alkene (14.17g, 0.071mol), glycidyl methyl ether Alkene (14.0g, 0.100mol), and thiol Alkene (39.50 g, 0.168 mol). Oxygen was removed from the reaction medium by flowing dry N ₂ for 30 minutes in the solution. After the net completion was completed, 1.50 g (3.10 mmol) of bis(toluene)bis(perfluorophenyl)nickel dissolved in 8 ml of toluene was injected into the reactor. The reaction mixture was stirred at room temperature (23 ° C) for 18 hours, followed by the addition of a peracetic acid solution [150 mmol of peracetic acid (50 mol equivalent relative to the nickel catalyst), 57 ml of glacial acetic acid diluted with 130 ml of deionized water, and The mixture was mixed with 30 ml of hydrogen peroxide diluted with about 100 ml of deionized water to prepare a peracetic acid solution, and stirred for 18 hours.

Stirring was stopped and placed, and the aqueous layer was separated from the solvent layer. Then, the water layer was removed, and the remaining solvent layer was washed three times with 500 ml of distilled water, and stirred for 20 minutes. After standing, it was separated into two layers of an aqueous layer and a solvent layer, and then the aqueous layer was removed. . Then, adding excess acetone to the washed solvent layer to lower the The copolymer of the olefin skeleton was precipitated, recovered by filtration, and then dried overnight at 60 ° C in a vacuum oven. After drying, 66.1 g is obtained and is a drop A cyclic olefin resin (A-1-1) of a copolymer of an olefin skeleton (conversion ratio: 92%). The molecular weight of the cyclic olefin resin (A-1-1) was measured by GPC using a polystyrene standard, and it was confirmed that Mw was 105, 138, Mn was 46, 439, and polydispersity (PDI) was 2.26. The cyclic olefin resin (A-1-1) was measured by ¹ H-NMR, and it was confirmed that it was 20.2 mol% of phenethyl Aene, 29.1 mol% glycidyl methyl ether Alkene, and 50.7mol% sulfhydryl group a copolymer of olefins.

228 g (100 parts by weight) of the cyclic olefin resin (A-1-1) synthesized above was dissolved in 342 g of 2-heptanone, and then added: 4-methylphenyl-4-(1-methyl-ethyl) Phenyl hydrazine (pentafluorophenyl) borate (C) (12.768g, 1.25 × 10 ^-2 mol), 1-chloro-4-propoxy-9H-thioxanthone (2.736g, 8.98 ×10 ^-3 mol), phenolthiophene (1.025 g, 5.14×10 ^-3 mol), pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (11.40 g, 9.68 × 10 ^-3 mol), 3 - glycidoxypropyltrimethoxydecane (11.40 g, 4.82 x 10 ^-2 mol), 1,4-cyclohexanedimethanol divinyl ether (11.40 g, 5.81 x 10 ^-2 mol), 1, 6-bis(trimethoxydecyl)hexane (B1-1) (22.80 g (10 parts by weight), 6.98 x 10 ^-3 mol), and 4,4,13,13-tetraethoxy-3, 14-two -8,9-dithio-4,13-dihexadecane (B2-1) (6.84 g (3 parts by weight), 1.41 × 10 ^-2 mol), after dissolution, filtered with 0.2 μm fluororesin The filter was applied to obtain a photosensitive resin composition using a cyclic olefin resin.

Using the photosensitive resin composition prepared above, the following evaluation was carried out, and the results were summarized in Table 1. Further, regarding the composition in Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted, and the blending amount is described by weight.

[preservation assessment]

The photosensitive resin composition obtained was applied onto a ruthenium wafer by a spin coater, and then dried at 120 ° C for 5 minutes using a hot plate to obtain a film having a film thickness of about 10 μm. NSR-4425i [Nikon (shares), Ltd.] by using the coating film i-line stepper, exposure step performed by ^{100mJ / cm 2 ~ 1300mJ / cm} 2 through the mask. Then, heating was performed at 90 ° C for 4 minutes using a hot plate to promote heating of the crosslinking reaction of the exposed portion.

Next, the unexposed portion was dissolved and removed by immersing in cyclopentanone for 20 seconds, and then washed with propylene glycol monomethyl ether acetate for 20 seconds. As a result, it was confirmed that a pattern had been formed. The residual film ratio (film thickness after development/film thickness before development) at this time was 99.6%, which was a very high value. Further, the sensitivity at this time (the minimum exposure amount at which no pattern peeling was observed) was 190 mJ/cm ² .

The photosensitive resin composition which was left in the clean room for one week was subjected to pattern formation in accordance with the same conditions as above. The sensitivity at this time was 180 mJ/cm ² , and the rate of change from before the placement was only 5%.

[Adhesion evaluation 1]

After the photosensitive resin composition was cured to a thickness of 5 μm, it was applied onto a copper-plated 6-inch wafer by a spin coater, and then dried at 120 ° C for 5 minutes using a hot plate, and then used. The mask was attached to an exposure machine MA-8 (manufactured by Suss MicroTec AG), and exposed to light at 500 mJ/cm ² without passing through a photomask, and then heated at 90 ° C for 4 minutes using a hot plate. Then, it was heat-hardened by using a dust-free oven at an oxygen concentration of 1000 ppm or less and at 180 ° C for 60 minutes. The obtained coating film was cut into 100 squares of 1 mm square. The cellophane tape (Cellotape) (registered trademark) was pasted, but it was not torn, and the number of peeled coating films was 0, and it was confirmed that the cured film was excellent in adhesion to metal.

[Adhesion evaluation 2]

The substrate in the adhesion evaluation 1 was replaced with a 6-inch bare wafer, and the same adhesion was evaluated. As a result, it was confirmed that the number of peeling of the coating film was zero.

[Evaluation of Semiconductor Devices]

On the semiconductor wafer on which the circuit has been formed, a coating film of the photosensitive resin composition obtained above is formed, and then the semiconductor wafer and the lead frame are bonded, and the gold wire bonding wire is electrically connected, and epoxy is used. The sealing resin is subjected to sealing molding to obtain a semiconductor device. Then, the operation of the semiconductor device was confirmed, and as a result, it was confirmed that it functions normally as a semiconductor device.

(Example 2)

Drying at 110 ° C for 18 hours, then moving into a reaction vessel in a nitrogen-treated hand-held work box, adding ethyl acetate (600 g), cyclohexane (600 g), butyl drop Alkene (72.83g, 0.485mol), phenethyl group Alkene (64.07g, 0.323mol), glycidyl methyl ether Alkene (87.36g, 0.485mol), and thiol Alkene (75.74 g, 0.323 mol). Oxygen was removed from the reaction medium by flowing dry N ₂ for 30 minutes in the solution. After the net completion was completed, 6.58 g (0.0136 mol) of bis(toluene)bis(perfluorophenyl)nickel dissolved in 66 ml of acetone was injected into the reactor. The temperature was raised from 40 ° C to 60 ° C over 10 minutes, and while maintaining the temperature, the system was stirred for 3 hours, and then 245.0 g of glacial acetic acid was dissolved in 705.0 g of pure water (the pure water system was added to the obtained solution). 462.0 g of 30% hydrogen peroxide water was added, and after stirring at 50 ° C for 5 hours, 150 g of isopropyl alcohol was added to the system.

After the stirring was stopped and the separated aqueous layer was removed, 450 g of pure water and 150 g of isopropyl alcohol were added in three portions in the remaining organic layer, and the mixture was stirred for 20 minutes, and washed with water. The washed organic layer was diluted with 400 mL of cyclohexane, and added to 6 times the amount of methanol (7200 mL), and the precipitated polymer was collected by filtration. The obtained solid fraction was air-dried in air for 18 hours, and then dried under a reduced pressure of 1 mmHg for 24 hours to obtain 284.7 g of dried and belonged to a drop. A cyclic olefin resin (A-1-2) of a copolymer of an olefin skeleton (conversion rate: 96%). The molecular weight of the cyclic olefin resin (A-1-2) was measured by GPC using a polystyrene standard, and it was confirmed that Mw was 75,300. The cyclic olefin resin (A-1-2) was measured by ¹ H-NMR, and it was confirmed that it was 20.6 mol% of phenethyl group. Alkene, 30.3 mol% glycidyl methyl ether Alkene, 19.4mol% thiol drop Alkene, and 29.7 mol% butyl drop a copolymer of olefins.

Except that the copolymer (A-1-1) of Example 1 was replaced by the above-mentioned synthesized sulfhydryl group. Alkene/butyl group Alkene/phenethyl reduction Alkene/glycidoxymethyl drop Except for the copolymer (A-1-2) having an ene = 20/30/20/30, the production and evaluation of the photosensitive resin composition were carried out in the same manner. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Example 3)

The photosensitive resin composition was similarly applied except that the organic fluorene compound (B1-1) of Example 1 was replaced with 1,8-bis(trimethoxydecyl)octane (B1-2). Production and evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Example 4)

The preparation of the photosensitive resin composition was carried out in the same manner as in the above except that the organic ruthenium compound (B2-1) of Example 1 was replaced with γ-thiol propyl triethoxy decane (B2-2). Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Example 5)

The photosensitive resin composition was produced in the same manner as in the case where the organic ruthenium compound (B1-1) of Example 1 was 5 parts by weight, and the organic ruthenium compound (B2-1) was 1.5 parts by weight. Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Example 6)

The production of the photosensitive resin composition was carried out in the same manner as in the case where the organic ruthenium compound (B1-1) of Example 1 was 15 parts by weight, and the organic ruthenium compound (B2-1) was 4.5 parts by weight. Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Example 7)

The photosensitive resin composition was produced in the same manner as in the case where the organic ruthenium compound (B1-1) of Example 1 was used in an amount of 10 parts by weight, and the organic ruthenium compound (B2-1) was used in an amount of 2 parts by weight. Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Example 8)

The photosensitive resin composition was produced in the same manner as in the case where the organic ruthenium compound (B1-1) of Example 1 was 5 parts by weight, and the organic ruthenium compound (B2-1) was used in an amount of 3 parts by weight. Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Example 9)

The photosensitive resin composition was produced in the same manner as in the case where the organic ruthenium compound (B1-1) of Example 1 was used in an amount of 5 parts by weight, and the organic ruthenium compound (B2-1) was 0.3 parts by weight. Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Comparative Example 1)

The photosensitive resin composition was produced in the same manner as in the case where the organic ruthenium compound (B1-1) of Example 1 was used in an amount of 5 parts by weight, and the organic ruthenium compound (B2-1) was changed to 0 part by weight. Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

(Comparative Example 2)

The photosensitive resin composition was produced in the same manner as in the case where the organic ruthenium compound (B1-1) of Example 1 was used in an amount of 0 part by weight, and the organic ruthenium compound (B2-1) was changed to 5 parts by weight. Evaluation. Regarding the composition of Table 1, only the cyclic olefin resin (A) and the organic ruthenium compounds (B1) and (B2) are described, and the other components are omitted. The results of the physical property evaluation are shown in Table 1.

* Unable to evaluate due to stripping.

(industrial availability)

The present invention is a photosensitive resin composition which is excellent in preservability at normal temperature and excellent in adhesion, and can be suitably used as a surface protective film or an interlayer insulating film of a semiconductor element.

Claims (19)

A photosensitive resin composition comprising a cyclic olefin resin (A), an organic ruthenium compound (B1) represented by the following general formula (1), and a sulfur-containing organic ruthenium compound (B2): [Chemical Formula 1] (R ² O) ₃ -Si-R ¹ -Si-(OR ² ) ₃ (1) (In the formula (1), R ¹ is an alkylene group having 5 to 30 carbon atoms, or at least one or more aromatic rings The organic group; R ² is an alkyl group having 1 to 10 carbon atoms; the sulfur-containing organic cerium compound (B2) is an organic cerium compound represented by the following general formula (2) and the following general formula (3) One or more of the organic ruthenium compounds shown are selected: (In the formula (2), R ³ and R ⁴ are an alkyl group having 1 to 10 carbon atoms; and R ⁵ and R ⁶ are linear or branched alkyl groups, and have a carbon number of 1 to 10; k And l is 0 or 1; m is an integer from 1 to 10; n is 0, 1 or 2); (In the formula (3), R ⁷ and R ⁸ are an alkyl group having 1 to 10 carbon atoms; p is an integer of 0 to 10; and q is 0, 1 or 2). For example, the photosensitive resin composition of claim 1 of the patent scope, wherein (B2) The compounding amount ratio [(B1) weight / (B2) weight] of the above organic cerium compound (B1) is 1 or more and 10 or less. The photosensitive resin composition of the first aspect of the invention, wherein the compounding amount of the organic cerium compound (B1) is 1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the cyclic olefin resin (A). The photosensitive resin composition of the first aspect of the invention, wherein the R ¹ of the organic hydrazine compound (B1) is an alkylene group having 6 to 8 carbon atoms. The photosensitive resin composition of the first aspect of the invention, wherein the cyclic olefin resin (A) has a cyclic olefin resin having a structural unit represented by the following general formula (6): (In the formula (6), any one of an X-based oxygen atom (-O-) or a methylene group (-CH ₂ -); r is an integer of 0 to 5; and R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group ; R ¹¹ ~ R ¹⁴ systems may be the same or different). The photosensitive resin composition of claim 5, wherein in the cyclic olefin resin (A), the structural unit represented by the general formula (6) is present in an amount of 10 to 100 mol% based on the total structural unit. . The photosensitive resin composition of the first aspect of the invention, wherein the cyclic olefin resin (A) is a cyclic olefin resin (A-1) having an acid polymerizable functional group, and further contains a photoacid generator (C). The photosensitive resin composition of the seventh aspect of the invention, wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is one of the structural units represented by the following general formula (6). Or a cyclic olefin resin having two or more kinds, and at least one of R ¹¹ to R ¹⁴ is a structural unit of a functional group having an epoxy group, and is a total structural unit of 5 to 95 mol %; (In the formula (6), any one of an X-based oxygen atom (-O-) or a methylene group (-CH ₂ -); r is an integer of 0 to 5; and R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group ; R ¹¹ ~ R ¹⁴ series may be the same or different). The photosensitive resin composition of the seventh aspect of the invention, wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is a structural unit represented by the following general formula (7-1). It is constituted by a structural unit represented by the following general formula (7-2); (In the formulae (7-1) and (7-2), R ²¹ to R ²⁷ are hydrogen, alkyl, alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, having an ester Any of a functional group, a functional group having a keto group, or a functional group having an ether group). The photosensitive resin composition of the seventh aspect of the invention, wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is a structural unit represented by the following general formula (8-1). The structural unit shown in the general formula (8-2) and the structural unit shown in the following general formula (8-3); (In the formulae (8-1), (8-2) and (8-3), R ³¹ to R ⁴⁰ are hydrogen, alkyl, alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, An alkoxyalkyl group, a functional group having an ester group, a functional group having a keto group, or a functional group having an ether group; s is an integer of 0 to 5). The photosensitive resin composition of claim 10, wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group is a structural unit represented by the following formula (9-1), and the following formula ( 9-2) The structural unit shown and the structural unit shown in the following formula (9-3); The photosensitive resin composition of the ninth aspect of the invention, wherein the above-mentioned general cyclic olefin resin (A-1) having an acid polymerizable functional group The existence ratio of the structural unit represented by the formula (7-1) is 20 to 80 mol% of the total structural unit. The photosensitive resin composition of claim 10, wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group has a ratio of the structural unit represented by the above general formula (8-1) , 20~80 mol% of the total structural unit. The photosensitive resin composition of claim 13, wherein the cyclic olefin resin (A-1) having an acid polymerizable functional group has a structural unit ratio of the general formula (9-1) , 20~80 mol% of the total structural unit. The photosensitive resin composition of the first aspect of the invention, wherein the cyclic olefin resin (A) is reduced by the following general formula (5) a cyclic olefin resin obtained by polymerizing one or more of the ethylenic cyclic olefin monomers; (In the formula (5), any one of an X-based oxygen atom (-O-) or a methylene group (-CH ₂ -); r is an integer of 0 to 5; and R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group ; R ¹¹ ~ R ¹⁴ systems may be the same or different). The photosensitive resin composition of the first aspect of the invention, wherein the cyclic olefin resin (A) is a cyclic olefin resin (A-2) having a photopolymerizable functional group. The photosensitive resin composition of claim 16 wherein the cyclic olefin resin (A-2) having a photopolymerizable functional group is one of the structural units represented by the following general formula (6). Or a cyclic olefin resin having two or more kinds, and a ratio of the structural unit of at least one of R ¹¹ to R ¹⁴ being an alkenyl group or an alkynyl group is 20 to 60 mol% of the total structural unit; (In the formula (6), any one of an X-based oxygen atom (-O-) or a methylene group (-CH ₂ -); r is an integer of 0 to 5; and R ¹¹ to R ¹⁴ are hydrogen, an alkyl group, Alkenyl, alkynyl, nonylalkyl, aryl, aralkyl, alkoxyalkyl, functional group having an ester group, a functional group having a keto group, a functional group having an ether group, or a functional group having an epoxy group ; R ¹¹ ~ R ¹⁴ systems may be the same or different). The photosensitive resin composition of claim 1 further contains an antioxidant (D). A semiconductor device produced by using the photosensitive resin composition according to any one of claims 1 to 18.