Radiation-sensitive composition for forming insulating films, resin film having a pattern, and semiconductor circuit board

Abstract

To provide a radiation-sensitive composition for forming insulating films that has a low dielectric constant, low dielectric loss tangent, excellent elongation properties, and high reliability, and that also possesses photolithographic properties. [Solution] A radiation-sensitive composition for forming an insulating film, comprising a specific polyfunctional styryl compound (A-2), a polymer (B) having a group Y at its terminus that reacts with the styryl group of the polyfunctional styryl compound (A-2), and a photopolymerization initiator (C), wherein the polymer (B) is a polymer having a specific repeating structural unit, and the group Y is represented by the following formula (Y1). TIFF2026091294000041.tif25170

Description

[Technical Field]

[0001] The present invention relates to a radiation-sensitive composition for forming an insulating film, a resin film having a pattern, and a semiconductor circuit substrate. [Background technology]

[0002] With the recent advancements in the performance of information terminal devices and the dramatic progress in network technology, electrical signals used in the information and communication field are becoming higher frequencies to achieve higher speeds and larger capacities. In semiconductor circuit boards used in such devices, measures are being taken to reduce transmission loss, which is a challenge when transmitting and processing high-frequency electrical signals.

[0003] To address these challenges, insulating films used in semiconductor circuit boards are required to have low dielectric constant and low dielectric loss tangent in the high-frequency range (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-29504 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] To increase the density and performance of semiconductor circuit boards, packaging technologies using silicon interposers and fan-out type packaging technologies using molded substrates have been proposed. However, because the thermal expansion coefficients of these substrate materials and insulating films differ, warping deformation can easily occur due to temperature changes in the semiconductor circuit board manufacturing process and the operating environment of information terminal equipment. If the elongation of the insulating film is low, there is a problem that the insulating film may break due to its inability to withstand warping deformation. Furthermore, high reliability that can maintain elongation is required in environmental load tests (e.g., PCT tests) that simulate the operating environment of information terminal equipment.

[0006] Furthermore, insulating films used in semiconductor circuit boards are used between fine-pitch electrode pads and wiring. For this reason, compositions for forming patterned insulating films and other resin films (hereinafter also referred to as "patterned resin films") require photolithographic properties that allow for patterning by exposure and development.

[0007] The present invention aims to solve the above problems by providing a radiation-sensitive composition for forming an insulating film that has a low dielectric constant, low dielectric loss tangent, excellent stretchability, and high reliability, and is photolithographic; a patterned resin film with a low dielectric constant, low dielectric loss tangent, excellent stretchability, and high reliability, and a method for manufacturing the same; and a semiconductor circuit board including a patterned resin film with a low dielectric constant, low dielectric loss tangent, excellent stretchability, and high reliability. [Means for solving the problem]

[0008] The inventors diligently conducted research to solve the above problems. As a result, they found that the above problems can be solved by a radiation-sensitive composition for forming an insulating film containing a specific polyfunctional compound, a specific polymer, and a photopolymerization initiator, and thus completed the present invention. Examples of embodiments of the present invention are shown below.

[0009] [1] At least one polyfunctional compound (A) selected from polyfunctional maleimide compounds (A-1) and polyfunctional styryl compounds (A-2), A polymer (B) having a group Y that reacts with the maleimide group of the polyfunctional maleimide compound (A-1) or the styryl group of the polyfunctional styryl compound (A-2), and It contains a photopolymerization initiator (C), The polymer (B) is a polymer having repeating structural units represented by the following formula (a2), A radiation-sensitive composition for forming an insulating film, wherein the group Y is represented by the following formula (Y1).

[0010] [ka] [In formula (a2), each of the two X independently represents a single bond, an oxygen atom, a sulfur atom, an amide bond, -NH-C(O)-NH- or -SO2-, and at least one X is an oxygen atom, a sulfur atom, an amide bond, -NH-C(O)-NH- or -SO2-, R a21 This refers to a divalent hydrocarbon group, or a divalent group in which a hydrogen atom in the said divalent hydrocarbon group is substituted with a functional group other than a heterocyclic group. R a22 This refers to a divalent hydrocarbon group, a divalent group in which a hydrogen atom in the divalent hydrocarbon group is substituted with a functional group other than a heterocyclic group, or a heterocyclic group. R a21 and R a22 It may have the aforementioned base Y.

[0011] [ka] [In formula (Y1), R Y1 L represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y1 The symbols indicate a single bond, an alkanediyl group having 1 to 5 carbon atoms, -C(O)O-, -NH-C(O)-NH-, or a combination thereof, and * indicates the position where it bonds to the main chain or side chain constituting polymer (B).

[0012] [2] Polyfunctional maleimide compound (A-1), A polymer (B) having a group Y that reacts with the maleimide group of the polyfunctional maleimide compound (A-1), and It contains a photopolymerization initiator (C), The polymer (B) is a polymer having repeating structural units represented by the following formula (a2), A radiation-sensitive composition for forming an insulating film, wherein the group Y is represented by the following formula (Y1).

[0013] [ka] [In formula (a2), each of the two Xs independently represents a single bond, an oxygen atom, a sulfur atom, an amide bond, -NH-C(O)-NH-, or -SO2-, and at least one X is an oxygen atom, a sulfur atom, an amide bond, -NH-C(O)-NH-, or -SO2-. R a21 represents a divalent hydrocarbon group or a divalent group in which a hydrogen atom in the divalent hydrocarbon group is substituted with a functional group other than a heterocyclic ring. R a22 represents a divalent hydrocarbon group, a divalent group in which a hydrogen atom in the divalent hydrocarbon group is substituted with a functional group other than a heterocyclic ring, or a heterocyclic ring-containing group. R a21 and R a22 may have the group Y.]

[0014]

Chemical formula

[0015] [3] The radiation-sensitive composition for forming an insulating film according to item [2], further containing a polyfunctional styryl compound (A-2).

[0016] [4] The radiation-sensitive composition for forming an insulating film according to any one of items [1] to [3], wherein the polyfunctional maleimide compound (A-1) has three or more maleimide groups. [5] The radiation-sensitive composition for forming an insulating film according to any one of items [1] to [4], wherein the polyfunctional maleimide compound (A-1) has a phenolic hydroxyl group.

[0017] [6] The radiation-sensitive composition for forming an insulating film according to any one of items [1] to [5], wherein the polymer (B) is a polyimide, a polyimide precursor, a polybenzoxazole, a polybenzoxazole precursor, or a polyphenylene ether. [7] The radiation-sensitive composition for forming an insulating film according to any one of the items [1] to [6], wherein the polymer (B) has the group Y at its terminal.

[0018] [8] The aforementioned R a21 A radiation-sensitive composition for forming an insulating film according to any one of items [1] to [7], wherein the group is an arylene group. [9] The aforementioned R a22 The radiation-sensitive composition for forming an insulating film according to any one of items [1] to [8], wherein the group is a divalent group obtained by removing two hydrogen atoms from a pyrimidine, or an arylene group.

[0019]

[10] A method for producing a patterned resin film, comprising the steps of: (1) forming a coating film of an insulating film-forming radiation-sensitive composition described in any one of items [1] to [9] on a substrate; (2) selectively exposing the coating film; and (3) developing the exposed coating film with a developer containing an organic solvent.

[0020]

[11] A patterned resin film obtained by curing a radiation-sensitive composition for forming an insulating film as described in any one of items [1] to [9].

[12] A semiconductor circuit board comprising a resin film having the pattern described in item

[11] . [Effects of the Invention]

[0021] According to the present invention, it is possible to provide a radiation-sensitive composition for forming an insulating film that has a low dielectric constant, low dielectric loss tangent, excellent stretchability, and high reliability, and also has photolithographic properties. Furthermore, it is possible to provide a patterned resin film with a low dielectric constant, low dielectric loss tangent, excellent stretchability, and high reliability, a method for manufacturing the same, and a semiconductor circuit board including a patterned resin film with a low dielectric constant, low dielectric loss tangent, excellent stretchability, and high reliability. [Modes for carrying out the invention]

[0022] The present invention will be described in detail below. [Radiation-sensitive composition for forming an insulating film] The radiation-sensitive composition for forming insulating films of the present invention (hereinafter also simply referred to as "the composition of the present invention") contains at least one polyfunctional compound (A) selected from a polyfunctional maleimide compound (A-1) and a polyfunctional styryl compound (A-2), a polymer (B) having a group Y that reacts with the maleimide group of the polyfunctional maleimide compound (A-1) or the styryl group of the polyfunctional styryl compound (A-2), and a photopolymerization initiator (C).

[0023] <Polyfunctional compound (A)> The polyfunctional compound (A) used in the present invention is at least one selected from a polyfunctional maleimide compound (A-1) and a polyfunctional styryl compound (A-2).

[0024] ≪Polyfunctional maleimide compound (A-1)≫ The polyfunctional maleimide compound (A-1) used in the present invention is a compound having two or more maleimide groups, preferably three or more, in its molecule, with an upper limit of preferably 10, more preferably 4, maleimide groups.

[0025] The maleimide group is a group that directly acts on group Y, which will be described later, during photocrosslinking and thermal crosslinking, and it is thought that the following reactions may proceed, for example.

[0026] [ka]

[0027] Therefore, by containing the polyfunctional maleimide compound (A-1) in the composition of the present invention, a crosslinked structure can be formed, for example, by consuming the group Y of polymer (B) during exposure, thereby obtaining a highly reliable cured film.

[0028] Examples of the polyfunctional maleimide compound (A-1) include the compound represented by formula (A1) (hereinafter also referred to as "crosslinkable maleimide compound (A1)"). By using the crosslinkable maleimide compound (A1), the cured film formed from the composition of the present invention can exhibit the above-mentioned effects of improved elongation and reliability.

[0029] [ka]

[0030] In formula (A1), R A1 This is an organic group, and examples of organic groups include aromatic ring-containing groups such as alkanediyl groups and arylene groups, alicyclic ring-containing groups such as cycloalkylene groups, and groups derived from dimer acids obtained from unsaturated fatty acids.

[0031] The number of carbon atoms in the alkanediyl group is usually 1 to 20, preferably 2 to 10. Examples of aromatic ring-containing groups and alicyclic ring-containing groups include arylene groups with 6 to 20 carbon atoms and cycloalkylene groups with 3 to 20 carbon atoms, as well as -ZX A1 A base represented by -Z-, -ZOZX A1 The base represented by -ZOZ-, -R A2 -ZR A2 A group represented by - is an example. Z is a benzene ring or a cyclohexane ring, each independently having one or more substituents such as an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. A1 R is a direct bond, -O-, -SO2-, an alkanediyl group having 1 to 10 carbon atoms, or an alicyclic group having 3 to 20 carbon atoms. A2 This is an alkanediyl group having 1 to 10 carbon atoms.

[0032] Examples of alkanediyl groups include methylene, ethanediyl, propanediyl, hexanediyl, octanediyl, nonanediyl, and decanediyl groups. Examples of arylene groups include phenylene, methylphenylene, t-butylphenylene, and naphthylene groups. Examples of cycloalkylene groups include cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl groups. Examples of alkyl groups include methyl, ethyl, and propyl groups. Examples of alkoxy groups include methoxy and ethoxy groups. Examples of alicyclic rings include cyclohexane rings and tricyclodecane rings.

[0033] Specific examples of crosslinkable maleimide compounds (A1) include, for example, N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(2,2,4-trimethylhexane)bismaleimide ("BMI-TMH" manufactured by Yamato Chemical Industries, Ltd.), N,N'-p-phenylenebismaleimide, and N,N'-m-phenylenebismaleimide (manufactured by Yamato Chemical Industries, Ltd.). (BMI-3000 manufactured by Daiwa Chemical Industries, Ltd.), N,N'-4-methyl-1,3-phenylenebismaleimide (BMI-7000 manufactured by Daiwa Chemical Industries, Ltd.), N,N'-2,4-trylenebismaleimide, N,N'-2,6-trylenebismaleimide, N,N'-p-xylylenebismaleimide, N,N'-m-xylylenebismaleimide, N,N'-(1,3-dimethyl Examples include N,N'-(1,4-dimethylethylenecyclohexane)bismaleimide, N,N'-(4,4'-biphenylene)bismaleimide, N,N'-(4,4'-diphenylmethane)bismaleimide (manufactured by Yamato Chemical Industries, Ltd. as "BMI-1000"), N,N'-(3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane)bismaleimide (manufactured by Yamato Chemical Industries, Ltd. as "BMI-5100"), N,N'-(4,4'-dicyclohexylmethane)bismaleimide, N,N'-(4,4'-diphenyloxy)bismaleimide, N,N'-(4,4'-diphenylsulfone)bismaleimide, and compounds represented by the following formula (manufactured by Yamato Chemical Industries, Ltd. as "BMI-4000").

[0034] [ka]

[0035] Other specific examples of crosslinkable maleimide compounds (A1) include bis[4-(4-maleimidophenoxy)phenyl]methane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis[4-(4-maleimidophenoxy)phenyl]octane, bis[4-(4-maleimidophenoxy)phenyl]decane, bis[4-(4-maleimidophenoxy)phenyl]cyclohexane, and bis[4-(4-maleimidophenoxy)phenyl]-tricyclo-[5.2.1.O 2.6 Deccan is one example.

[0036] At least one hydrogen atom in the benzene ring and cyclohexane ring of the above example compound is independently C 1-10 It may be substituted with an alkyl group. Examples of alkyl groups include a methyl group, an ethyl group, and a propyl group.

[0037] In addition, bismaleimide compounds in which both ends of a polyoxyalkylenediamine are sealed with maleic anhydride can also be used. Examples include bismaleimide compounds in which both ends of a polyoxyethylenediamine are sealed with maleic anhydride, bismaleimide compounds in which both ends of a polyoxypropylenediamine are sealed with maleic anhydride, and bismaleimide compounds in which both ends of a polyoxybutylenediamine are sealed with maleic anhydride.

[0038] The polyfunctional maleimide compound (A-1) is a compound represented by formula (0) described in International Publication No. 2019 / 167359, and has at least two R 1A However, polyfunctional maleimide compounds, which are maleimide groups having 4 to 30 carbon atoms and may have substituents, can also be used. In addition, various polyfunctional maleimide compounds obtained by methods described in International Publication No. 2019 / 167359

[0207] to

[0255] , etc., can also be used.

[0039] As the aldehydes used in the method described in International Publication No. 2019 / 167359, for example, dialdehyde compounds having phenolic hydroxyl groups, as shown below, can be used. This makes it possible to obtain polyfunctional maleimide compounds having phenolic hydroxyl groups.

[0040] [ka]

[0041] Examples of polyfunctional maleimide compounds (A-1) containing a polyfunctional maleimide compound having a phenolic hydroxyl group, obtained by the method described in International Publication No. 2019 / 167359, include the compound (A-M1) represented by the following formula (M1), or a polymer of said compound (A-M1).

[0042] [ka]

[0043] In formula (M1), R M11 These each independently represent a monovalent organic group having either a hydroxyl group or a maleimide group. R M12 This represents a hydroxyl group, an alkoxy group, or a thiol group. L M11 This refers to a single bond, an alkanediyl group having 1 to 5 carbon atoms, a divalent aromatic ring-containing group, or a group combining these. n M11 This represents an integer from 1 to 4. Multiple R M11 Two or more of these are monovalent organic groups containing a maleimide group.

[0044] Examples of the C1-C5 alkanediyl group include a methylene group, an ethanediyl group, a propanediyl group, a butanediyl group, and a pentanediyl group. Examples of the aforementioned divalent aromatic ring-containing group include those similar to those exemplified as aromatic ring-containing groups in formula (A1).

[0045] Examples of monovalent organic groups having the maleimide group include the groups represented by the following formulas (M31) to (M33).

[0046] [ka]

[0047] In equations (M31), (M32), and (M33), * represents R in equation (M1). M11 This represents the bond with the carbon atom to which it is bonded.

[0048] In formula (M31), R M311 n represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, or a hydroxyl group. M311 This represents an integer between 0 and 4.

[0049] In formula (M32), R M321 n represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, or a hydroxyl group. M321 represents an integer from 0 to 4, and n M322 This represents either 0 or 1.

[0050] In formula (M33), R M331 n represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, or a hydroxyl group. M331 represents an integer from 0 to 4, and n M332 This represents either 0 or 1.

[0051] Examples of the group represented by the above formula (M31) include the N-phenylmaleimide group, the 3-ethyl-5-methyl-4-maleimoidphenyl group, the 3-methoxy-4-maleimoidphenyl group, and the 3-phenyl-4-maleimoidphenyl group.

[0052] Examples of the polymer of the aforementioned compound (A-M1) include the compound (A-M2) represented by the following formula (M2).

[0053] [ka]

[0054] In formula (M2), R M21 Each independently represents either a hydrogen atom or a maleimide group. R M12 , L M11 and n M11 R in equation (M1) M12 , L M11 and n M11 It is synonymous with, n M22 This represents an integer from 1 to 10. Multiple R M21 Two or more of these are maleimide groups.

[0055] Commercially available polyfunctional maleimide compounds (A-1) may be used. Examples of commercially available polyfunctional maleimide compounds (A-1) include "BMI-2000" and "BMI-2300" manufactured by Yamato Chemical Industries, Ltd., represented by the following formula (M41); "MIR-3000" and "MIR-5000" manufactured by Nippon Kayaku Co., Ltd., represented by the following formula (M42); and "SLK-3000", "SLK-6895", "SLK-1500", "SLK-2500", and "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd.

[0056] [ka]

[0057] n in the above formula (M41)M411 n represents the number of repeating units; in the case of BMI-2000, n M411 ≈2, in the case of BMI-2300, n M411 ≈ 2 to 5. Also, in the above formula (M42), n M421 n represents the number of repeating units, and in the case of MIR-3000, n M421 It is approximately 2 to 5.

[0058] The polyfunctional maleimide compound (A-1) can be used alone or in combination of two or more types.

[0059] ≪Polyfunctional Styryl Compound (A-2)≫ The polyfunctional styryl compound (A-2) used in the present invention is a compound having two or more styryl groups, preferably three or more, in its molecule, with an upper limit of preferably 10, more preferably 4, styryl groups.

[0060] The styryl group is a group that directly acts on group Y, which will be described later, during photocrosslinking and thermal crosslinking, and it is thought that the following reaction may proceed, for example.

[0061] [ka] In the above formula, R represents a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms.

[0062] Therefore, by containing a polyfunctional styryl compound (A-2) in the composition of the present invention, a crosslinked structure can be formed, for example, by consuming group Y of polymer (B) during exposure, thereby obtaining a highly reliable cured film.

[0063] Examples of the polyfunctional styryl compound (A-2) include the compound represented by formula (A2) (hereinafter also referred to as "crosslinkable styryl compound (A2)"). By using the crosslinkable styryl compound (A2), the cured film formed from the composition of the present invention can exhibit the above-mentioned effects of improved elongation and reliability.

[0064] [ka]

[0065] In formula (A2), n A2 R is an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, A2 n is derived from organic compounds A2 n A2 It is a valence organic group. Examples of the organic group include aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, heterocyclic compounds, and two or more of these compounds with single bonds, -O-, -S-, -SO2-, -NR N1 From compounds linked by -, -CO-, -COO-, and -CONH- A2 An example is a group from which a certain number of hydrogen atoms have been removed. N1 R is a group obtained by removing one hydrogen atom from a hydrogen atom or the above organic compound. A3 R is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. A4 n is an alkyl group having 1 to 10 carbon atoms. A4 R is an integer between 0 and 4. Note that a single molecule can contain multiple Rs. A3 , R A4 and R N1 If present, each unit may be identical or different.

[0066] The number of carbon atoms in aliphatic hydrocarbon compounds is usually 1 to 20, preferably 2 to 10. Aromatic ring hydrocarbon compounds include, for example, aromatic hydrocarbon compounds with 6 to 20 carbon atoms, such as benzene, naphthalene, anthracene, and fluorene. Heterocyclic compounds include nitrogen-containing heterocyclic compounds such as pyrrole, imidazole, pyrazole, pyridine, pyrimidine, triazine, pyridazine, and pyrazine; oxygen-containing heterocyclic compounds such as furan and pyran; sulfur-containing heterocyclic compounds such as thiophene and thioxanthene; and oxazoles and thiazoles containing multiple heteroatoms.

[0067] Specific examples of polycyclic styryl compounds (A2) include, for example, divinylbenzene and compounds represented by the following formula.

[0068] [ka]

[0069] At least one hydrogen atom in the benzene ring of the above example compound may be independently substituted with an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups include a methyl group, an ethyl group, and a propyl group.

[0070] The polyfunctional styryl compound (A-2) can be used alone or in combination of two or more types. Furthermore, it is preferable to use the polyfunctional styryl compound (A-2) in combination with the polyfunctional maleimide compound (A-1). Using the polyfunctional styryl compound (A-2) and the polyfunctional maleimide compound (A-1) in combination improves the residual film rate (the percentage of the patterned thin film that remains adequately).

[0071] In the composition of the present invention, the total content of the polyfunctional compound (A) is usually 0.1 to 200 parts by mass, preferably 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of polymer (B). When the content of the polyfunctional compound (A) is within the above range, the cured film obtained from the composition of the present invention exhibits excellent photolithography properties, chemical resistance, and crack resistance.

[0072] <Polymer (B)> The polymer (B) used in the present invention has a group Y (hereinafter sometimes referred to as "reactive group Y") that reacts with the maleimide group of the polyfunctional maleimide compound (A-1) or the styryl group of the polyfunctional styryl compound (A-2), and is a polymer having a repeating structural unit (hereinafter also referred to as "repeating structural unit (a2)") represented by the following formula (a2), wherein the group Y is represented by the following formula (Y1). Polymer (B) may be a polymer having one type of repeating structural unit (a2), or a polymer having two or more types of repeating structural units (a2).

[0073] [ka]

[0074] [ka]

[0075] The meanings of the symbols in equations (a2) and (Y1) are as follows:

[0076] 《X》 In formula (a2), the two X's independently represent an oxygen atom, a sulfur atom, an amide bond, -NH-C(O)-NH-, or -SO2-, and at least one X is an oxygen atom, a sulfur atom, an amide bond, -NH-C(O)-NH-, or -SO2-. Among these, oxygen atoms, amide bonds, and -NH-C(O)-NH- are preferred because the composition of the present invention can be used to form a patterned resin film with low dielectric constant, low dielectric loss tangent, and excellent stretchability, and the polymer (B) has excellent solubility in organic solvents and storage stability.

[0077] 《R a21 and R a22 》 In formula (a2), R a21 R represents a divalent hydrocarbon group, or a divalent group in which a hydrogen atom in the said divalent hydrocarbon group is substituted with a functional group other than a heterocyclic group (hereinafter also referred to as a "divalent substituted hydrocarbon group"). a21 It may have the aforementioned base Y.

[0078] In formula (a2), R a22 R represents a divalent hydrocarbon group, a divalent group in which a hydrogen atom in the divalent hydrocarbon group is substituted with a functional group other than a heterocyclic group (a divalent substituted hydrocarbon group), or a heterocyclic group. a22 It may have the aforementioned base Y.

[0079] R a21 As for the group, a divalent hydrocarbon group is preferred, R a22Preferably, the reactive group is a heterocyclic group without the reactive group or a divalent hydrocarbon group, and more preferably a heterocyclic group without the reactive group. This embodiment is preferable because it reduces the dipole moment in the short axis direction of polymer (B) (perpendicular to the main chain direction of polymer (B)), and allows for the formation of a patterned resin film with low dielectric constant, low dielectric loss tangent, and excellent elongation using the composition of the present invention.

[0080] (Divalent hydrocarbon group) R a21 and R a22 Examples of divalent hydrocarbon groups include alkanediyl groups, alicyclic hydrocarbon groups, and aromatic ring-containing hydrocarbon groups. Among these, aromatic ring-containing hydrocarbon groups are preferred because a patterned resin film with excellent heat resistance can be formed using the composition of the present invention. Hydrocarbon groups having both alicyclic and aromatic rings are classified as aromatic ring-containing hydrocarbon groups.

[0081] The number of carbon atoms in the alkanediyl group is usually 1 to 30, preferably 1 to 20. Examples of alkanediyl groups include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, and decane-1,10-diyl group; and branched alkanediyl groups obtained by adding one or more side chains consisting of alkyl groups having 1 to 4 carbon atoms to the linear alkanediyl groups exemplified above.

[0082] The carbon number of the alicyclic hydrocarbon group is usually 3 to 30, preferably 5 to 20. The alicyclic, i.e., aliphatic hydrocarbon ring, is, for example, a monocyclic aliphatic hydrocarbon ring such as a cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclodecane ring; norbornane ring, norbornene ring, adamantane ring, tricyclo[5.2.1.0 2,6 ] Decane ring, tricyclo[5.2.1.0 2,6Examples include polycyclic aliphatic hydrocarbon rings such as heptane rings. The alicyclic hydrocarbon group may have the aliphatic hydrocarbon ring as, for example, a monovalent group (e.g., a cycloalkyl group) or a divalent group (e.g., a cycloalkanediyl group); for example, a group in which at least one hydrogen atom in the alkanediyl group is substituted with a monovalent aliphatic hydrocarbon ring, or a group in which a divalent aliphatic hydrocarbon ring and an alkanediyl group are linked.

[0083] Examples of aromatic ring-containing hydrocarbon groups include the arylene group, -R 3 -Ar-R 3 - A divalent group represented by the above formula is shown. In the above formula, Ar is an arylene group; R 3 These are each independently an alkanediyl group (the number of carbon atoms in this alkanediyl group is usually 1 to 6).

[0084] In this specification, an arylene group means a divalent hydrocarbon group having one or more aromatic rings, i.e., aromatic hydrocarbon rings, and having two bonds located on the aromatic hydrocarbon rings. If an arylene group has multiple aromatic hydrocarbon rings, the two bonds may be located on the same aromatic hydrocarbon ring or on different aromatic hydrocarbon rings.

[0085] Examples of aromatic hydrocarbon rings included in the arylene group are benzene rings, naphthalene rings, anthracene rings, tetracene rings, pentacene rings, and other benzo-fused rings. The number of carbon atoms in the arylene group is preferably 6 to 50, and more preferably 6 to 30.

[0086] Examples of arylene groups include phenylene groups, naphthalene diyl groups, anthracenediyl groups, tetracenediyl groups, pentacenediyl groups, and divalent groups shown in formulas (a1-1) to (a1-4) below. Each aromatic hydrocarbon ring (e.g., benzene ring) contained in these groups may have one or more substituents, and examples of such substituents include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups having 1 to 30 carbon atoms. When an aromatic hydrocarbon ring has two or more substituents, each substituent may be the same or different.

[0087] [ka] In equations (a1-1) to (a1-4), * represents a combination.

[0088] In formula (a1-1), Z is independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. n is an integer from 0 to 3. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include alkanediyl groups such as methylene group, ethylene group, 1,1-dimethylmethane-1,1-diyl group, and decane-1,1-diyl group; aryl group-substituted alkanediyl groups such as diphenylmethylene group; cycloalkanediyl groups such as cyclohexane-1,1-diyl group and 3,3,5-trimethylcyclohexane-1,1-diyl group; phenylene group and fluorenylidene group.

[0089] In formulas (a1-2) to (a1-4), R 11 Each of these is independently a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms.

[0090] (Divalent substituted hydrocarbon group) R a21 and R a22The divalent substituted hydrocarbon group in this formula is a group into which a functional group other than the reactive group and heterocyclic group is introduced to the divalent hydrocarbon group. Examples of the functional group include halogen atoms, nitro groups, cyano groups, allyl groups, and vinyl groups, and other than the reactive group. Furthermore, from the viewpoint of low dielectric properties, it is preferable that the functional group is not a highly polar functional group such as a hydroxyl group.

[0091] (Heterocycle-containing group) R a22 Examples of heterocyclic ring-containing groups in this context include cyclic imide groups, alicyclic imide ring-containing groups having a structure in which a cyclic imide group is fused to an alicyclic hydrocarbon group, heteroaromatic ring-containing groups, and aromatic imide ring-containing groups having a structure in which a cyclic imide group is fused to an aromatic ring. Examples of the cyclic imide group and alicyclic imide ring-containing groups having a structure in which a cyclic imide group is fused to an alicyclic hydrocarbon group include groups represented by the following formula.

[0092] [ka] In the above equation, * represents a bond.

[0093] Examples of the aforementioned heteroaromatic rings include nitrogen-containing aromatic rings such as pyrimidine rings, pyrazine rings, pyridazine rings, pyridine rings, pyrrole rings, and pyrazole rings; oxygen-containing aromatic rings such as furan rings; sulfur-containing aromatic rings such as thiophene rings; nitrogen- and oxygen-containing aromatic rings such as benzoxazole rings and isoxazole rings; and nitrogen- and sulfur-containing aromatic rings such as isothiazole rings. An example of the aforementioned aromatic imide ring-containing group is a phthalimide group.

[0094] The heterocycle may have one or more substituents bonded to it, for example, 1 to 2 substituents. Examples of substituents include monovalent hydrocarbon groups having 1 to 20 carbon atoms, such as halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, allyl groups, and vinyl groups; monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms; nitro groups; and cyano groups, and other than the reactive groups. Furthermore, from the viewpoint of low dielectric properties, it is preferable that the functional group is not a highly polar functional group such as a hydroxyl group. The number of carbon atoms in the hydrocarbon group and halogenated hydrocarbon group is preferably 1 to 3. When the heterocycle has two or more substituents, each substituent may be the same or different.

[0095] Among the heteroaromatic ring-containing groups, a patterned resin film with low dielectric constant and excellent low dielectric loss tangent can be formed using the composition of the present invention. Therefore, a divalent group obtained by removing two hydrogen atoms from a benzoxazole ring-containing group, an aromatic imide ring-containing group, a pyrimidine, a pyrazine, or a pyridazine is preferred, a divalent group obtained by removing two hydrogen atoms from a pyrimidine, a pyrazine, or a pyridazine is more preferred, and a divalent group obtained by removing two hydrogen atoms from a pyrimidine is particularly preferred.

[0096] ≪R Y1 ≫ In formula (Y1), R Y1 The symbol represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and 3-pentyl groups.

[0097] R Y1 Preferably, it is a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

[0098] ≪L Y1 ≫ In formula (Y1), L Y1represents a single bond, an alkanediyl group having 1 to 5 carbon atoms, -C(O)O-, -NH-C(O)-NH-, or a group formed by combining these. Examples of the alkanediyl group having 1 to 5 carbon atoms include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group.

[0099] L Y1 is preferably a single bond, a methylene group, an ethylene group, -C(O)O-, -NH-C(O)-NH-, -C(O)O-(CH2) y -, -C(O)O-(CH2) y -OC(O)- or -C(O)O-(CH2) y -NH-C(O)-NH- (where y represents an integer of 1 to 3), and more preferably a single bond, -C(O)O-(CH2)2-OC(O)- or -C(O)O-(CH2)2-NH-C(O)-NH-.

[0100] In formula (Y1), * indicates the position of bonding to the main chain or side chain constituting polymer (B).

[0101] 《Preferred Configuration》 In the above formula (a2), the R a21 is preferably an aromatic ring-containing hydrocarbon group, and more preferably an arylene group. Also, in the above formula (a2), the R a22 is preferably an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group, and more preferably an arylene group or a divalent group obtained by removing two hydrogen atoms from pyrimidine.

[0102] When polymer (B) has the above preferred configuration, a patterned resin film excellent in low dielectric constant and low dielectric tangent can be formed using the composition of the present invention.

[0103] Preferred embodiments of polymer (B) include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polyphenylene ether.

[0104] The polymer (B) is preferably a linear polymer having the group Y at the polymer chain end, particularly a linear polymer represented by the following formula (BB), because a patterned resin film excellent in stretchability can be formed using the composition of the present invention.

[0105]

Chemical formula

[0106] In formula (BB), R a21 , R a22 , and X have the same meanings as the same symbols in formula (a2), and R a23 and R a24 each have the same meanings as R a21 and R a22 , respectively. Y means the reactive group Y. n indicates that the structure in () is a repeating structural unit, that is, the repeating structural unit (a2) is bonded as... -R a22 -X-R a21 -X-R a22 -X-R a21 -X-.... The repeating structural unit (a2) may be one kind or two or more kinds. m and p each independently represent an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 10, more preferably an integer of 0 or 1 to 5. For example, when p is an integer of 2 or more, -(X-R a23 ) p - is bonded as -X-R a23 -X-R a23 -... and indicates that the structure in () is a repeating structural unit, and the repeating structural unit may be one kind or two or more kinds. The same applies when m is 2 or more. In formula (BBB), R a21 , R a22 , and X have the same meanings as the same symbols in formula (a2), and Y, n, m, and p have the same meanings as the same symbols in formula (BB). R a25 and R a26 each have the same meanings as R a21 and R a22This is synonymous, but when a reactive group Y is bonded, it takes on a valency corresponding to the number of reactive groups Y. q and r are each independent integers of 2 or more, preferably integers from 2 to 8, more preferably integers from 2 to 4.

[0107] Composition of polymer (B) In polymer (B), the content of repeating structural units (a2) is usually 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on 100% by mass of polymer (B). In this embodiment, the composition of the present invention exhibits excellent resolution, and the resin film obtained from the composition of the present invention tends to have a low dielectric constant, a low dielectric loss tangent, and excellent elongation. The content of repeating structural units (a2) is, 13 It can be measured by 13C-NMR.

[0108] The group Y contained in polymer (B) can be qualitatively or quantitatively analyzed by combining matrix-assisted laser desorption / ionization, three-dimensional nuclear magnetic resonance spectroscopy, and titration methods.

[0109] The weight-average molecular weight (Mw) of polymer (B), measured by gel permeation chromatography, is typically 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 5,000 to 100,000, in polystyrene terms, from the viewpoint of the resolution of the composition of the present invention and the elongation of the resin film obtained from the composition of the present invention. Details of the method for measuring Mw are as described in the examples.

[0110] Polymer (B) may be used alone or in combination of two or more types. The lower limit of the content of polymer (B) in 100% by mass of the solid content of the composition of the present invention is usually 20% by mass, preferably 40% by mass, and more preferably 60% by mass; the upper limit is usually 99% by mass, preferably 95% by mass. When the content of polymer (B) is above the lower limit or below the upper limit, a radiation-sensitive composition for forming an insulating film capable of forming a patterned resin film with high resolution tends to be obtained. The solid content refers to all components other than the organic solvent (E) described later that may be included in the composition of the present invention.

[0111] Method for producing polymer (B) Polymer (B) can be produced, for example, by polycondensation. More specifically, when X is an oxygen atom, a bisphenol compound, a dihalogen compound, and an alkali metal compound can be used as monomers; when X is a sulfur atom, a bisthiol compound, a dihalogen compound, and an alkali metal compound can be used as monomers; and when X is an amide bond, a diamine compound, an acidic dianhydride, and an acidic dichloride can be used as monomers. Examples of reactive group Y modifiers include compounds that have one functional group identical to the functional group that reacts during the polycondensation of the above monomers, and that also have one or more groups Y.

[0112] Below, as an example of polymer (B), polymer (B11) is described, in formula (a2) where X is an oxygen atom and the reactive group Y is an α-methylstyryl group. Polymer (B11) can be obtained, for example, by polymerizing a phenol compound (bb1) having two phenolic hydroxyl groups, a halogen compound (bb2) having two halogen atoms, and a reactive group Y modifier (bb3) having one phenolic hydroxyl group and one α-methylstyryl group. The reactive group Y modifier can be represented by the following formula (YM).

[0113] [ka]

[0114] In formula (YM), R Y1 and L Y1 R in equation (Y1) Y1 and L Y1 It is synonymous with Z YM The group is not particularly limited as long as it is a group that can react with the functional group at the end of the main chain or side chain of polymer (B). For example, if the end of polymer (B) is an amino group, it can be an isocyanate group, an acid anhydride group, or a chlorine atom. If the end of the main chain or side chain of polymer (B) is a phenolic hydroxyl group, it can be a chlorine atom. If the end of the main chain or side chain of polymer (B) is a carboxyl group or an acid anhydride group, it can be an amino group or a hydroxyl group. If the end of the main chain or side chain of polymer (B) is a chlorinated heteroaromatic ring, it can be a hydroxyl group or an amino group.

[0115] In the synthesis of polymer (B11), for example, a phenol compound (bb1), a halogen compound (bb2), and a reactive group Y modifier (bb3) are polymerized in a suitable polymerization solvent in the presence of an alkali metal compound. The amount of phenol compound (bb1) used is usually less than 100 moles per 100 moles of halogen compound (bb2), preferably 90.0 to 99.9 moles. The amount of reactive group Y modifier (bb3) used is usually less than 50 moles per 100 moles of halogen compound (bb2), preferably 0.1 to 20.0 moles.

[0116] Examples of alkali metal compounds include carbonates, bicarbonates, and hydroxides of alkali metals such as lithium, sodium, and potassium. Among these, carbonates and hydroxides are preferred, and potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide are more preferred.

[0117] For polymers (B) in formula (a2) where X is not an oxygen atom, they can be produced, for example, by known polycondensation.

[0118] <Photopolymerization initiator (C)> The composition of the present invention contains a photopolymerization initiator (C). The photopolymerization initiator (C) is a compound that generates an active species that promotes the crosslinking reaction between the group Y in the polymer (B) and the polyfunctional compound (A) upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, or X-rays. The photopolymerization initiator (C) may be used alone or in combination of two or more types.

[0119] It is believed that exposure treatment of a coating film formed from the composition of the present invention promotes the crosslinking reaction between the group Y in the polymer (B) and the polyfunctional compound (A), forming a crosslinked structure in the exposed area and reducing its solubility in the developer.

[0120] As the photopolymerization initiator (C), a photosensitive radical polymerization initiator that generates radicals upon light irradiation is preferred, and examples include oxime compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, oxime compounds, particularly photoradical polymerization initiators having an oxime ester structure, are preferred in terms of sensitivity.

[0121] Photoradical polymerization initiators having an oxime ester structure may have geometric isomers due to the double bond in the oxime, but these are not distinguished and are both included in photoradical polymerization initiator (C).

[0122] Examples of photoradical polymerization initiators having an oxime ester structure include those described in WO2010 / 146883, JP 2011-132215, JP 2008-506749, JP 2009-519904, and JP 2009-519991.

[0123] Specific examples of photoradical polymerization initiators having an oxime ester structure include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl Examples include 9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime), etc.

[0124] These photopolymerization initiators (C) may be used individually or in combination of two or more. The lower limit of the content of photopolymerization initiator (C) per 100 parts by mass of polymer (B) in the composition of the present invention is usually 0.01 parts by mass, preferably 0.1 parts by mass, and more preferably 0.5 parts by mass; the upper limit is usually 30 parts by mass, preferably 20 parts by mass, and more preferably 10 parts by mass. If the content of photopolymerization initiator (C) is above the lower limit, the curing of the exposed area is sufficient, and the heat resistance of the patterned resin film tends to improve. If the content of photopolymerization initiator (C) is below the upper limit, a patterned resin film with high resolution is easily obtained without a decrease in transparency to the light used for exposure.

[0125] <Surfactant (D)> The composition of the present invention may contain a surfactant (D) from the viewpoint of improving applicability, defoaming properties, leveling properties, etc. The surfactant is not particularly limited, and known nonionic surfactants, fluorinated surfactants, and silicone surfactants can be used.

[0126] Examples of commercially available surfactants include BM-1000, BM-1100 (manufactured by BM Chemie), Megafac F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, S-113, S-131, S-141, S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone Co., Ltd.), and NBX-15 (manufactured by Neos Co., Ltd.). Examples include fluorine-based surfactants sold under names such as (manufactured by Kyoeisha Chemical Co., Ltd.); silicone-based surfactants sold under names such as KL-245, KL-270 (manufactured by Kyoeisha Chemical Co., Ltd.), SH28PA (manufactured by Toray Dow Corning Co., Ltd.); and nonionic surfactants sold under names such as Nonion S-6, Nonion 0-4, Pronon 201, Pronon 204 (manufactured by Nippon Oil & Fats Co., Ltd.), Emulgen A-60, A-90, A-500 (manufactured by Kao Corporation), KL-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0127] The surfactant (D) may be used alone or in combination of two or more types. The surfactant (D) is preferably used in an amount of 5 parts by mass or less, more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the polymer (B).

[0128] <Organic solvent (E)> The composition of the present invention may contain an organic solvent (E). By using an organic solvent (E), the handling properties of the composition of the present invention can be improved, and its viscosity and storage stability can be adjusted.

[0129] The organic solvent (E) is not particularly limited as long as it is an organic solvent capable of dissolving or dispersing each component, such as the polyfunctional compound (A), polymer (B), and photopolymerization initiator (C). Examples of organic solvents (E) include ketone solvents, alcohol solvents, ether solvents, ester solvents, amide solvents, and hydrocarbon solvents.

[0130] Examples of ketone solvents include linear ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone (methyl amyl ketone), ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; and 2,4-pentanedione, acetonylacetone, and acetophenone.

[0131] Examples of alcohol solvents include aliphatic monoalcohol solvents having 1 to 18 carbon atoms, such as 4-methyl-2-pentanol and n-hexanol; alicyclic monoalcohol solvents having 3 to 18 carbon atoms, such as cyclohexanol; polyhydric alcohol solvents having 2 to 18 carbon atoms, such as 1,2-propylene glycol; and polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether.

[0132] Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole.

[0133] Examples of ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; polyhydric alcohol carboxylate solvents such as propylene glycol acetate; polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate; polyhydric carboxylic acid diester solvents such as diethyl oxalate; lactone solvents such as γ-butyrolactone and δ-valerolactone; and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.

[0134] Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone; and chain-like amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0135] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, such as n-pentane and n-hexane; and aromatic hydrocarbon solvents having 6 to 16 carbon atoms, such as toluene and xylene.

[0136] As the organic solvent (E), at least one selected from ketone solvents, ester solvents, and amide solvents is preferred.

[0137] The composition of the present invention may contain one or more organic solvents (E). The amount of organic solvent (E) in the composition of the present invention is such that the solid content concentration in the composition is typically 10 to 50% by mass.

[0138] <Other ingredients> In addition to the components described above, the compositions of the present invention may contain other components, to the extent that they do not impair the purpose and properties of the present invention. Examples of other components include crosslinking agents other than the polyfunctional compound (A); polymers other than polymer (B); and additives such as low molecular weight phenol compounds, adhesion aids, crosslinked microparticles, leveling agents, sensitizers, inorganic fillers, and quenchers.

[0139] <Method for producing a radiation-sensitive composition for forming an insulating film> The composition of the present invention can be produced by uniformly mixing each component constituting the composition of the present invention. Furthermore, in order to remove foreign matter, the mixture obtained after uniformly mixing each component can be filtered using a filter or the like.

[0140] <Characteristics of radiation-sensitive compositions for forming insulating films> The patterned resin film obtained by curing the composition of the present invention exhibits excellent elongation. This is presumed to be due to the following reasons: Since polymer (B) has the reactive groups substantially only at the polymer chain ends, when the composition of the present invention is crosslinked, crosslinking occurs in such a way that the polymer chains in polymer (B) are extended, resulting in a low crosslinking density. On the other hand, it is thought that the polymer chains become highly intertwined, leading to loose interactions between the polymer chains. Therefore, it is presumed that the elongation of the resulting patterned resin film was improved.

[0141] Furthermore, the patterned resin film obtained from the composition of the present invention has a low dielectric constant and a low dielectric loss tangent. In order to obtain such low dielectric properties, it is preferable that the dipole moment in the short axis direction (perpendicular to the main chain direction of the polymer) of the repeating structural unit of the polymer used is small, and polymer (B) is suitable from this viewpoint. Moreover, as described above, since crosslinking mainly occurs at the polymer chain ends rather than in the repeating structural unit (a2) of polymer (B), it is presumed that the change in the dipole moment is small through the formation of the patterned resin film.

[0142] A coating film made from the composition of the present invention can be developed with a developer containing an organic solvent, as described later. When an aqueous solution containing an alkaline compound is used as the developer, highly polar, hygroscopic functional groups such as phenolic hydroxyl groups may be introduced into the repeating structural units of the polymer to impart alkaline developability to the polymer. In this case, a large amount of the highly polar functional groups introduced into the polymer is required, which is thought to result in high dielectric constant and dielectric loss tangent. In the present invention, since a developer containing an organic solvent can be used to form a patterned resin film, the amount of the highly polar functional groups introduced into the polymer can be reduced, and therefore low dielectric constant and low dielectric loss tangent can be achieved.

[0143] [Method for manufacturing a resin film having a pattern] The present invention provides a method for producing a patterned resin film (patterned resin film), comprising the steps of: (1) forming a coating film of the composition of the present invention on a substrate; (2) selectively exposing the coating film to light; and (3) developing the exposed coating film with a developer containing an organic solvent.

[0144] <Process (1)> In step (1), the composition of the present invention is typically applied to a substrate such that the final thickness of the patterned resin film obtained is, for example, 0.1 to 100 μm. The substrate after the composition has been applied is heated in an oven or on a hot plate, typically at 50 to 140°C for 10 to 360 seconds. In this way, a coating film consisting of the composition of the present invention is formed on the substrate.

[0145] Examples of substrates include silicon wafers, compound semiconductor wafers, wafers with metal thin films, glass substrates, quartz substrates, ceramic substrates, aluminum substrates, and substrates having semiconductor chips on their surfaces. Examples of coating methods include dipping, spraying, bar coating, roll coating, spin coating, curtain coating, gravure printing, screen printing, and inkjet printing.

[0146] <Process (2)> In step (2), the coating is selectively exposed using, for example, a contact aligner, stepper, or scanner. "Selectively" specifically means through a photomask on which a predetermined mask pattern is formed.

[0147] Examples of exposure light include ultraviolet light and visible light, and typically light with a wavelength of 200-500 nm (e.g., i-line (365 nm)) is used. The amount of irradiation due to exposure varies depending on the type and proportion of each component in the composition of the present invention and the thickness of the coating film, but the exposure amount is usually 100-1500 mJ / cm². 2 That is the case.

[0148] Furthermore, in order to allow the crosslinking reaction to proceed sufficiently, it is preferable to perform a heat treatment (post-exposure baking) after exposure. The conditions for the post-exposure heat treatment vary depending on the content of each component in the composition of the present invention and the thickness of the coating film, but are usually 70 to 250°C, preferably 80 to 200°C, for about 1 to 60 minutes.

[0149] <Process (3)> In step (3), the exposed coating is developed with a developer containing an organic solvent to dissolve and remove the unexposed areas, thereby forming a desired patterned resin film on the substrate. Examples of development methods include shower development, spray development, immersion development, and paddle development. Development conditions are typically 20-40°C for 1-10 minutes.

[0150] The developer contains one or more organic solvents. Examples of organic solvents in the developer include ketone solvents, alcohol solvents, ether solvents, ester solvents, amide solvents, hydrocarbon solvents, or liquids containing such organic solvents. Specific examples of these organic solvents include the compounds exemplified as organic solvent (E). Among these, at least one selected from ketone solvents, ester solvents, and amide solvents is preferred. Examples of components other than organic solvents in the developer include water, silicone oil, and surfactants.

[0151] The organic solvent content in the developing solution is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more.

[0152] Furthermore, after developing the exposed coating film using a developer containing an organic solvent to form a patterned resin film, the patterned resin film can be washed with water or the like and then dried.

[0153] The shape of the pattern in the patterned resin film is not particularly limited as long as it has an uneven structure, but examples include line-and-space patterns, dot patterns, hole patterns, and grid patterns.

[0154] <Process (4)> The method for manufacturing a patterned resin film of the present invention may include, after step (3), a step (4) of sufficiently curing the patterned resin film by heat treatment (post-bake) as needed, in order to fully exhibit its properties as an insulating film. The curing conditions are not particularly limited, but depending on the application of the patterned resin film, for example, heating at a temperature of 100 to 250°C for 30 minutes to 10 hours may be performed.

[0155] The patterned resin film obtained by the manufacturing method of the present invention can be suitably used as an insulating film (e.g., surface protective film, interlayer insulating film, planarization film) on a semiconductor circuit substrate.

[0156] [Semiconductor circuit boards] By using the composition of the present invention, a semiconductor circuit board can be manufactured that includes a resin film having the above-described pattern (patterned resin film). The semiconductor circuit board is useful as a high-frequency circuit board because it has a patterned resin film formed from the above-described composition of the present invention, preferably a surface protective film, an interlayer insulating film, and a patterned insulating film such as a planarization film. [Examples]

[0157] The present invention will be described more specifically below based on examples, but the present invention is not limited in any way to these examples. In the following descriptions of examples, unless otherwise specified, "parts" will be used to mean "parts by mass".

[0158] <Synthesis of polymer (B)> The weight-average molecular weight (Mw) of polymer (B) obtained in the synthesis example below was measured by gel permeation chromatography under the following conditions. • Column: Product name "TSKgelα-M" (manufactured by Tosoh Corporation) • Solvent: N-methyl-2-pyrrolidone ·Temperature: 40℃ • Detection method: Refractive index method • Standard material: Polystyrene • GPC device: Manufactured by Tosoh Corporation, device name "HLC-8320-GPC"

[0159] [Synthesis Example 1] Synthesis of Polymer (B1) In a four-necked flask, 177.65 mmol of 4,6-dichloropyrimidine was added as a halogen compound, 153.00 mmol of bisphenol A and 17.00 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane as phenol compounds, 17.00 mmol of 4-hydroxy-α-methylstyrene as a reactive group Y modifier, 239.83 mmol of potassium carbonate as an alkali metal compound, and N-methyl-2-pyrrolidone (0.5 g per 1 mmol of the total amount of halogen compounds, phenol compounds, and reactive group Y modifier) ​​as a polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 130°C for 6 hours, and the water generated during heating was removed from the Dean-Stark tube as needed. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain polymer (B1). The obtained polymer (B1) was then processed. 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (B1). The weight-average molecular weight (Mw) of polymer (B1) was 14,000.

[0160] [ka]

[0161] [Synthesis Example 2] Synthesis of Polymer (B2) In a four-necked flask, 153.46 mmol of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was added as the acidic dianhydride, 170.52 mmol of 2,2-bis[4-(4-aminophenoxy)phenyl]propane as the diamine, and N-methyl-2-pyrrolidone (2.0 g per 1 mmol total amount of acidic dianhydride and diamine) was added as the polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 40°C for 4 hours, and then further heated at 180°C for 4 hours. 170.52 mmol of 3-isopropenyl-α,α-dimethylbenzyl isocyanate was added as a reactive group Y modifier, and the contents of the flask were heated at 70°C for 4 hours. After the contents of the flask were cooled to room temperature, methanol was added, the precipitated solids were washed with methanol, and these solids were dried to obtain polymer (B2). The obtained polymer (B2) was then processed. 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (B2). The weight-average molecular weight (Mw) of polymer (B2) was 24,000.

[0162] [ka]

[0163] [Synthesis Example 3] Synthesis of Polymer (B3) In a four-necked flask, 157.31 mmol of pyromellitic anhydride was added as the acidic dianhydride, 174.79 mmol of 4,4'-diaminodiphenyl ether as the diamine, and N-methyl-2-pyrrolidone (1.0 g per 1 mmol of total acidic dianhydride and diamine) was added as the polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 40°C for 4 hours. After the contents of the flask were cooled to room temperature, 349.58 mmol of N,N-dimethylformamide dimethyl acetal was added and the contents of the flask were stirred at room temperature for 4 hours. As a reactive group Y modifier, 174.79 mmol of 3-isopropenyl-α,α-dimethylbenzyl isocyanate was added and the contents of the flask were heated at 70°C for 4 hours. After the contents of the flask were cooled to room temperature, methanol was added, the precipitated solids were washed with methanol, and these solids were dried to obtain polymer (B3). The obtained polymer (B3) 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (B3). The weight-average molecular weight (Mw) of polymer (B3) was 21,000.

[0164] [ka]

[0165] [Synthesis Example 4] Synthesis of Polymer (B4) In a four-necked flask, 162.23 mmol of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was added as the acidic dianhydride, 175.39 mmol of 2,2-bis[4-(4-aminophenoxy)phenyl]propane as the diamine, and N-methyl-2-pyrrolidone (2.0 g per 1 mmol total amount of acidic dianhydride and diamine) was added as the polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 40°C for 4 hours, and then further heated at 180°C for 4 hours. After the contents of the flask were cooled to room temperature, 105.23 mmol of 2-isocyanatoethyl methacrylate was added as a reactive group Y modifier, and the contents of the flask were heated at 40°C for 4 hours. After the contents of the flask were cooled to room temperature, methanol was added, the precipitated solids were washed with methanol, and these solids were dried to obtain polymer (B4). The obtained polymer (B4) 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (B4). The weight-average molecular weight (Mw) of polymer (B4) was 27,000.

[0166] [ka]

[0167] [Synthesis Example 5] Synthesis of Polymer (B5) In a four-necked flask, 173.04 mmol of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride was added as the acidic dianhydride, 346.07 mmol of 2-hydroxyethyl methacrylate was added as the reactive group Y modifier, 346.07 mmol of pyridine was added as the base, and N-methyl-2-pyrrolidone (2.0 g per 1 mmol of the total amount of acidic dianhydride and diamine) was added as the polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 40°C for 4 hours. After the contents of the flask were cooled to room temperature, 181.69 mmol of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was added as the diamine, and then 346.07 mmol of dicyclohexylcarbodiimide (DCC) was added under ice cooling, and the contents of the flask were stirred at room temperature for 4 hours. The precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain polymer (B5). The obtained polymer (B5) 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (B5). The weight-average molecular weight (Mw) of polymer (B5) was 20,000.

[0168] [ka]

[0169] [Synthesis Example 6] Synthesis of Polymer (B6) In a four-necked flask, 171.56 mmol of 4,6-dichloropyrimidine was added as a halogen compound, 150.00 mmol of bisphenol A and 37.50 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane as phenol compounds, 231.61 mmol of potassium carbonate as an alkali metal compound, and N-methyl-2-pyrrolidone (0.5 g per 1 mmol of the total amount of halogen compounds, phenol compounds, and reactive group Y modifier) ​​as a polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 130°C for 6 hours, with water generated during heating being removed from the Dean-Stark tube as needed. After the contents of the flask were cooled to room temperature, 150.00 mmol of 4-(chloromethyl)styrene was added as a reactive group Y modifier and 150.00 mmol of potassium carbonate as an alkali metal compound, and the contents of the flask were heated at 80°C for 4 hours. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain polymer (B6). The obtained polymer (B6) 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (B6). The weight-average molecular weight (Mw) of polymer (B6) was 12,000.

[0170] [ka]

[0171] [Synthesis Example 7] Synthesis of Polymer (B7) In a four-necked flask, 162.23 mmol of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was added as the acidic dianhydride, 175.39 mmol of 2,2-bis[4-(4-aminophenoxy)phenyl]propane as the diamine, and N-methyl-2-pyrrolidone (2.0 g per 1 mmol total amount of acidic dianhydride and diamine) was added as the polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 40°C for 4 hours, and then further heated at 180°C for 4 hours. After the contents of the flask were cooled to room temperature, 420.94 mmol of 4-(chloromethyl)styrene was added as a reactive group Y modifier, and 420.94 mmol of potassium carbonate was added as an alkali metal compound, and the contents of the flask were heated at 40°C for 4 hours. After the contents of the flask were cooled to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain polymer (B7). The obtained polymer (B7) was then processed. 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (B7). The weight-average molecular weight (Mw) of polymer (B7) was 19,000.

[0172] [ka]

[0173] [Synthesis Example 8] Synthesis of Polymer (RB1) In a four-necked flask, 171.56 mmol of 4,6-dichloropyrimidine was added as a halogen compound, 150.00 mmol of bisphenol A and 37.50 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane as phenol compounds, 231.61 mmol of potassium carbonate as an alkali metal compound, and N-methyl-2-pyrrolidone (0.5 g per 1 mmol of the total amount of halogen compound, phenol compound, and reactive group Y modifier) ​​as a polymerization solvent. After purging the flask with nitrogen, the contents of the flask were heated at 130°C for 6 hours, and the water generated during heating was removed from the Dean-Stark tube as needed. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain polymer (RB1). The obtained polymer (RB1) 13 Analysis using 1C-NMR revealed that the polymer has the structure shown in formula (RB1). The weight-average molecular weight (Mw) of polymer (RB1) was 12,000.

[0174] [ka]

[0175] Table 1 below shows the types and amounts of monomers used in Synthesis Examples 1 to 8, as well as the weight-average molecular weight (Mw) of the resulting polymers.

[0176] [Table 1]

[0177] [Synthesis Example 9] Synthesis of polyfunctional styryl compound (A2-1) Into a four-necked flask, 157.69 mmol of bisphenol A as a phenolic compound, 946.17 mmol of 4-(chloromethyl)styrene as a halogen compound, 946.17 mmol of potassium carbonate as an alkali metal compound, and N-methyl-2-pyrrolidone (0.5 g per 1 mmol of the total amount of the halogen compound and the phenolic compound) as a synthetic solvent were added. After replacing the inside of the flask with nitrogen, the contents of the flask were heated at 80 °C for 4 hours. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain a polyfunctional styryl compound (A2-1). The obtained compound (A2-1) was 13 Analyzed by 13C-NMR etc., it was revealed that it is a polymer having the structure shown in formula (A2-1).

[0178] [Chemical formula]

[0179] [Synthesis Example 10] Synthesis of polyfunctional styryl compound (A2-2) Into a four-necked flask, 151.66 mmol of 4,6-dihydroxypyrimidine as a phenolic compound, 909.98 mmol of 4-(chloromethyl)styrene as a halogen compound, 909.98 mmol of potassium carbonate as an alkali metal compound, and N-methyl-2-pyrrolidone (0.5 g per 1 mmol of the total amount of the halogen compound and the phenolic compound) as a synthetic solvent were added. After replacing the inside of the flask with nitrogen, the contents of the flask were heated at 80 °C for 4 hours. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain a polyfunctional styryl compound (A2-2). The obtained compound (A2-2) was 13 Analyzed by 13C-NMR etc., it was revealed that it is a polymer having the structure shown in formula (A2-2).

[0180] [Chemical formula]

[0181] <Production of Radiation-Sensitive Composition> [Examples and Comparative Examples] Using the polyfunctional maleimide compound, polyfunctional styryl compound, polymer, photoinitiator, and other components shown in Tables 2-1 to 2-3 below (hereinafter collectively referred to as "Table 2") in the amounts shown in Table 2, using the organic solvent shown in Table 2, and uniformly mixing them to obtain the solid content concentration shown in Table 2, radiation-sensitive compositions of Examples 1 to 16 and Comparative Examples 1 to 5 were produced. The following evaluations were performed on the obtained radiation-sensitive compositions. The results are shown in Table 2.

[0182] ≪Resolution≫ The radiation-sensitive composition was spin-coated on a 6-inch silicon wafer, and then heated at 110 °C for 5 minutes using a hot plate to form a coating film (film thickness: 10 μm). Next, using an aligner (manufactured by Suss Microtec, model "MA-150"), ultraviolet light from a high-pressure mercury lamp was irradiated onto the coating film through a photomask so that the exposure amount at a wavelength of 365 nm was 500 mJ / cm 2 Subsequently, development was carried out by immersion in a developer (cyclopentanone) at 23 °C for 3 minutes. The coating film after development was heated using an oven under a nitrogen atmosphere under the heating conditions (curing temperature, curing time) shown in Table 2 to produce a resin film having a pattern. The resin film having the produced pattern was observed with an electron microscope and evaluated according to the following criteria. ○: A square pattern with a length of 50 μm and a width of 50 μm could be formed. ×: A square pattern with a length of 50 μm and a width of 50 μm could not be formed.

[0183] ≪Elongation≫ The radiation-sensitive composition was applied onto a substrate with a release agent, and then heated at 110 °C for 5 minutes using an oven to form a coating film. Next, using an aligner (manufactured by Suss Microtec, model "MA-150"), ultraviolet light from a high-pressure mercury lamp was irradiated so that the exposure amount at a wavelength of 365 nm was 500 mJ / cm 2The entire surface of the coating was irradiated in such a manner. Next, it was heated in an oven under a nitrogen atmosphere using the heating conditions (curing temperature, curing time) shown in Table 2.

[0184] A resin film with a thickness of 15 μm was obtained by peeling off the coating film after heating in post-bake from a substrate with a release agent. The obtained resin film was cut into strips measuring 5 cm in length and 0.5 cm in width. The tensile elongation at break (%) of the strip-shaped resin film was measured using a tensile and compression testing machine (product name "SDWS-0201", manufactured by Imada Seisakusho Co., Ltd.). The measurement conditions were: chuck distance = 2.5 cm, tensile speed = 5 mm / min, and measurement temperature = 23°C. The average of five measured values ​​was taken as the "elongation (initial value)" and evaluated according to the following criteria. ○: Growth of 20% or more △: Growth of 10% or more ×: Elongation is less than 10% or cannot be measured.

[0185] The tensile test specimens prepared as described above were subjected to three reflow cycles under air (maximum temperature 260°C), and then exposed to an environment of 130°C / 85%RH / 96hr. The tensile elongation of the specimens after exposure was measured in the same manner as the elongation (initial value) and was defined as "elongation (after PCT test)".

[0186] The "elongation maintenance rate" is calculated from the elongation (initial value) and elongation (after PCT test) measured above using the following formula: "Growth (after PCT trial)" / "Growth (initial value)" × 100 = Growth maintenance rate (%) The calculations were performed and evaluated according to the following criteria. ○: Maintenance rate of 70% or higher △: Maintenance rate of 50% or more ×: Maintenance rate is less than 50% or cannot be measured.

[0187] Dielectric properties The radiation-sensitive composition was applied to a substrate with a release agent, and then heated in an oven at 110°C for 5 minutes to create a coating. Next, using an aligner (Suss Microtec, model "MA-150"), ultraviolet light from a high-pressure mercury lamp was applied at a wavelength of 365 nm with an exposure dose of 500 mJ / cm². 2It was irradiated onto the entire surface of the coating film so as to achieve this. Next, using an oven, it was heated under a nitrogen atmosphere under the heating conditions (curing temperature, curing time) shown in Table 2.

[0188] From the substrate with a release agent, the coating film after heating in post-baking was peeled off to obtain a resin film with a thickness of 10 μm. The relative permittivity (ε r ) and dielectric loss tangent (tanδ) of the obtained resin film at 10 GHz were measured by the cavity resonator perturbation method using a dielectric property measuring device (a cavity resonator for 10 GHz manufactured by Kanto Electronics Application Development Co., Ltd.) under the conditions of 23°C and a relative humidity of 50%RH.

[0189]

Table 2-1

[0190]

Table 2-2

[0191]

Table 2-3

[0192] Each component in Table 2 is as follows. (A1-1): A polyfunctional maleimide compound represented by the following formula (A1-1) ("BMI-2000" manufactured by Daiwa Kasei Kogyo Co., Ltd.) (A1-2): A polyfunctional maleimide compound represented by the following formula (A1-2) ("BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd.) (A1-3): A polyfunctional maleimide compound represented by the following formula (A1-3) ("BMI-4000" manufactured by Daiwa Kasei Kogyo Co., Ltd.) (A1-4): A polyfunctional maleimide compound represented by the following formula (A1-4) ("MIR-3000" manufactured by Nippon Kayaku Co., Ltd.)

[0193]

Chemical formula

[0194] (A2-1): Polyfunctional styryl compound synthesized in Synthesis Example 9 (A2-1) (A2-2): Polyfunctional styryl compound synthesized in Synthesis Example 10 (A2-2)

[0195] (B1): Polymer polymerized in Synthesis Example 1 (B1) (B2): Polymer polymerized in Synthesis Example 2 (B2) (B3): Polymer polymerized in Synthesis Example 3 (B3) (B4): Polymer polymerized in Synthesis Example 4 (B4) (B5): Polymer polymerized in Synthesis Example 5 (B5) (B6): Polymer polymerized in Synthesis Example 6 (B6) (B7): Polymer polymerized in Synthesis Example 7 (B7) (RB1): Polymer (RB1) polymerized in Synthesis Example 8 (RB2): Cresol novolac resin consisting of m-cresol / p-cresol = 60 / 40 (molar ratio) (Mw = 6,500)

[0196] (C1): BASF Corporation's "Irgacure OXE02" (D1): Fluorine-based surfactant (NBX-15 manufactured by Neos Co., Ltd.) (E1): Cyclohexanone (E2): Gamma-butyrolactone

[0197] (F1): Polyfunctional acrylate (NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) (F2): Hexamethoxymethylated melamine ("Cymel 300" manufactured by Mitsui Chemicals, Inc.) (F3): Photoacid generator shown below (F4): 1,2,3-benzotriazole

[0198] [ka]

Claims

1. A polyfunctional styryl compound represented by the following formula (A2) (A-2), A polymer (B) having a group Y at its terminus that reacts with the styryl group of the polyfunctional styryl compound (A-2), and It contains a photopolymerization initiator (C), The polymer (B) is a polymer having repeating structural units represented by the following formula (a2), A radiation-sensitive composition for forming an insulating film, wherein the group Y is represented by the following formula (Y1). 【Chemistry 1】 [In formula (a2), each of the two X independently represents a single bond, an oxygen atom, or -NH-C(O)-NH-, and at least one X is an oxygen atom.] R a21 This indicates a divalent aromatic ring-containing hydrocarbon group, R a22 This indicates a divalent aromatic ring-containing hydrocarbon group or a heterocyclic-containing group. The aforementioned aromatic ring-containing hydrocarbon group is a group having an aromatic ring in its main chain. The aforementioned heterocyclic ring-containing group is a heteroaromatic ring-containing group having an N-containing aromatic ring in its main chain, or an aromatic imide ring-containing group having a structure in which a cyclic imide group is fused to the aromatic ring in its main chain. 【Chemistry 2】 [In formula (Y1), R Y1 L represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y1 The symbols indicate a single bond, an alkanediyl group having 1 to 5 carbon atoms, -C(O)O-, -NH-C(O)-NH-, or a combination thereof, and * indicates the position where it bonds to the main chain or side chain constituting polymer (B). 【Transformation 3】 [In formula (A2), n Ａ２ is an integer greater than or equal to 2, R Ａ２ n from organic compounds Ａ２ n is a hydrogen atom that has been removed. Ａ２ It is a valence organic group, The organic compound is an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, a heterocyclic compound, or a compound in which two or more of these compounds are linked by a single bond, -O-, -S-, -SO 2 -, -NR N1 -, -CO-, -COO-, -CONH-, and is a compound linked by these The aforementioned R N1 However, it is a group from which one hydrogen atom has been removed from a hydrogen atom or the organic compound. R Ａ３ This is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R Ａ４ This is an alkyl group having 1 to 10 carbon atoms. n Ａ４ [This is an integer between 0 and 4.]

2. The radiation-sensitive composition for forming an insulating film according to claim 1, wherein the polymer (B) is a polyimide or a polyphenylene ether.

3. The aforementioned R a21 The radiation-sensitive composition for forming an insulating film according to claim 1 or 2, wherein the group is an arylene group.

4. The aforementioned R a22 The radiation-sensitive composition for forming an insulating film according to any one of claims 1 to 3, wherein the group is a divalent group obtained by removing two hydrogen atoms from a pyrimidine, or an arylene group.

5. A method for producing a patterned resin film, comprising the steps of: (1) forming a coating film of an insulating film-forming radiation-sensitive composition according to any one of claims 1 to 4 on a substrate; (2) selectively exposing the coating film to light; and (3) developing the exposed coating film with a developer containing an organic solvent.

6. A patterned resin film obtained by curing a radiation-sensitive composition for forming an insulating film according to any one of claims 1 to 4.

7. A semiconductor circuit substrate comprising a resin film having the pattern described in claim 6.

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