Photosensitive resin composition, photosensitive resin film, photosensitive dry film, and pattern forming process

Abstract

To provide a photosensitive resin composition capable of yielding a photosensitive resin film that has a shielding function, has dispersion stability in varnish, can reduce aggregates in a film, and can form a fine pattern, the photosensitive resin film, a photosensitive dry film, and a pattern forming process using the composition.SOLUTION: The present invention is a photosensitive resin composition including a silicone skeleton-containing polymer (A), an anthraquinone-based dye (B), and a photoacid generator (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method using the composition. [Background technology]

[0002] Some optical devices have a hollow structure in which a sensor is bonded to a cover glass via a partition wall formed around the sensor. This partition wall is typically formed by a lithography process using a photosensitive resin composition. While information from light entering through the cover glass is typically transmitted to the sensor, if light leaking in from the partition wall also enters the sensor, problems can occur in image processing, so the sensor must have a light-blocking function. A photosensitive resin composition with a cured film that provides light-blocking properties has been proposed, which is a photosensitive silicone composition primarily composed of a silphenylene skeleton-containing silicone polymer to which carbon black has been added (Patent Document 1).

[0003] However, there are problems such as carbon black settling in the varnish and aggregates remaining in the cured film.Furthermore, further improvement in the level of miniaturization by pattern formation is desired. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-016879 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern formation method using the composition, which have a shielding function, have dispersion stability in a varnish, suppress agglomerations in a film, and are capable of providing a photosensitive resin film that can form a fine pattern. [Means for solving the problem]

[0006] In order to solve the above problems, the present invention provides a photosensitive resin composition comprising (A) a silicone skeleton-containing polymer, (B) an anthraquinone dye, and (C) a photoacid generator.

[0007] The photosensitive resin composition of the present invention can provide a photosensitive resin composition containing an anthraquinone dye that has a shielding function, dispersion stability in a varnish, suppresses agglomerations in a film, and can provide a photosensitive resin film that can form a fine pattern; a photosensitive resin film; a photosensitive dry film; a pattern formation method using the composition; and a pattern formation method using the photosensitive dry film.

[0008] In the photosensitive resin composition of the present invention, the silicone skeleton-containing polymer (A) preferably contains repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4). [ka] (In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and m is an integer of 1 to 600. a 1 ~a 4 and b 1 ~b 4 is 0≦a 1 < 1, 0 ≤ a 2 < 1, 0 ≤ a 3 < 1, 0 ≤ a 4 < 1, 0 ≤ b 1 < 1, 0 ≤ b 2 < 1, 0 ≤ b 3< 1, 0 ≤ b 4 <1, 0 1 +a 2 +a 3 +a 4 <1, 0 1 +b 2 +b 3 +b 4 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 =1. X 1 is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2): 3 is a divalent group represented by the following formula (X3): 4 is a divalent group represented by the following formula (X4): [ka] (In the formula, Z 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11 and R 12 are each independently a hydrogen atom or a methyl group. 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer of 0 to 7. 1 and q 2 are each independently an integer of 0 to 2. [ka] (In the formula, Z 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group.​​21 and R 22 are each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer of 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. [ka] (In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer of 0 to 7. [ka] (In the formula, R 41 and R 42 are each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. 1 and u 2 are each independently an integer of 0 to 7, and v is an integer of 0 to 600.

[0009] The photosensitive resin composition of the present invention can provide a photosensitive resin film that has good adhesion to laminates, substrates, etc., good pattern-forming ability, crack resistance, and heat resistance.

[0010] Furthermore, the photosensitive resin composition of the present invention preferably contains one or more of (D) a crosslinking agent, (E) a solvent, (F) a quencher, and (G) an antioxidant.

[0011] Such a photosensitive resin composition can easily form a pattern, further increase the strength of the cured product, improve resolution, suppress changes in sensitivity after exposure, reduce substrate dependency or environmental dependency, and improve exposure latitude and pattern shape.

[0012] The photosensitive resin composition of the present invention preferably contains 0.01 to 50 parts by mass of the anthraquinone dye (B) relative to 100 parts by mass of the component (A).

[0013] Furthermore, in the photosensitive resin composition of the present invention, the anthraquinone dye (B) preferably has a maximum absorption wavelength of 800 nm or less.

[0014] Such a photosensitive resin composition can have a stronger shielding function, has dispersion stability in a varnish, can suppress aggregation in a film, and further allows for the formation of finer patterns.

[0015] The photosensitive resin composition of the present invention is preferably used for optical components.

[0016] Such a photosensitive resin composition has excellent dispersion stability in the varnish, suppresses aggregation in the film, and can be used as a material for optical components that require shielding.

[0017] The present invention provides a photosensitive resin film obtained from the photosensitive resin composition of the present invention.

[0018] Such a photosensitive resin film has a shielding function, has dispersion stability in a varnish, suppresses agglomeration in a film, and allows the formation of a fine pattern.

[0019] The present invention also provides a photosensitive dry film comprising a support film and the photosensitive resin film of the present invention on the support film.

[0020] By using such a photosensitive dry film, the photosensitive resin film of the present invention can be easily obtained in the required thickness.

[0021] The present invention provides a pattern formation method using the photosensitive resin composition of the present invention, comprising the steps of forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention, exposing the photosensitive resin film to light, and developing the exposed photosensitive resin film with a developer to form a pattern.

[0022] The present invention also provides a pattern formation method using the photosensitive dry film of the present invention, comprising the steps of forming a photosensitive resin film on a substrate using the photosensitive dry film, exposing the photosensitive resin film to light, and developing the exposed photosensitive resin film with a developer to form a pattern.

[0023] Such a pattern forming method makes it possible to form a contact hole pattern with good perpendicularity.

[0024] Furthermore, the pattern forming method using the photosensitive resin composition of the present invention preferably includes a step of post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

[0025] The pattern forming method including such a post-curing step can increase the crosslink density of the photosensitive resin composition of the present invention and remove residual volatile components, and is more preferable from the viewpoints of adhesion to the substrate, heat resistance, strength, electrical properties, and adhesive strength. [Effects of the Invention]

[0026] As described above, the photosensitive resin composition of the present invention can provide a photosensitive resin composition containing an anthraquinone dye that has a shielding function, dispersion stability in a varnish, suppresses agglomerations in a film, and can provide a photosensitive resin film that can form a fine pattern, a photosensitive resin film, a photosensitive dry film, a pattern formation method using the composition, and a pattern formation method using the photosensitive dry film. DETAILED DESCRIPTION OF THE INVENTION

[0027] As described above, there has been a need for the development of a photosensitive resin composition that has a shielding function, dispersion stability in a varnish, suppresses agglomeration in a film, and is capable of providing a photosensitive resin film that allows the formation of a fine pattern.

[0028] As a result of extensive research into the above-mentioned problems, the present inventors have found that by using an anthraquinone dye as a light absorbing material for providing a shielding function, a photosensitive resin composition can be obtained that has dispersion stability in a varnish, suppresses aggregation in a film, and is capable of forming fine patterns, and have completed the present invention.

[0029] That is, the present invention is a photosensitive resin composition comprising (A) a silicone skeleton-containing polymer, (B) an anthraquinone dye, and (C) a photoacid generator.

[0030] The present invention will be described in detail below, but the present invention is not limited thereto.

[0031] [(A) Silicone skeleton-containing polymer] The silicone skeleton-containing polymer of component (A) is not particularly limited, but is preferably one containing repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4) (hereinafter, for convenience, also referred to as repeating units a1 to a4 and b1 to b4, respectively). [ka]

[0032] In formulas (a1) to (a4), R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 1 to 600. When m is an integer of 2 or greater, each R 3 may be the same or different, and each R 4 may be the same or different. When there are two or more siloxane units among the repeating units a1 to a4, the siloxane units may all be the same, or two or more different types of siloxane units may be included. When two or more different types of siloxane units are included (i.e., when m is an integer of 2 or more), the siloxane units may be bonded randomly or alternately, or may include multiple blocks of the same type of siloxane units.

[0033] The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, hexyl, and cyclohexyl groups, and structural isomers thereof, and aryl groups such as phenyl. Of these, methyl and phenyl groups are preferred because of the ease of availability of raw materials.

[0034] In the formulas (a1) to (a4), m is an integer of 1 to 600, preferably an integer of 1 to 400, and more preferably an integer of 1 to 200. If it is in the range of 1 to 600, flexibility can be imparted and film formation becomes easier, so this is preferable.

[0035] In formulas (a1) and (b1), X 1 is a divalent group represented by the following formula (X1). [ka]

[0036] In formula (X1), Z 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11and R 12 are each independently a hydrogen atom or a methyl group. 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer of 0 to 7. 1 and q 2 are each independently an integer of 0 to 2.

[0037] The alkyl group may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and structural isomers thereof. The alkoxy group may be linear, branched, or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and structural isomers thereof.

[0038] In formulas (a2) and (b2), X 2 is a divalent group represented by the following formula (X2). [ka]

[0039] In formula (X2), Z 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 21 and R 22 are each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer of 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. Examples of the alkyl group and alkoxy group include the same as those mentioned above.

[0040] In formulas (a3) and (b3), X 3 is a divalent group represented by the following formula (X3). [ka]

[0041] In formula (X3), R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer of 0 to 7.

[0042] In formulas (a4) and (b4), X 4 is a divalent group represented by the following formula (X4). [ka]

[0043] In formula (X4), R 41 and R 42 are each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. 1 and u 2 are each independently an integer of 0 to 7. v is an integer of 0 to 600, preferably an integer of 0 to 400, and more preferably an integer of 0 to 200. If it is in the range of 0 to 600, flexibility can be imparted and film formation becomes easier, so it is preferable. As the monovalent hydrocarbon group, the above R 1 ~R 4 In the group represented by formula (X4), when v is an integer of 2 or greater, the siloxane units represented by the subscript v may be randomly bonded or alternately bonded, or may contain multiple blocks of the same type of siloxane units.

[0044] The silicone skeleton-containing polymer of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, and more preferably 5,000 to 200,000. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent.

[0045] In the formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 is 0≦a 1 < 1, 0 ≤ a 2 < 1, 0 ≤ a 3 < 1, 0 ≤ a 4 < 1, 0 ≤ b 1 < 1, 0 ≤ b 2 < 1, 0 ≤ b 3 < 1, 0 ≤ b 4 <1, 0 1 +a 2 +a 3 +a 4 <1, 0 1 +b 2 +b 3 +b 4 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1, but 0≦a 1 ≦0.8, 0≦a 2 ≦0.8, 0≦a 3 ≦0.8, 0≦a 4 ≦0.8, 0≦b 1 ≦0.95, 0≦b 2 ≦0.95, 0≦b 3 ≦0.95, 0≦b 4 ≦0.95, 0.05≦a 1 +a 2 +a 3 +a 4 ≦0.8, 0.2≦b 1 +b 2 +b 3 +b​​4 ≦0.95, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number satisfying 0≦a 1 ≦0.7, 0≦a 2 ≦0.7, 0≦a 3 ≦0.7, 0≦a 4 ≦0.7, 0≦b 1 ≦0.9, 0≦b 2 ≦0.9, 0≦b 3 ≦0.9, 0≦b 4 ≦0.9, 0.1≦a 1 +a 2 +a 3 +a 4 ≦0.7, 0.3≦b 1 +b 2 +b 3 +b 4 ≦0.9, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number that satisfies =1 is more preferable.

[0046] The silicone skeleton-containing polymer of component (A) preferably has a crosslinking group such as an epoxy group or a hydroxy group or a reactive site at which a crosslinking reaction occurs in the molecule. That is, the polymer preferably contains at least one type selected from repeating units a1 to a3 and at least one type selected from repeating units b1 to b3. In this case, in the formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 is 0≦a 1 < 1, 0 ≤ a 2 < 1, 0 ≤ a 3 < 1, 0 ≤ a 4 < 1, 0 ≤ b 1 < 1, 0 ≤ b 2 < 1, 0 ≤ b 3 < 1, 0 ≤ b4 <1, 0 1 +a 2 +a 3 <1, 0 1 +b 2 +b 3 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number satisfying 0≦a 1 ≦0.8, 0≦a 2 ≦0.8, 0≦a 3 ≦0.8, 0≦a 4 ≦0.8, 0≦b 1 ≦0.95, 0≦b 2 ≦0.95, 0≦b 3 ≦0.95, 0≦b 4 ≦0.95, 0.05≦a 1 +a 2 +a 3 ≦0.8, 0.2≦b 1 +b 2 +b 3 ≦0.95, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1 is more preferable, and 0≦a 1 ≦0.7, 0≦a 2 ≦0.7, 0≦a 3 ≦0.7, 0≦a 4 ≦0.7, 0≦b 1 ≦0.9, 0≦b 2 ≦0.9, 0≦b 3 ≦0.9, 0≦b 4 ≦0.9, 0.1≦a 1 +a 2 +a 3 ≦0.7, 0.3≦b 1 +b 2 +b 3 ≦0.9, and a 1 +a 2 +a 3 +a 4 +b​​1 +b 2 +b 3 +b 4 A number satisfying .gtoreq.1 is more preferable.

[0047] In particular, the silicone skeleton-containing polymer of component (A) preferably contains repeating units a3 and b3. In this case, in the formulae (a1) to (a4) and (b1) to (b4), 1 ~a 4 and b 1 ~b 4 is 0≦a 1 < 1, 0 ≤ a 2 <1, 0 3 < 1, 0 ≤ a 4 < 1, 0 ≤ b 1 < 1, 0 ≤ b 2 <1, 0 3 < 1, 0 ≤ b 4 <1, 0 1 +a 2 +a 3 +a 4 <1, 0 1 +b 2 +b 3 +b 4 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number satisfying 0≦a 1 <0.8, 0≦a 2 <0.8, 0 3 ≦0.8, 0≦a 4 <0.8, 0≦b 1 <0.95, 0 ≤ b 2 <0.95, 0 3 ≦0.95, 0≦b 4 <0.95, 0.05≦a 1 +a 2 +a 3 +a 4 ≦0.8, 0.2≦b 1 +b 2 +b 3 +b 4 ≦0.95, and a 1 +a 2 ​​​​​​+a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1 is more preferable, and 0≦a 1 <0.7, 0≦a 2 <0.7, 0 3 ≦0.7, 0≦a 4 <0.7, 0≦b 1 <0.9, 0≦b 2 <0.9, 0 3 ≦0.9, 0≦b 4 <0.9, 0.1≦a 1 +a 2 +a 3 +a 4 ≦0.7, 0.3≦b 1 +b 2 +b 3 +b 4 ≦0.9, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number satisfying .gtoreq.1 is more preferable.

[0048] The repeating units may be bonded randomly or as a block polymer. The siloxane units in each repeating unit may be bonded randomly or may contain multiple blocks of the same type of siloxane units. The silicone resin preferably has a silicone (siloxane unit) content of 30 to 80% by mass.

[0049] The silicone skeleton-containing polymer of component (A) functions to impart film-forming ability, and the resulting resin film has good adhesion to laminates and substrates, good pattern-forming ability, crack resistance, and heat resistance.

[0050] The silicone skeleton-containing polymer of component (A) may be used alone or in combination of two or more types.

[0051] ​​ [Method of manufacturing silicone skeleton-containing polymer] The silicone skeleton-containing polymer of component (A) can be produced by addition polymerization, in the presence of a metal catalyst, of a compound represented by the following formula (1) (hereinafter also referred to as compound (1)), a compound represented by the following formula (2) (hereinafter also referred to as compound (2)), a compound represented by the following formula (3) (hereinafter also referred to as compound (3)), a compound represented by the following formula (4) (hereinafter also referred to as compound (4)), a compound represented by the following formula (5) (hereinafter also referred to as compound (5)), and a compound represented by the following formula (6) (hereinafter also referred to as compound (6)).

[0052] [ka] (In the formula, R 1 ~R 4 and m are the same as above.)

[0053] [ka] (In the formula, R 11 ~R 14 , R 21 ~R 24 , R 31 , R 32 , R 41 ~R 44 , Z 1 , Z 2 , p 1 , p 2 , q 1 , q 2 , r 1 , r 2 , s 1 , s 2 , t 1 , t 2 , u 1 , u 2 and v are the same as above.)

[0054] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chlorides, chloroplatinic acids, and chloroplatinic salts such as HPtCl·xH2O, HPtCl·xH2O, NaHPtCl·xH2O, KHPtCl·xH2O, NaPtCl·xH2O, KPtCl·xH2O, PtCl·xH2O, PtCl, and NaHPtCl·xH2O (where x is preferably an integer of 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, that described in U.S. Pat. No. 3,220,972); ); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), and the like can be used.

[0055] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 parts by mass, more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the total of the compounds (1) to (6).

[0056] In the above addition polymerization reaction, a solvent may be used if necessary, and the solvent is preferably a hydrocarbon solvent such as toluene or xylene.

[0057] The polymerization temperature is preferably 40 to 150°C, more preferably 60 to 120°C, from the viewpoint of not deactivating the catalyst and enabling the polymerization to be completed in a short time. The polymerization time varies depending on the type and amount of the resin to be obtained, but is preferably approximately 0.5 to 100 hours, more preferably 0.5 to 30 hours, in order to prevent the intrusion of moisture into the polymerization system. After the reaction is complete, if a solvent was used, it can be distilled off to obtain the silicone skeleton-containing polymer of component (A).

[0058] The reaction method is not particularly limited, but examples thereof include a method in which at least one selected from the above compounds (3) to (6) is first heated, a metal catalyst is added thereto, and then the above compounds (1) and (2) are added dropwise over 0.1 to 5 hours.

[0059] The raw material compounds are preferably blended so that the molar ratio of the total of the hydrosilyl groups contained in the compound (1) and the compound (2) to the total of the alkenyl groups contained in at least one compound selected from the compounds (3) to (6) is preferably 0.67 to 1.67, more preferably 0.83 to 1.25.

[0060] The Mw of the silicone skeleton-containing polymer of component (A) can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight modifier.

[0061] [(B) Anthraquinone dyes] There are no particular restrictions on the anthraquinone dye of component (B).

[0062] The anthraquinone dye (B) contained in the photosensitive resin composition of the present invention is not particularly limited, but specifically, the following dyes can be used: 2-anilino-1,3,4-trifluoroanthraquinone, (2) 2-(o-ethoxycarbonylanilino)-1,3,4-trifluoroanthraquinone, (3) 2-(p-ethoxycarbonylanilino)-1,3,4-trifluoroanthraquinone, (4) 2-(m-ethoxycarbonylanilino)-1,3,4-trifluoroanthraquinone, (5) 2-(o-cyanoanilino)-1,3,4-trifluoroanthraquinone, (6) 2-(p-cyanoanilino)-1,3,4-trifluoroanthraquinone. quinone, (7) 2-(m-cyanoanilino)-1,3,4-trifluoroanthraquinone, (8) 2-(o-nitroanilino)-1,3,4-trifluoroanthraquinone, (9) 2-(p-nitroanilino)-1,3,4-trifluoroanthraquinone, (10) 2-(m-nitroanilino)-1,3,4-trifluoroanthraquinone, (11) 2-(p-tert-butylanilino)-1,3,4-trifluoroanthraquinone, (12) 2-(o-methoxyanilino)-1,3,4-trifluoroanthraquinone fluoroanthraquinone, (13) 2-(2,6-diisopropylanilino)-1,3,4-trifluoroanthraquinone, (14) 2-(2,6-dichloroanilino)-1,3,4-trifluoroanthraquinone, (15) 2-(2,6-difluoroanilino)-1,3,4-trifluoroanthraquinone, (16) 2-(3,4-dicyanoanilino)-1,3,4-trifluoroanthraquinone, (17) 2-(2,4,6-trichloroanilino)-1,3,4-trifluoroanthraquinone, (18) 2 -(2,3,5,6-tetrachloroanilino)-1,3,4-trifluoroanthraquinone, (19) 2-(2,3,5,6-tetrafluoroanilino)-1,3,4-trifluoroanthraquinone, (20) 3-(2,3,4,5-tetrafluoroanilino)-2-butoxy-1,4-difluoroanthraquinone, (21) 3-(4-cyano-3-chloroanilino)-2-octyloxy-1,4-difluoroanthraquinone, (22) 3-(3,4-dicyanoanilino)-2-hexyloxy-1,4-Difluoroanthraquinone, (23) 3-(4-cyano-3-chloroanilino)-1,2-dibutoxy-4-fluoroanthraquinone, (24) 3-(p-cyanoanilino)-2-phenoxy-1,4-difluoroanthraquinone, (25) 3-(p-cyanoanilino)-2-(2,6-diethylphenoxy)-1,4-difluoroanthraquinone, (26) 3-(2,6-dichloroanilino)-2-(2,6-dichlorophenoxy)-1,4-difluoroanthraquinone, (27) 3-(2,3,5,6-tetrachloroanilino)-2-( 2,6-dimethoxyphenoxy)-1,4-difluoroanthraquinone, (28) 2,3-dianilino-1,4-difluoroanthraquinone, (29) 2,3-bis(p-tert-butylanilino)-1,4-difluoroanthraquinone, (30) 2,3-bis(p-methoxyanilino)-1,4-difluoroanthraquinone, (31) 2,3-bis(2-methoxy-6-methylanilino)-1,4-difluoroanthraquinone, (32) 2,3-bis(2,6-diisopropylanilino)-1,4-difluoroanthraquinone, (33) 2,3 -Bis(2,4,6-trichloroanilino)-1,4-difluoroanthraquinone, (34) 2,3-bis(2,3,5,6-tetrachloroanilino)-1,4-difluoroanthraquinone, (35) 2,3-bis(2,3,5,6-tetrafluoroanilino)-1,4-difluoroanthraquinone, (36) 2,3-bis(p-cyanoanilino)-1-methoxyethoxy-4-fluoroanthraquinone, (37) 2-(2,6-dichloroanilino)-1,3,4-trichloroanthraquinone, (38) 2-(2,3,5,6-tetrafluoroanilino)-4-fluoroanthraquinone (39) 3-(2,6-dichloroanilino)-2-(2,6-dichlorophenoxy)-1,4-dichloroanthraquinone, (40) 2-(2,6-dichloroanilino)anthraquinone, (41) 2-(2,3,5,6-tetrafluoroanilino)anthraquinone, (42) 3-(2,6-dichloroanilino)-2-(2,6-dichlorophenoxy)anthraquinone, (43) 2,3-bis(2-methoxy-6-methylanilino)-1,4-dichloroanthraquinone, (44) 2,3-bis(2,6-diisopropylanilino)anthraquinone, (45) 2-butylamino-1,3,4-trifluoroanthraquinone, (46) 1,4-bis(n-butylamino)-2,3-difluoroanthraquinone, (47) 1,4-bis(n-octylamino)-2,3-difluoroanthraquinone, (48) 1,4-bis(hydroxyethylamino)-2,3-difluoroanthraquinone, (49) 1,4-bis(cyclohexylamino)-2,3-difluoroanthraquinone Examples of such anthraquinone include (50) 1,4-bis(cyclohexylamino)-2-octyloxy-3-fluoroanthraquinone, (51) 1,2,4-tris(2,4-dimethoxyphenoxy-3-fluoroanthraquinone, (52) 2,3-bis(phenylthio)-1-phenoxy-4-fluoroanthraquinone, and (53) 1,2,3,4-tetra(p-methoxyphenoxy)-anthraquinone, and these can be used alone or in combination of two or more.

[0063] Commercially available products can be used as the anthraquinone dye of component (B). Specific examples include CI Solvent Yellow 117, 163, 167, 189, CI Solvent Orange 77, 86, CI Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, and CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 63, 68, 69, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 9, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI Solvent Green 3, 28, 29, 32, 33, CI Acid Red 80, CI Acid Green 25, 27, 28, 41, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112, CI Disperse Yellow 51, CI Disperse Violet 26, 27, CI Disperse Blue 1, 14, 56, 60, CI Direct Blue 40, CI Mordant Red 3, 11, and CI Mordant Blue 8.

[0064] The anthraquinone dye of component (B) preferably has a maximum absorption wavelength of 800 nm or less, more preferably 300 to 800 nm, and is preferably a dye containing a pigment having a maximum absorption wavelength of 800 nm or less, since leakage light in the visible light region can be blocked.

[0065] The photosensitive resin composition of the present invention preferably contains 0.01 to 50 parts by mass, more preferably 0.01 to 30 parts by mass, even more preferably 0.01 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass of the anthraquinone dye (B) per 100 parts by mass of the silicone skeleton-containing resin (A). An amount of 0.01 part by mass or more is preferred because it exhibits a light-blocking function against leaked light, while an amount of 50 parts by mass or less is preferred because it can suppress poor compatibility and the occurrence of aggregates.

[0066] [(C) Photoacid generator] The photoacid generator (C) is not particularly limited as long as it decomposes upon irradiation with light and generates an acid, but it is preferably one that generates an acid upon irradiation with light having a wavelength of 190 to 500 nm. The composition used in the present invention has excellent compatibility with acid generators, allowing the use of a wide range of acid generators.

[0067] The photoacid generator (C) is used as a curing catalyst. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

[0068] The onium salts include sulfonium salts represented by the following formula (C1) and iodonium salts represented by the following formula (C2). [ka]

[0069] In the above formulas (C1) and (C2), R 101 ~R 105 are each independently an alkyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. - is a non-nucleophilic counterion.

[0070] The alkyl group may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the aryl group include phenyl, naphthyl, and biphenylyl. Examples of the aralkyl group include benzyl and phenethyl.

[0071] Examples of the substituent include an oxo group, a linear, branched, or cyclic alkoxy group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an arylthio group having 6 to 24 carbon atoms.

[0072] R 101 ~R 105 Preferred examples of the alkyl group include alkyl groups which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, or a 2-oxocyclohexyl group; aryl groups which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, an m- or p-tert-butoxyphenyl group, a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, or a biphenylylthiophenyl group; and aralkyl groups which may have a substituent such as a benzyl group or a phenethyl group. Of these, aryl groups which may have a substituent and aralkyl groups which may have a substituent are more preferred.

[0073] Above A -Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ion; and borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion.

[0074] The diazomethane derivatives include compounds represented by the following formula (C3). [ka]

[0075] In formula (C3), R 111 and R 112 are each independently an alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0076] The alkyl group may be linear, branched, or cyclic. Specific examples thereof include R 101 ~R 105 Examples of the halogenated alkyl group include the same as those exemplified in the description of 1. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group.

[0077] Examples of the aryl group which may have the above-mentioned substituent include a phenyl group; an alkoxyphenyl group such as a 2-, 3-, or 4-methoxyphenyl group, a 2-, 3-, or 4-ethoxyphenyl group, and a 3- or 4-tert-butoxyphenyl group; an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group; and a halogenated aryl group such as a fluorophenyl group, a chlorophenyl group, and a 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0078] The glyoxime derivatives include compounds represented by the following formula (C4). [ka]

[0079] In the above (C4), R 121 ~R 124 are each independently an alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms. 123 and R 124 may be bonded to each other to form a ring together with the carbon atoms to which they are attached, and when they form a ring, R 123 and R 124 The group formed by bonding is a linear or branched alkylene group having 1 to 12 carbon atoms.

[0080] The alkyl group, halogenated alkyl group, optionally substituted aryl group, and aralkyl group include R 111 and R 112 Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0081] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate sulfonium trifluoromethanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, p-toluenesulfone dicyclohexylphenylsulfonium acid, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate,Examples include triphenylsulfonium tetrakis(pentafluorophenyl)borate and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0082] Specific examples of the diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(t 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, and 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane.

[0083] Specific examples of the glyoxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0084] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0085] Specific examples of the disulfone derivative include diphenyl disulfone and dicyclohexyl disulfone.

[0086] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0087] Specific examples of the sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0088] Specific examples of the imide-yl sulfonate derivative include phthalimide-yl triflate, phthalimide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl triflate, 5-norbornene-2,3-dicarboximide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0089] Specific examples of the oxime sulfonate derivatives include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile.

[0090] Specific examples of the iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile.

[0091] Specific examples of the triazine derivative include 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine.

[0092] Also suitable for use are 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like.

[0093] As the photoacid generator of the component (C), the above-mentioned onium salts are preferred, and the above-mentioned sulfonium salts are more preferred.

[0094] From the viewpoint of photocurability, the content of component (C) is preferably 0.05 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of component (A). A content of component (C) of 0.05 parts by mass or more is preferred because it generates a sufficient amount of acid and allows the crosslinking reaction to proceed sufficiently. Furthermore, a content of 20 parts by mass or less is preferred because it prevents an increase in the absorbance of the acid generator itself and ensures sufficient transparency. The component (C) may be used alone or in combination of two or more.

[0095] In addition to (A) the silicone skeleton-containing polymer, (B) the anthraquinone dye, and (C) the photoacid generator, the photosensitive resin composition of the present invention preferably further contains one or more of (D) a crosslinking agent, (E) a solvent, (F) a quencher, and (G) an antioxidant.

[0096] [(D) Crosslinking agent] The crosslinking agent (D) is a phenolic hydroxy group of the above-mentioned component (A) or R 13 , R 14 , R 23 or R 24This component undergoes a condensation reaction with the alkoxy group represented by the formula (I) and facilitates pattern formation, while also further increasing the strength of the cured product.

[0097] The crosslinking agent of component (D) is preferably a resin with an Mw of 150 to 10,000, particularly 200 to 3,000. If the Mw is 150 or more, sufficient photocurability can be obtained, and if it is 10,000 or less, there is no risk of the heat resistance of the composition being deteriorated after curing, which is preferable.

[0098] Furthermore, preferred crosslinking agents for component (D) include nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds, which contain an average of two or more methylol groups and / or alkoxymethyl groups per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having an average of two or more methylol groups or alkoxymethyl groups per molecule; and epoxy compounds having an average of two or more epoxy groups per molecule.

[0099] The melamine compound may be one represented by the following formula (D1). [ka]

[0100] In formula (D1), R 201 ~R 206 are each independently a methylol group, an alkoxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, and at least one is a methylol group or an alkoxymethyl group. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

[0101] Examples of the melamine compound represented by formula (D1) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, and hexaethoxymethyl melamine.

[0102] The melamine compound represented by formula (D1) can be obtained, for example, by first methylolating a melamine monomer with formaldehyde according to a known method, or by further alkoxylating the melamine monomer with an alcohol, preferably a lower alcohol having 1 to 4 carbon atoms.

[0103] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0104] Examples of the glycoluril compound include tetramethylol glycoluril and tetrakis(methoxymethyl) glycoluril.

[0105] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0106] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0107] The modified melamine condensate may be obtained by subjecting the compound represented by formula (D1) or a polymer thereof (e.g., an oligomer such as a dimer or trimer) to addition-condensation polymerization with formaldehyde according to a conventional method until a desired molecular weight is reached.

[0108] Examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate.

[0109] The modified urea condensate can be obtained, for example, by methylolating a urea condensate of a desired molecular weight with formaldehyde according to a known method, or by further alkoxylating the urea condensate with an alcohol.

[0110] Examples of the phenol compound having two or more methylol groups or alkoxymethyl groups on average per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0111] Examples of the epoxy compound having two or more epoxy groups per molecule on average include bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins, novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins, triphenolalkane-type epoxy resins, biphenyl-type epoxy resins, dicyclopentadiene-modified phenol novolac-type epoxy resins, phenol aralkyl-type epoxy resins, biphenyl aralkyl-type epoxy resins, naphthalene ring-containing epoxy resins, glycidyl ester-type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

[0112] When the photosensitive resin composition of the present invention contains component (D), the content thereof is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of component (A). If the content is 0.5 parts by mass or more, sufficient curability can be obtained upon light irradiation, and if the content is 50 parts by mass or less, the proportion of component (A) in the photosensitive resin composition does not decrease, allowing the cured product to fully exhibit the effects of the present invention. The crosslinking agent of component (D) can be used alone or in combination of two or more different types.

[0113] [(E) Solvent] The solvent for component (E) is not particularly limited as long as it is a solvent that can dissolve components (A) to (D) and the various additives described below, but organic solvents are preferred because they have excellent solubility for these components.

[0114] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl 2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. These organic solvents can be used alone or in combination. In particular, ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof, which have the best solubility for the photoacid generator, are preferred.

[0115] From the viewpoint of compatibility and viscosity of the photosensitive resin composition, the amount of component (E) used is preferably 50 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, and particularly preferably 50 to 100 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C).

[0116] [(F)Quencher] The quencher (F) is preferably a compound capable of suppressing the diffusion rate of the acid generated by the photoacid generator when it diffuses through the photosensitive resin film. The incorporation of such a quencher improves resolution, suppresses changes in sensitivity after exposure, reduces substrate dependency or environmental dependency, and improves exposure latitude and pattern shape.

[0117] Examples of the quencher of the component (F) include primary, secondary, or tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives.

[0118] Examples of the primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine.

[0119] Examples of the secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine.

[0120] Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, and N,N,N',N'-tetramethyltetraethylenepentamine.

[0121] Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

[0122] Examples of the aromatic amines and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, and pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrroline, lysine, pyrrolidinone, N-methyl-2-pyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives. ,

[0123] Examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine).

[0124] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

[0125] Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2 ... 1-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyyulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, and N-(2-hydroxyethyl)isonicotinamide.

[0126] Examples of the amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide.

[0127] Examples of the imide derivative include phthalimide, succinimide, and maleimide.

[0128] As the quencher of the component (F), a compound represented by the following formula (F1) can also be used. [ka]

[0129] In formula (F1), w is 1, 2 or 3. 301 R is any one of the substituents selected from the substituents represented by the following formulas (F2) to (F4). 302 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may contain an ether bond or a hydroxy group. 301 If there are two or more R 301 may be bonded to each other to form a ring together with the nitrogen atom to which they are attached. 301 When there are two or more, they may be the same or different, and R 302 When there are two or more, they may be the same or different. [ka]

[0130] In formulas (F2) to (F4), R 303 , R 305 and R 308 are each independently a linear or branched alkanediyl group having 1 to 4 carbon atoms. 304 and R 307are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and may contain at least one selected from a hydroxy group, an ether bond, an ester bond, and a lactone ring. 306 R is a single bond or a linear or branched alkanediyl group having 1 to 4 carbon atoms. 309 is an alkyl group having 1 to 20 carbon atoms, which may contain at least one selected from a hydroxy group, an ether bond, an ester bond, and a lactone ring.

[0131] Examples of the compound represented by formula (F1) include tris[2-(methoxymethoxy)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, tris[2-(2-methoxyethoxymethoxy)ethyl]amine, tris[2-(1-methoxyethoxy)ethyl]amine, tris[2-(1-ethoxyethoxy)ethyl]amine, tris[2-(1-ethoxypropoxy)ethyl]amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diamine, Azabicyclo[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine N,N-bis(2-acetoxyethyl) 2-(acetoxyacetoxy)ethylamine, tris(2-methoxycarbonyloxyethyl)amine, tris(2-tert-butoxycarbonyloxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, tris[2-(methoxycarbonylmethyl)oxyethyl]amine, tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine, Tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine amine, N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)ethylamine, N,N-Bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxy

[0033] Examples of the amines include, but are not limited to, N-butylbis[2-(2-methoxyethoxycarbonyl)ethyl]amine, N-methylbis(2-acetoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine, N-methylbis(2-pivaloyloxyethyl)amine, N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine, N-ethylbis[2-(tert-butoxycarbonyloxy)ethyl]amine, tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine, N-butylbis(methoxycarbonylmethyl)amine, N-hexylbis(methoxycarbonylmethyl)amine, and β-(diethylamino)-δ-valerolactone.

[0132] The content of component (F) is 0 to 3 parts by mass per 100 parts by mass of component (A), but when contained, from the viewpoint of sensitivity, it is preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass. The component (F) can be used alone or in combination of two or more types.

[0133] [(G) Antioxidants] The antioxidant (G) can improve the heat resistance and transparency of the photosensitive resin composition more easily. Examples of the antioxidant (G) include hindered phenol compounds, ammonia, primary aliphatic amines, and hindered amine compounds.

[0134] The hindered phenol compound is not particularly limited, but the following are preferred: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (trade name: IRGANOX 1330), 2,6-di-tert-butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butyl-hydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester (trade name: IRGANOX 1330), 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) (trade name: Adekastab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (trade name: Sumilizer GS), 2,2'-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (trade name: Seenox 226M), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX 1520L), 2,2'-ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-Tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: Adekastab AO-30), tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (trade name: Adekastab AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (trade name: IRGANOX 565), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) (trade name: IRGANOX 1098), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzyl ethyl phosphonate) calcium / polyethylene wax mixture (50:50) (trade name: IRGANOX 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1135), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R), and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine (trade name: Sumilizer GP).

[0135] Examples of the primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine.

[0136] The hindered amine compound is not particularly limited, but the following compounds are preferred. For example, p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade names: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (trade name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (trade name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac CD), p,p-toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-phenyl-N'-(3-methacloryloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name: Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (trade name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] (trade name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-Triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 123), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 770), bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate (trade name: TINUVIN 144), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: TINUVIN 765), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (trade name: LA-52), mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62), mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name: LA-67), 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol Examples of suitable esters include a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-63P), a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-68LD), (2,2,6,6-tetramethylene-4-piperidyl)-2-propylenecarboxylate (trade name: Adekastab LA-82), and (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylenecarboxylate (trade name: Adekastab LA-87).

[0137] The content of the component (G) is not particularly limited, but when it is contained, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention.

[0138] [Other additives] The photosensitive resin composition of the present invention may contain other additives in addition to the above-mentioned components, such as surfactants commonly used to improve coatability.

[0139] The surfactant is preferably a nonionic surfactant, such as a fluorine-containing surfactant, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, or fluorine-containing organosiloxane compound. Commercially available surfactants may be used, such as Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne (registered trademark) DS-401, DS-4031, and DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.). Of these, Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant is preferably 0.01 to 5 parts by mass per 100 parts by mass of component (A).

[0140] The photosensitive resin composition of the present invention may contain a silane coupling agent as another additive. The inclusion of a silane coupling agent can further enhance the adhesion of the resin film obtained from the composition to the substrate. Examples of silane coupling agents include epoxy group-containing silane coupling agents and aromatic group-containing aminosilane coupling agents. These can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited, but when contained, it is preferably 0.01 to 5 mass % in the photosensitive resin composition of the present invention.

[0141] The photosensitive resin composition of the present invention can be prepared by a conventional method, for example, by stirring and mixing the above-mentioned components, and then filtering the mixture using a filter or the like as needed.

[0142] The photosensitive resin composition of the present invention has excellent dispersion stability in the form of a varnish, suppresses aggregation in the form of a film, and is used as a material for optical members that require shielding (optical member applications).

[0143] [Pattern Forming Method Using Photosensitive Resin Composition] The pattern forming method using the photosensitive resin composition of the present invention comprises the steps of: (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention; (ii) exposing the photosensitive resin film to light; (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. It includes:

[0144] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention. Examples of the substrate include silicon wafers, silicon wafers for through-hole electrodes, silicon wafers thinned by backside polishing, plastic or ceramic substrates, and substrates having metals such as Ni and Au on the entire surface or part of the substrate by ion sputtering or plating. Substrates having either or both grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm may also be used. The opening width and depth of the grooves or holes in the substrate can be measured using a scanning electron microscope.

[0145] The photosensitive resin film of the present invention can be formed, for example, by applying the photosensitive resin composition of the present invention to the substrate by a method such as dipping, spin coating, or roll coating, and then pre-heating (pre-baking: PB) as necessary to efficiently carry out the photocuring reaction. Pre-heating can be carried out, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0146] The amount of the photosensitive resin composition to be applied can be appropriately selected depending on the purpose, but it is preferable that the amount be such that the film thickness becomes 0.1 to 200 μm, preferably 1 to 150 μm.

[0147] In order to improve the film thickness uniformity on the substrate surface, a solvent may be dripped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dripped and its amount can be appropriately selected depending on the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as PGME, etc. are preferred, but the solvent used in the photosensitive resin composition of the present invention can also be used.

[0148] Next, (ii) the photosensitive resin film is exposed to light. The exposure is preferably carried out with light having a wavelength of 1 to 600 nm, more preferably with light of 10 to 600 nm, and even more preferably with light of 190 to 500 nm. Examples of light with such wavelengths include light of various wavelengths generated by a radiation generator, such as ultraviolet light such as g-line, h-line, and i-line, and far ultraviolet light (248 nm, 193 nm). Of these, light with a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is 10 to 10,000 mJ / cm. 2 is preferred.

[0149] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out therein. The material of the photomask is not particularly limited, but is preferably one that blocks light of the above wavelengths. For example, a photomask having a light-shielding film such as chromium is preferably used.

[0150] Furthermore, to enhance development sensitivity, post-exposure bake (PEB) may be performed. PEB is preferably performed at 40 to 150°C for 0.5 to 10 minutes. PEB crosslinks the exposed areas, forming an insolubilized pattern that is insoluble in the developer solvent.

[0151] After exposure or PEB, (iii) the pattern is formed by development with a developer. As the developer, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as PGME, etc. are preferred, but the solvent used in the photosensitive resin composition of the present invention can also be used. Examples of the development method include a conventional method, such as immersing the patterned substrate in the developer. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a photosensitive resin film having the desired pattern.

[0152] Furthermore, (iv) it is preferable to post-cure the patterned photosensitive resin film using an oven or hot plate at 100 to 250°C, preferably 150 to 220°C. A post-cure temperature of 100 to 250°C increases the crosslink density of the photosensitive resin composition and removes remaining volatile components, making it more preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, electrical properties, and adhesive strength. The post-cure time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. By using the photosensitive resin composition of the present invention, a film with excellent film properties can be obtained even when post-cure is performed at a relatively low temperature of around 200°C. The film thickness of the post-cure film (cured film) is usually 1 to 200 μm, preferably 5 to 50 μm.

[0153] When it is not necessary to form a pattern, for example, when it is desired to simply form a uniform photosensitive resin film, the film can be formed by exposing the film to light of an appropriate wavelength without using a photomask in step (ii) of the pattern formation method.

[0154] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin film obtained from the photosensitive resin composition of the present invention on the support film.

[0155] The photosensitive dry film (support film and photosensitive resin film) is solid, and the photosensitive resin film does not contain a solvent, so there is no risk of bubbles due to volatilization remaining inside the photosensitive resin film or between the film and the uneven substrate. Taking into consideration the flatness on the uneven substrate, step coverage, and the substrate stacking distance, there is an appropriate film thickness range. Therefore, the film thickness of the photosensitive resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0156] Furthermore, the viscosity and fluidity of the photosensitive resin film are closely related, and the photosensitive resin film can exhibit appropriate fluidity within an appropriate viscosity range, allowing it to penetrate deep into narrow gaps and strengthen adhesion to the substrate by softening the resin. Therefore, from the viewpoint of the fluidity of the photosensitive resin film, the viscosity of the photosensitive resin film is preferably 10 to 5,000 Pa·s at a temperature of 80 to 120°C, more preferably 30 to 2,000 Pa·s, and even more preferably 50 to 300 Pa·s. In the present invention, the viscosity is measured using a rotational viscometer.

[0157] When the photosensitive dry film of the present invention is adhered to an uneven substrate (for example, a substrate having grooves and / or holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm), the photosensitive resin film conforms to the unevenness to provide a coating, thereby achieving high flatness. In particular, the photosensitive resin film of the present invention is flexible, so that even higher flatness can be achieved. Furthermore, when the photosensitive resin film is adhered to the substrate in a vacuum environment, the occurrence of gaps can be more effectively prevented.

[0158] Next, the photosensitive dry film of the present invention can be produced by applying the photosensitive resin composition of the present invention to a substrate (support film) and drying it to form a photosensitive resin film. A film coater typically used for producing adhesive products can be used as a production device for the photosensitive dry film. Examples of the film coater include a comma coater, a comma reverse coater, a multi-coater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three-roll bottom reverse coater, and a four-roll bottom reverse coater.

[0159] The support film is unwound from the unwinding shaft of the film coater and passed through the coater head of the film coater. The photosensitive resin composition of the present invention is applied to the support film at a predetermined thickness, and then the film is passed through a hot air circulating oven at a predetermined temperature and time to dry on the support film, forming a photosensitive resin film, thereby obtaining a photosensitive dry film. Optionally, the photosensitive dry film, together with a protective film unwound from another unwinding shaft of the film coater, is passed through a laminating roll at a predetermined pressure to bond the photosensitive resin film on the support film to the protective film, and then the film is wound around the winding shaft of the film coater, thereby producing a photosensitive dry film with a protective film. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0160] The support film may be a single-layer film made of a single film or a multilayer film made of multiple polymer films laminated together. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Polyethylene terephthalate is preferred because of its moderate flexibility, mechanical strength, and heat resistance. These films may also be subjected to various treatments, such as corona treatment or application of a release agent. Commercially available products may be used, such as Cerapeel WZ (RX) and Cerapeel BX8 (R) (Toray Advanced Film Co., Ltd.), E7302 and E7304 (Toyobo Co., Ltd.), Purex G31 and Purex G71T1 (Teijin DuPont Films Co., Ltd.), PET38x1-A3, PET38x1-V8, and PET38x1-X08 (Nippa Corporation).

[0161] The protective film may be the same as the support film described above, but polyethylene terephthalate and polyethylene, which have appropriate flexibility, are preferred. Commercially available products can be used for these, and examples of polyethylene terephthalate include those already exemplified, and examples of polyethylene include GF-8 (manufactured by Tamapoly Corporation) and PE Film 0 Type (manufactured by Nippa Corporation).

[0162] The thickness of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoints of stability in the production of the photosensitive dry film and prevention of the tendency to wind around the core and so-called curling.

[0163] [Pattern formation method using photosensitive dry film] The pattern formation method using a photosensitive dry film is as follows: (i) forming a photosensitive resin film on a substrate using the photosensitive dry film of the present invention; (ii) exposing the photosensitive resin film to light; (iii) A step of developing the exposed photosensitive resin film with a developer to form a pattern. It includes:

[0164] First, in the above step (i), a photosensitive resin film is formed on a substrate using a photosensitive dry film. Specifically, the photosensitive resin film of the photosensitive dry film is attached to the substrate, thereby forming the photosensitive resin film on the substrate. If a protective film is laminated on the photosensitive dry film, the protective film is peeled off from the photosensitive dry film, and then the photosensitive resin film of the photosensitive dry film is attached to the substrate. The attachment can be performed, for example, using a film attachment device.

[0165] The substrate may be the same as that described in the pattern formation method using a photosensitive resin composition. A vacuum laminator is preferred as the film laminating device. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is adhered to the substrate on a table at a predetermined temperature using a laminating roll at a predetermined pressure in a vacuum chamber at a predetermined vacuum level. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum level is preferably 50 to 500 Pa.

[0166] To obtain a photosensitive resin film of the required thickness, the film may be applied multiple times as necessary. For example, the number of times of application is about 1 to 10, which can obtain a photosensitive resin film of about 10 to 1,000 μm, particularly about 100 to 500 μm thick.

[0167] In order to efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-heating (pre-baking) may be carried out as necessary. Pre-baking can be carried out, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0168] As in the case of the pattern formation method using the photosensitive resin composition, the photosensitive resin film attached to the substrate can be patterned by (ii) exposing the photosensitive resin film to light, (iii) developing the exposed photosensitive resin film with a developer, and, if necessary, (iv) performing a post-curing treatment. Note that the support film of the photosensitive dry film is peeled off before pre-baking or PEB, or removed by other methods, depending on the process. [Example]

[0169] The present invention will be explained in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

[0170] In the synthesis examples below, the molecular weight (Mw) of each silicone resin was measured by GPC using a TSKgel Super HZM-H column (manufactured by Tosoh Corporation) under analysis conditions of a flow rate of 0.6 mL / min, tetrahydrofuran as an eluent, and a column temperature of 40°C, with monodisperse polystyrene as the standard.

[0171] In the following Synthesis Examples 1-1 to 1-4, silicone resins (polymers) were synthesized that were used in preparing the photosensitive resin compositions of Examples 1 to 9. The compounds (S-1) to (S-6) used in the synthesis of the silicone resins are as follows. [ka]

[0172] [1] Synthesis of silicone-based polymers [Synthesis Example 1-1] Synthesis of Silicone Resin (1) A 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser was charged with 17.6 g (0.28 mol) of compound (S-1), 79.5 g (0.30 mol) of compound (S-2), and 79.9 g (0.43 mol) of compound (S-3), followed by the addition of 2,000 g of toluene and heating to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, followed by the addition of 67.9 g (0.35 mol) of compound (S-5) and compound (S-6) (y 1 399.8 (0.65 mol) of hydroxypropyl methylcellulose (HMP) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain silicone resin (1). Silicone resin (1) was 1 It was confirmed by H-NMR (Bruker) that the silicone resin (1) contained repeating units a1, b1, a3, b3, a4, and b4. The molecular weight (Mw) of the silicone resin (1) was 35,000, and the silicone content was 64.4% by mass.

[0173] [Synthesis Example 1-2] Synthesis of Silicone Resin (2) A 3 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 109.2 g (0.26 mol) of compound (S-1), 64.5 g (0.15 mol) of compound (S-4), and 18.6 g (0.10 mol) of compound (S-3), followed by the addition of 2,000 g of toluene and heating to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, followed by the addition of 54.2 g (0.30 mol) of compound (S-5) and compound (S-6) (y 1 589.2 g (0.4 mol) of hydroxypropyl methylcellulose (HMP) (=38) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain silicone resin (2). Silicone resin (2) was 1 H-NMR (Bruker) confirmed that the silicone resin (2) contained repeating units a1, b1, a2, b2, a4, and b4. The molecular weight (Mw) of the silicone resin (2) was 42,000, and the silicone content was 72.6% by mass.

[0174] [Synthesis Example 1-3] Synthesis of Silicone Resin (3) A 3 L flask equipped with a stirrer, a thermometer, a nitrogen purge device, and a reflux condenser was charged with 185.5 g (0.70 mol) of compound (S-2) and 90.3 g (0.21 g) of compound (S-4), followed by 2,000 g of toluene, and the mixture was heated to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, followed by 155.2 g (0.80 mol) of compound (S-5) and 155.2 g (0.80 mol) of compound (S-6) (y 1 589.2 g (0.2 mol) of hydroxypropyl methylcellulose (HMP) (=38) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain silicone resin (3). Silicone resin (3) was 1 H-NMR (Bruker) confirmed that the silicone resin (3) contained repeating units a2, b2, a3, b3, a4, and b4. The molecular weight (Mw) of the silicone resin (3) was 32,000, and the silicone content was 75.5% by mass.

[0175] [Synthesis Example 1-4] Synthesis of Silicone Resin (4) A 3 L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 126.0 g (0.30 g) of compound (S-1), 55.7 g (0.21 mol) of compound (S-2), and 215.0 g (0.50 mol) of compound (S-4), followed by the addition of 2,000 g of toluene and heating to 70° C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, followed by the addition of 67.9 g (0.35 mol) of compound (S-5) and compound (S-6) (y 1 399.8 g (0.65 mol) of hydroxypropyl methylcellulose (HMP-8) was added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain silicone resin (4). Silicone resin (4) was 1H-NMR (Bruker) confirmed that the silicone resin (4) contained repeating units a1, b1, a2, b2, a3, and b3. The molecular weight (Mw) of the silicone resin (4) was 36,000, and the silicone content was 58.4% by mass.

[0176] [2] Synthesis of acrylic resin In the following Synthesis Examples 2-1 to 2-3, the acrylic resins (polymers) used in preparing the photosensitive resin compositions of Comparative Examples 1 to 7 were synthesized.

[0177] [Synthesis Example 2-1] Synthesis of acrylic resin (1) A flask equipped with a stirrer, reflux condenser, inert gas inlet, and thermometer was charged with 1 g of 2,2'-azobisisobutyronitrile (AIBN), 70 g of PGMEA (propylene glycol methyl ether acetate), and 70 g of toluene. Next, 55 g of acrylic acid and 56 g of methacrylic acid were added, and the mixture was thoroughly stirred under a nitrogen atmosphere. The temperature was then raised to 80°C and stirred for 6 hours while maintaining the reaction temperature at 80°C ± 2°C, yielding a solution of acrylic resin (1). PGMEA was added to the resulting solution so that the concentration of acrylic resin (1) was 60% by mass. The molecular weight (Mw) of the acrylic resin (1) was 28,000.

[0178] [Synthesis Example 2-2] Synthesis of acrylic resin (2) A flask equipped with a stirrer, reflux condenser, inert gas inlet, and thermometer was charged with 1 g of 2,2'-azobisisobutyronitrile (AIBN), 70 g of PGMEA (propylene glycol methyl ether acetate), and 70 g of toluene. Next, 50 g of acrylic acid and 79 g of methyl acrylate were added, and the mixture was thoroughly stirred under a nitrogen atmosphere. The temperature was then raised to 80°C and stirred for 6 hours while maintaining the reaction temperature at 80°C ± 2°C, yielding a solution of acrylic resin (2). PGMEA was added to the resulting solution so that the concentration of acrylic resin (2) was 60% by mass. The molecular weight (Mw) of the acrylic resin (2) was 32,000.

[0179] [3] Preparation of photosensitive resin composition [Examples 1 to 9, Comparative Examples 1 to 7] Each component was blended according to the blending amounts shown in Table 1, then stirred, mixed, and dissolved at room temperature, and then microfiltered through a 1.0 μm Teflon (registered trademark) filter to obtain the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7.

[0180] [Table 1]

[0181] [Table 2]

[0182] The anthraquinone dyes B-1, B-2, and B-3, the photoacid generator PAG-1, the photopolymerization initiator, the crosslinking agents CL-1 and CL-2, the antioxidants F-1 and F-2, and the quencher AM-1 listed in Tables 1 and 2 are as follows.

[0183] B-1: SDO-14 (manufactured by Arimoto Chemical Industry Co., Ltd.): maximum absorption wavelength 758.5 nm (JIS K 0115:2020 compliant), melting point 250°C B-2: Macrolex Green G (Bayer AG) maximum absorption wavelength: 690 nm [ka] B-3: Sumiplast Green G (manufactured by Sumika Chemtex Co., Ltd.) Maximum absorption wavelength: 645 nm [ka]

[0184] PAG-1 [ka]

[0185] Photopolymerization initiator: Irgacure OXE01: BASF Japan Ltd.

[0186] CL-1, CL-2 [ka]

[0187] F-1: CHIMASSORB 119FL (BASF) F-2: IRGANOX 3114 (BASF)

[0188] AM-1 [ka] Carbon black: Acetylene black (HS-100 manufactured by Denka Co., Ltd.: average primary particle diameter 45 nm)

[0189] [4] Preparation of photosensitive dry film Using a die coater as the film coater and a polyethylene terephthalate film (38 μm thick) as the support film, the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 were each applied onto the support film. The film was then dried by passing it through a hot air circulating oven (4 m long) set at 100°C for 5 minutes, forming a photosensitive resin film on the support film, thereby obtaining a photosensitive dry film. A polyethylene film (40 μm thick) was attached as a protective film to the photosensitive resin film using a laminating roll at a pressure of 1 MPa, producing a photosensitive dry film with a protective film. The film thickness of each photosensitive resin film is shown in Tables 3 and 4. The film thickness (μm) was measured using an optical interference film thickness measuring instrument (manufactured by SCREEN Semiconductor Solutions Co., Ltd.).

[0190] [5] Evaluation of photosensitive resin film (1) Evaluation of pattern formation The protective film was peeled off from the photosensitive dry film with the protective film. Using a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation), the vacuum level in the vacuum chamber was set to 80 Pa, and the photosensitive resin film on the support film was adhered to a textured silicone substrate. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator and the support film was peeled off. Next, to improve adhesion to the substrate, the substrate was pre-baked at 110°C for 5 minutes on a hot plate. To form a line-and-space pattern and a contact hole pattern, the resulting photosensitive resin film was exposed to light through a mask using a contact aligner-type exposure device at 365 nm exposure conditions. After exposure, the substrate was subjected to PEB on a hot plate at 130°C for 5 minutes, cooled, and spray-developed with PGMEA (propylene glycol methyl ether acetate) for 300 seconds to form a pattern.

[0191] The photosensitive resin film on the substrate, patterned using the above method, was post-cured in an oven at 180°C for 2 hours while purging with nitrogen. The cross sections of the resulting contact hole patterns (50 μm, 40 μm, 30 μm, 20 μm, 10 μm, and 5 μm) were then observed using a scanning electron microscope (SEM). The diameter of the smallest hole pattern that penetrated all the way to the bottom of the film was defined as the limiting resolution. Furthermore, the perpendicularity of the 40 μm contact hole pattern was evaluated using the resulting cross-sectional photographs: perpendicular patterns were rated as ◎, slightly reverse-tapered patterns as ○, reverse-tapered patterns as △, and poor openings as ×. The results are shown in Tables 3 and 4.

[0192] (2) Evaluation of compatibility Each of the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 was left to stand at 23°C for 24 hours, and the presence or absence of precipitation was visually confirmed. Those that showed no precipitation after 24 hours were marked with an ⊚, those that were fine for 12 hours but showed precipitation within 24 hours were marked with a △, and those that showed precipitation within 12 hours were marked with an ×. The results are shown in Tables 3 and 4.

[0193] (3) Evaluation of reliability (adhesion, crack resistance) Each of the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 was applied to a silicon wafer using a spin coater to a thickness of 10 μm, and then heated on a hot plate at 100° C. for 3 minutes to remove the solvent, followed by drying. The entire surface of the photosensitive resin composition coated on the wafer was irradiated with light (wavelength 365 nm) from a high-pressure mercury lamp using a SUSS MicroTec MA8 mask aligner without a mask, and the wafer was subjected to PEB at 140°C for 5 minutes, followed by immersion in PGMEA for 5 minutes. The film remaining after this process was heated in an oven at 190°C for 1 hour to obtain a photosensitive resin film. The resulting wafer was cut using a dicing saw equipped with a dicing blade (DISCO Corporation, DAD685, spindle rotation speed: 40,000 rpm, cutting speed: 20 mm / sec) to obtain 10 mm x 10 mm square test pieces. The resulting test pieces (10 pieces each) were subjected to a heat cycle test (10 minutes at -25°C, 10 minutes at 125°C, repeated 1,000 times), and the peeling state of the resin film from the wafer and the presence or absence of cracks after the heat cycle test were examined using an optical microscope. A sample with no peeling or cracking was rated as good, a sample with at least one peeling and a sample with at least one crack was rated as peeled, and a sample with at least one crack was rated as cracked. The results are shown in Tables 3 and 4.

[0194] (4) Heat resistance evaluation The mass of the test specimens prepared for reliability evaluation was measured before testing, and then the specimens were placed in an oven heated to 200°C for 1,000 hours. The specimens were then removed from the oven and their masses were measured. A mass change of less than 0.5% before and after testing was judged to be good, and a mass change of 0.5% or more before and after testing was judged to be bad. The results are shown in Tables 3 and 4.

[0195] (5) Light blocking test A photosensitive resin film was formed by laminating a photosensitive dry film onto a glass wafer. The entire surface was irradiated without a mask using a SUSS MicroTec MA8 mask aligner with a high-pressure mercury lamp (360 nm wavelength). The resulting film was then subjected to PEB and immersed in PGMEA. The remaining film was then further heated in an oven at 190°C for 2 hours to obtain a cured film. The transmittance (in %) of this film at wavelengths below 800 nm was measured using a U-3900H spectrophotometer (Hitachi High-Tech Science Corporation). The maximum transmittances are shown in Tables 3 and 4.

[0196] (6) Film agglomerates The dry film was cut out at random from a 1m section and checked for the presence or absence of aggregates using an optical microscope. Aggregates with a maximum diameter of less than 1µm were rated as ◯, and aggregates with a maximum diameter of 1µm or more were rated as ×.

[0197] The evaluation results of the resin films obtained using the photosensitive resin compositions and dry films shown in Tables 1 and 2 are shown in Tables 3 and 4, respectively.

[0198] [Table 3]

[0199] [Table 4]

[0200] As shown in Table 3, Examples 1 to 9, which used the photosensitive resin composition of the present invention, were found to have no film aggregates and to have good contact hole pattern shape, limiting resolution, compatibility, reliability (adhesion and crack resistance), and heat resistance, as well as light-shielding properties.On the other hand, as shown in Table 4, Comparative Examples 1 to 7 were found to be inferior to the Examples in terms of contact hole pattern shape, limiting resolution, compatibility, reliability (adhesion and crack resistance), and heat resistance.

[0201] From the above results, it was found that the photosensitive resin composition of the present invention has excellent dispersion stability of the varnish, is free of film aggregates, and can form a light-shielding cured product having good reliability (adhesion, crack resistance), heat resistance, and resolution.

[0202] The present specification includes the following aspects. [1]: A photosensitive resin composition comprising (A) a silicone skeleton-containing polymer, (B) an anthraquinone dye, and (C) a photoacid generator. [2]: The photosensitive resin composition according to [1], wherein the silicone skeleton-containing polymer (A) contains repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4): [ka] (In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and m is an integer of 1 to 600. a 1 ~a 4 and b 1 ~b 4 is 0≦a 1 < 1, 0 ≤ a 2 < 1, 0 ≤ a 3 < 1, 0 ≤ a 4 < 1, 0 ≤ b 1 < 1, 0 ≤ b 2 < 1, 0 ≤ b 3 < 1, 0 ≤ b 4 <1, 0 1 +a 2 +a 3 +a 4 <1, 0 1 +b 2 +b 3 +b 4 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 =1. X 1 ​​is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2): 3 is a divalent group represented by the following formula (X3): 4 is a divalent group represented by the following formula (X4): [ka] (In the formula, Z 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11 and R 12 are each independently a hydrogen atom or a methyl group. 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer of 0 to 7. 1 and q 2 are each independently an integer of 0 to 2. [ka] (In the formula, Z 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 21 and R 22 are each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer of 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. [ka] (In the formula, R 31and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer of 0 to 7. [ka] (In the formula, R 41 and R 42 are each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. 1 and u 2 are each independently an integer of 0 to 7, and v is an integer of 0 to 600. [3]: The photosensitive resin composition according to the above [1] or [2], further comprising one or more of (D) a crosslinking agent, (E) a solvent, (F) a quencher, and (G) an antioxidant. [4]: The photosensitive resin composition according to [1], [2] or [3], characterized in that it contains 0.01 to 50 parts by mass of (B) an anthraquinone dye. [5]: The photosensitive resin composition according to any one of [1] to [4], wherein the maximum absorption wavelength of (B anthraquinone dye) is 800 nm or less. [6]: The photosensitive resin composition according to any one of [1] to [5], which is used for optical members. [7]: A photosensitive resin film obtained from the photosensitive resin composition according to any one of the above [1] to [6]. [8]: A photosensitive dry film comprising a support film and the photosensitive resin film according to [7] on the support film. [9]: (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of the above [1] to [6]; (ii) exposing the photosensitive resin film to light; (iii) developing the exposed photosensitive resin film with a developer to form a pattern; A pattern forming method using a photosensitive resin composition comprising:

[10] : (i) forming a photosensitive resin film on a substrate using the photosensitive dry film described in [8] above; (ii) exposing the photosensitive resin film to light; (iii) developing the exposed photosensitive resin film with a developer to form a pattern; A pattern forming method using a photosensitive dry film, comprising:

[11] : The pattern forming method according to the above [9] or

[10] , further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

[0203] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A photosensitive resin composition comprising (A) a silicone skeleton-containing polymer, (B) an anthraquinone dye, and (C) a photoacid generator.

2. 2. The photosensitive resin composition according to claim 1, wherein the silicone skeleton-containing polymer (A) contains repeating units represented by the following formulas (a1) to (a4) and (b1) to (b4): 【Chemical 1】 (In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and m is an integer of 1 to 600. a 1 ~a 4 and b 1 ~b 4 is 0≦a 1 <1, 0≦a 2 <1, 0≦a 3 <1, 0≦a 4 <1, 0≦b 1 <1, 0≦b 2 <1, 0≦b 3 <1, 0≦b 4 <1, 0<a 1 +a 2 +a 3 +a 4 <1, 0<b 1 +b 2 +b 3 +b 4 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1. X 1 is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2): 3 is a divalent group represented by the following formula (X3): 4 is a divalent group represented by the following formula (X4): 【Chemistry 2】 (In the formula, Z 1 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 11 and R 12 are each independently a hydrogen atom or a methyl group. 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and p 2 are each independently an integer of 0 to 7. 1 and q 2 are each independently an integer of 0 to 2. 【Chemistry 3】 (In the formula, Z 2 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 21 and R 22 are each independently a hydrogen atom or a methyl group. 23 and R 24 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and r 2 are each independently an integer of 0 to 7. 1 and s 2 are each independently an integer of 0 to 2. 【Chemistry 4】 (In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 are each independently an integer from 0 to 7. 【Chemistry 5】 (In the formula, R 41 and R 42 are each independently a hydrogen atom or a methyl group. 43 and R 44 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. 1 and u 2 are each independently an integer of 0 to 7, and v is an integer of 0 to 600.

3. 2. The photosensitive resin composition according to claim 1, further comprising one or more of a crosslinking agent (D), a solvent (E), a quencher (F), and an antioxidant (G).

4. 2. The photosensitive resin composition according to claim 1, wherein the component (B) contains 0.01 to 50 parts by mass of an anthraquinone dye per 100 parts by mass of the component (A).

5. 2. The photosensitive resin composition according to claim 1, wherein the anthraquinone dye (B) has a maximum absorption wavelength of 800 nm or less.

6. 2. The photosensitive resin composition according to claim 1, which is used for optical components.

7. A photosensitive resin film obtained from the photosensitive resin composition according to claim 1.

8. A photosensitive dry film comprising a support film and the photosensitive resin film according to claim 7 on the support film.

9. (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to claim 1; (ii) exposing the photosensitive resin film to light; (iii) developing the exposed photosensitive resin film with a developer to form a pattern; A pattern forming method using a photosensitive resin composition comprising:

10. (i) forming a photosensitive resin film on a substrate using the photosensitive dry film according to claim 8; (ii) exposing the photosensitive resin film to light; (iii) developing the exposed photosensitive resin film with a developer to form a pattern; A pattern forming method using a photosensitive dry film, comprising:

11. 11. The pattern forming method according to claim 9, further comprising the step of (iv) post-curing the photosensitive resin film patterned by development at a temperature of 100 to 250°C.

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