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

Abstract

The technical problem of the present invention is to provide: a photosensitive resin composition which has a shielding function, has dispersion stability in a varnish, is suppressed in aggregation in the film, and is capable of forming a fine pattern; and a photosensitive resin coating film can be formed. [Solution] A photosensitive resin composition characterized by containing (A) a polymer containing an organosilicon skeleton, (B) an anthraquinone dye, and (C) a photoacid generator.

Description

Technical Field

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

[0002] Some optical devices have a hollow structure bonded to a cover glass by spacers formed around the sensor. These spacers are typically formed through a photolithography process using a photosensitive resin composition. While information from light incident from the cover glass is typically transmitted to the sensor, if light leaking from the spacers also enters, it can cause problems in image processing, thus requiring a light-shielding function. As a photosensitive resin composition with a cured film exhibiting this light-shielding function, a material has been proposed that incorporates carbon black into a photosensitive silicone composition primarily composed of a silicone polymer containing a silphenylene skeleton (Patent Document 1).

[0003] However, there is a problem that carbon black may precipitate in the varnish or aggregates may remain in the cured film. In addition, it is also desired to further improve the level of miniaturization by pattern formation.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-016879 Summary of the Invention

[0007] (1) Technical issues to be resolved

[0008] The present invention has been implemented in view of the above situation, and its purpose is to provide a photosensitive resin composition, a photosensitive resin film, a photosensitive dry film, and a pattern forming method using the composition. The photosensitive resin composition has a shielding function and has dispersion stability in a varnish, and aggregates in the film are suppressed and a fine pattern can be formed, and a photosensitive resin film can be formed.

[0009] (2) Technical solution

[0010] In order to solve the above technical 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.

[0011] The photosensitive resin composition of the present invention can provide: a photosensitive resin composition containing an anthraquinone-based dye, which has a shielding function, exhibits dispersion stability in a varnish, suppresses aggregation in the film, can form a fine pattern, and can form a photosensitive resin film; a photosensitive resin film; a photosensitive dry film; a pattern forming method using the composition; and a pattern forming method using the photosensitive dry film.

[0012] Furthermore, the polymer (A) containing a silicone skeleton in the photosensitive resin composition of the present invention preferably comprises repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4):

[0013] [Chemical Formula 1]

[0014]

[0015] Where R 1 ~R 4 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms; m represents an integer from 1 to 600; a 1 ~a 4 and b 1 ~b 4 To satisfy 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 number; 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),

[0016] [Chemical Formula 2]

[0017]

[0018] In formula (X1), Z 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 11 and R 12 are each independently a hydrogen atom or a methyl group; R 13 and R 14 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; 1 and p 2 Each independently represents an integer from 0 to 7; q 1 and q 2 are each independently an integer from 0 to 2,

[0019] [Chemical Formula 3]

[0020]

[0021] In formula (X2), Z 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 21 and R 22 are each independently a hydrogen atom or a methyl group; R 23 and R 24 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; 1 and r 2 Each independently represents an integer from 0 to 7; s 1 and s 2 are each independently an integer from 0 to 2,

[0022] [Chemical Formula 4]

[0023]

[0024] 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 from 0 to 7,

[0025] [Chemical Formula 5]

[0026]

[0027] In formula (X4), R 41 and R42 are each independently a hydrogen atom or a methyl group; R 43 and R 44 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms; 1 and u 2 are each independently an integer from 0 to 7; and v is an integer from 0 to 600.

[0028] The photosensitive resin composition of the present invention can provide a photosensitive resin film having good adhesion to a laminate, a substrate, etc., good pattern forming ability, crack resistance, and heat resistance.

[0029] The photosensitive resin composition of the present invention preferably further comprises at least one of (D) a crosslinking agent, (E) a solvent, (F) a quencher, and (G) an antioxidant.

[0030] Such a photosensitive resin composition facilitates pattern formation and further enhances the strength of the cured product. Furthermore, it can improve resolution, suppress sensitivity changes after exposure, reduce substrate and environmental dependence, and improve exposure latitude and pattern shape.

[0031] Furthermore, the photosensitive resin composition of the present invention preferably contains 0.01 to 50 parts by mass of the anthraquinone-based dye (B) relative to 100 parts by mass of the component (A).

[0032] Furthermore, it is preferred that the maximum absorption wavelength of the anthraquinone dye (B) in the photosensitive resin composition of the present invention is 800 nm or less.

[0033] Such a photosensitive resin composition can further have a shielding function, has dispersion stability in a varnish, suppresses aggregation in a film, and can form a fine pattern.

[0034] The photosensitive resin composition of the present invention is preferably used for optical members.

[0035] Such a photosensitive resin composition has excellent dispersion stability in a varnish, suppresses aggregation in a film, and can be used as a material for optical members requiring shielding.

[0036] The present invention provides a photosensitive resin coating, which is obtained from the photosensitive resin composition of the present invention.

[0037] Such a photosensitive resin coating has a shielding function, exhibits dispersion stability in a varnish, suppresses aggregation in the film, and enables formation of a fine pattern.

[0038] Furthermore, the present invention provides a photosensitive dry film comprising a support film and a photosensitive resin coating according to the present invention on the support film.

[0039] By using such an optical dry film, the photosensitive resin film of the present invention having a desired thickness can be easily obtained.

[0040] The present invention provides a method for forming a pattern using the photosensitive resin composition of the present invention, comprising: 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 using a developer to form a pattern.

[0041] In addition, the present invention provides a pattern forming method using the photosensitive dry film of the present invention, which includes: a process of forming a photosensitive resin film on a substrate using the above-mentioned photosensitive dry film; a process of exposing the photosensitive resin film; and a process of developing the exposed photosensitive resin film using a developer to form a pattern.

[0042] By using such a pattern forming method, a contact hole pattern with good verticality can be formed.

[0043] The pattern forming method using the photosensitive resin composition of the present invention preferably further comprises a step of post-curing the photosensitive resin film having the pattern formed by development at a temperature of 100 to 250°C.

[0044] This pattern forming method including a post-curing step can increase the crosslinking density of the photosensitive resin composition of the present invention and remove residual volatile components. Furthermore, this method is more preferred from the perspectives of adhesion to the substrate, heat resistance and strength, electrical properties, and adhesive strength.

[0045] (3) Beneficial effects

[0046] As described above, the photosensitive resin composition of the present invention can provide: a photosensitive resin composition containing an anthraquinone-based dye that has a shielding function, exhibits dispersion stability in a varnish, suppresses aggregation in the film, can form a fine pattern, and can form a photosensitive resin film; a photosensitive resin film; a photosensitive dry film; a pattern forming method using the composition; and a pattern forming method using the photosensitive dry film. DETAILED DESCRIPTION

[0047] As described above, a photosensitive resin composition has been sought to be developed which has a shielding function, has dispersion stability in a varnish, suppresses aggregation in a film, can form a fine pattern, and can form a photosensitive resin film.

[0048] The inventors of this application have repeatedly conducted in-depth studies on the above-mentioned technical problems and found that by using anthraquinone-based dyes as light-absorbing materials to impart shielding functions, a photosensitive resin composition can be obtained that has dispersion stability in varnish, suppresses aggregates in the film, and can form fine patterns, thereby completing the present invention.

[0049] That is, the present invention is a photosensitive resin composition comprising (A) a polymer containing an organosilicon skeleton, (B) an anthraquinone-based dye, and (C) a photoacid generator.

[0050] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0051] [(A) Polymer containing silicone skeleton]

[0052] The silicone skeleton-containing polymer of component (A) is not particularly limited, but preferably contains repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4) (hereinafter, for convenience, also referred to as repeating units a1 to a4 and b1 to b4, respectively).

[0053] [Chemical Formula 6]

[0054]

[0055] In formulas (a1) to (a4), R 1 ~R 4 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms. m represents an integer from 1 to 600. When m is an integer greater than 2, each R 3 They may be the same or different from each other. 4 They may be the same or different. When there are two or more siloxane units in repeating units a1 to a4, each siloxane unit may be the same, or may contain two or more different siloxane units. When containing two or more different siloxane units (i.e., when m is an integer of 2 or more), the siloxane units may be randomly bonded or alternately bonded, or may contain blocks of multiple siloxane units of the same type.

[0056] The monovalent hydrocarbon group may be linear, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, propyl, hexyl, and cyclohexyl, and isomers thereof; and aryl groups such as phenyl. Methyl and phenyl groups are preferred due to their ease of raw material availability.

[0057] In formulae (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. An integer in the range of 1 to 600 is preferred because flexibility can be imparted and film formation is facilitated.

[0058] In formulas (a1) and (b1), X 1 It is a divalent group represented by the following formula (X1).

[0059] [Chemical Formula 7]

[0060]

[0061] In formula (X1), Z 1 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 11 and R 12 R are each independently a hydrogen atom or a methyl group. 13 and R 14 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and p 2 Each independently represents an integer from 0 to 7. 1 and q 2 Each independently represents an integer from 0 to 2.

[0062] The alkyl group may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, propyl, butyl, and isomers thereof. The alkoxy group may be linear, branched, or cyclic, and specific examples thereof include methoxy, ethoxy, propoxy, butoxy, and isomers thereof.

[0063] In formulas (a2) and (b2), X 2 It is a divalent group represented by the following formula (X2).

[0064] [Chemical Formula 8]

[0065]

[0066] In formula (X2), Z 2 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 21 and R 22 R are each independently a hydrogen atom or a methyl group. 23 and R 24 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and r 2 Each independently represents an integer from 0 to 7. 1 and s 2Each independently represents an integer of 0 to 2. Examples of the alkyl group and the alkoxy group include the same groups as those described above.

[0067] In formulas (a3) and (b3), X 3 It is a divalent group represented by the following formula (X3).

[0068] [Chemical Formula 9]

[0069]

[0070] In formula (X3), R 31 and R 32 are each independently a hydrogen atom or a methyl group. 1 and t 2 Each independently represents an integer from 0 to 7.

[0071] In formulas (a4) and (b4), X 4 It is a divalent group represented by the following formula (X4).

[0072] [Chemical Formula 10]

[0073]

[0074] In formula (X4), R 41 and R 42 R are each independently a hydrogen atom or a methyl group. 43 and R 44 Each is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. 1 and u 2 Each independently represents an integer of 0 to 7. v represents an integer of 0 to 600, preferably an integer of 0 to 400, more preferably an integer of 0 to 200. If it is in the range of 0 to 600, it can impart flexibility and facilitate film formation, so it is preferred. As the monovalent hydrocarbon group, the following may be cited: 1 ~R 4 In the group represented by formula (X4), when v is an integer greater than 2, the siloxane units represented by the subscript v may be randomly bonded or alternately bonded, and may also contain blocks of multiple siloxane units of the same type.

[0075] The weight average molecular weight (Mw) of the silicone skeleton-containing polymer of component (A) is preferably 3,000 to 500,000, more preferably 5,000 to 200,000. In the present invention, Mw is a polystyrene-equivalent measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.

[0076] In formulas (a1) to (a4) and (b1) to (b4), a 1~a 4 and b 1 ~b 4 To satisfy 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, preferably 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 +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, more preferably a number that satisfies 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 =1.

[0077] The silicone-backbone-containing polymer of component (A) preferably has crosslinking groups such as epoxy groups and hydroxyl groups or reactive sites for crosslinking reactions in the molecule. In other words, the polymer preferably contains at least one selected from repeating units a1 to a3 and at least one selected from repeating units b1 to b3. In this case, in formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 It is preferred to satisfy 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 <1、0<b 1 +b 2 +b 3 <1 and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 =1, more preferably a number that satisfies 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, and more preferably satisfies 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 =1.

[0078] It is particularly preferred that the silicone skeleton-containing polymer of component (A) contains repeating units a3 and b3. In this case, in formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 It is preferred to satisfy 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<b3 <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, more preferably a number that satisfies 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 =1, and more preferably satisfies 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 =1.

[0079] The aforementioned repeating units may be randomly bonded or bonded in the form of a block polymer. Furthermore, the siloxane units in each repeating unit may be randomly bonded or may comprise blocks of multiple siloxane units of the same type. Furthermore, the organosilicon (siloxane unit) content in the silicone resin is preferably 30 to 80% by mass.

[0080] The silicone skeleton-containing polymer of component (A) functions as a substance imparting film-forming ability. Furthermore, the resulting resin film has good adhesion to laminates, substrates, etc., good patterning ability, crack resistance, and heat resistance.

[0081] The silicone skeleton-containing polymer of the component (A) may be used alone or in combination of two or more.

[0082] [Method for preparing polymer containing silicone skeleton]

[0083] The silicone skeleton-containing polymer of component (A) can be prepared by subjecting 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)), and at least one selected from the group consisting of 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)) to addition polymerization in the presence of a metal catalyst.

[0084] [Chemical Formula 11]

[0085]

[0086] In formula (2), R 1 ~R 4 and m and the above R 1 ~R 4 and m are the same.

[0087] [Chemical Formula 12]

[0088]

[0089] Where 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 and the above 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 Same as v.

[0090] As the metal catalyst, platinum (including platinum black), rhodium, palladium and other platinum group metal monomers can be used; platinum chloride, chloroplatinic acid and chloroplatinates such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (wherein x is preferably an integer from 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid ( For example, alcohol-modified chloroplatinic acid described in U.S. Patent No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, complexes of chloroplatinic acid and olefins described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, and U.S. Patent No. 3,775,452); substances in which a platinum group metal such as platinum black or palladium is supported on a carrier such as alumina, silica, or carbon; rhodium-olefin complexes; tris(triphenylphosphine)rhodium chloride (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinates and vinyl-containing siloxanes (particularly vinyl-containing cyclic siloxanes), etc.

[0091] 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, relative to 100 parts by mass of the total of compounds (1) to (6).

[0092] In the above-mentioned addition polymerization reaction, a solvent may be used as needed. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferred.

[0093] To avoid catalyst deactivation and to complete polymerization in a short time, the polymerization temperature is preferably 40-150°C, more preferably 60-120°C. The polymerization time varies depending on the type and amount of the resulting resin, but to prevent moisture from entering the polymerization system, it is preferably approximately 0.5-100 hours, more preferably 0.5-30 hours. After the reaction, if a solvent is used, it is distilled off to obtain the silicone skeleton-containing polymer of component (A).

[0094] The reaction method is not particularly limited. For example, a method may be mentioned in which at least one selected from the above compounds (3) to (6) is heated, a metal catalyst is added thereto, and then the above compounds (1) and (2) are added dropwise over 0.1 to 5 hours.

[0095] The raw material compounds may be blended so that the total molar ratio of the hydrosilyl groups contained in the above-mentioned compound (1) and the above-mentioned compound (2) to the total molar ratio of the alkenyl groups contained in at least one selected from the above-mentioned compounds (3) to (6) is preferably 0.67 to 1.67, more preferably 0.83 to 1.25.

[0096] The Mw of the silicone skeleton-containing polymer of the component (A) can be controlled by using a monoallyl compound such as o-allylphenol or a monohydrogenated silane or monohydrogenated siloxane such as triethylmonohydrogenated silane as a molecular weight modifier.

[0097] [(B) Anthraquinone dyes]

[0098] The anthraquinone dye of the component (B) is not particularly limited.

[0099] The anthraquinone-based dye of the component (B) to be blended in the photosensitive resin composition of the present invention is not particularly limited. Specifically, the following anthraquinone-based dyes can be used. Examples thereof include: (1) 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, (7) 2-(m-cyanoanilino)-1,3,4-trifluoroanthraquinone, (8) 2-(o-nitroanilino)-1,3,4-trifluoroanthraquinone, (9) 2-(p-nitroanilino)-1,3,4-trifluoroanthraquinone, (1 0) 2-(m-nitroanilino)-1,3,4-trifluoroanthraquinone, (11) 2-(p-tert-butylanilino)-1,3,4-trifluoroanthraquinone, (12) 2-(o-methoxyanilino)-1,3,4-trifluoroanthraquinone, (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-( (2) 2-(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-dimethylphenoxy)-1,4-difluoroanthraquinone, (28) 2,3-diphenylamino-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)-1,3,4-trichloroanthraquinone, (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 Fluoroanthraquinone, (49) 1,4-bis(cyclohexylamino)-2,3-difluoroanthraquinone, (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-tetrakis(p-methoxyphenoxy)anthraquinone, etc., can be used alone or in combination of two or more.

[0100] As the anthraquinone dye of component (B), commercially available products can be used. Specific examples thereof 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; CI Solvent Blue 14, 18, 35, 36, 45, 58, 59 9, 63, 68, 69, 78, 79, 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, etc.

[0101] The anthraquinone dye of component (B) is preferably a dye containing a pigment having a maximum absorption wavelength of 800 nm or less, preferably 300 to 800 nm. A maximum absorption wavelength of 800 nm or less is preferred because it can shield light leakage in the visible light region.

[0102] 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-based dye (component (B)) per 100 parts by mass of the silicone-backbone-containing resin (component (A)). An amount of 0.01 parts by mass or greater is preferred because it provides a light-shielding function against light leakage, while an amount of 50 parts by mass or less is preferred because it can suppress poor compatibility and the formation of aggregates.

[0103] [(C) Photoacid generator]

[0104] The photoacid generator (C) is not particularly limited as long as it decomposes upon irradiation with light to generate an acid. However, it is preferably a photoacid generator that decomposes upon irradiation with light having a wavelength of 190 to 500 nm to generate an acid. The composition used in the present invention has excellent compatibility with acid generators, allowing for the use of a wide range of acid generators.

[0105] The photoacid generator (component (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 derivatives, imidoylsulfonate derivatives, oximesulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

[0106] Examples of the onium salt include sulfonium salts represented by the following formula (C1) and iodonium salts represented by the following formula (C2).

[0107] [Chemical Formula 13]

[0108]

[0109] In the above formulas (C1) and (C2), R 101 ~R 105 Each is 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. - It is a non-nucleophilic counterion.

[0110] The alkyl group may be linear, branched, or cyclic. Specific examples 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 biphenyl. Examples of the aralkyl group include benzyl and phenethyl.

[0111] 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.

[0112] As R 101 ~R 105, preferably: an optionally substituted alkyl group such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, or 2-oxocyclohexyl; an optionally substituted aryl group such as phenyl, naphthyl, biphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, ethoxyphenyl, m-tert-butoxyphenyl, p-tert-butoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyloxyphenyl, or biphenylthiophenyl; and an optionally substituted aralkyl group such as benzyl or phenethyl. Among these, an optionally substituted aryl group or an optionally substituted aralkyl group is more preferred.

[0113] As the above A - Examples of the non-nucleophilic counter ions include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as methanesulfonate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonyl imide ion; fluoroalkanesulfonyl methide ions such as tris(trifluoromethanesulfonyl)methide ion; borate ions such as tetraphenylborate ion and tetrakis(pentafluorophenyl)borate ion, and the like.

[0114] Examples of the diazomethane derivative include compounds represented by the following formula (C3).

[0115] [Chemical Formula 14]

[0116]

[0117] In formula (C3), R 111 and R 112 Each is independently an alkyl group or a 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.

[0118] The above alkyl group may be any of linear, branched, and cyclic. Specific examples thereof include the following: 101 ~R 105 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.

[0119] Examples of the aryl group which may have a substituent include phenyl; alkoxyphenyl groups such as 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, and 3-tert-butoxyphenyl, 4-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; and halogenated aryl groups such as fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Examples of the aralkyl group include benzyl and phenethyl.

[0120] Examples of the glyoxime derivatives include compounds represented by the following formula (C4).

[0121] [Chemical Formula 15]

[0122]

[0123] In the above (C4), R 121 ~R 124 are each independently an alkyl group or a 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 They can bond to each other and form a ring together with the carbon atoms to which they are bonded. When a ring is formed, R 123 and R 124 The group formed by the bonding is a linear or branched alkylene group having 1 to 12 carbon atoms.

[0124] Examples of the alkyl group, halogenated alkyl group, aryl group and aralkyl group which may have a substituent include the following: 111 and R 112 The alkyl group, the halogenated alkyl group, the aryl group which may have a substituent, and the aralkyl group are the same as those exemplified above. Examples of the linear or branched alkylene group include methylene, ethylene, propylene, butylene, and hexylene.

[0125] 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)phenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tri(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, and trimethylsulfonium trifluoromethanesulfonate. Methanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(trifluoromethanesulfonyl) methide ([4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide), triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0126] Specific examples of the diazomethane derivatives include bis(phenylsulfonyl)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, and bis(n-propylsulfonyl)diazomethane. diazomethane, bis(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.

[0127] 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-pentanedioneglyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o(n-butanesulfonyl)-α-dimethylglyoxime, bis-o(n-butanesulfonyl)-α-diphenylglyoxime, bis-o(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-o(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, Oxime, bis-o-(methylsulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butylsulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime alkylsulfonyl)-α-dimethylglyoxime, bis-o-(phenylsulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorophenylsulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime and bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc.

[0128] Specific examples of the β-ketosulfone derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0129] Specific examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0130] Specific examples of the nitrobenzylsulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0131] Specific examples of the sulfonic acid ester derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0132] Specific examples of the imidosulfonate derivatives include phthalimidotrifluoromethanesulfonate, phthalimidotoluenesulfonate, 5-norbornene-2,3-dicarboximidotrifluoromethanesulfonate, 5-norbornene-2,3-dicarboximidotoluenesulfonate, 5-norbornene-2,3-dicarboximido-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0133] Specific examples of the oxime sulfonate derivatives include α-(phenylsulfonyloxyimino)-4-methylphenylacetonitrile and the like.

[0134] Specific examples of the imidosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-methylene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-methylene)-(2-methylphenyl)-acetonitrile.

[0135] Specific examples of the triazine derivatives include 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine.

[0136] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be preferably used.

[0137] As the photoacid generator of the component (C), the above-mentioned onium salts are preferred, and the above-mentioned sulfonium salts are more preferred.

[0138] From the perspective 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, relative to 100 parts by mass of component (A). If the content of component (C) is 0.05 parts by mass or more, sufficient acid is generated, and the cross-linking reaction proceeds fully, so it is preferred. In addition, if it is 20 parts by mass or less, the increase in the absorbance of the photoacid generator itself can be suppressed, and transparency is also sufficient, so it is preferred. Component (C) can be used alone or in combination of two or more.

[0139] In addition to (A) the polymer containing an organosilicon skeleton, (B) the anthraquinone dye, and (C) the photoacid generator, the photosensitive resin composition of the present invention preferably further comprises at least one of (D) a crosslinking agent, (E) a solvent, (F) a quencher, and (G) an antioxidant.

[0140] [(D) Cross-linking agent]

[0141] The crosslinking agent as the component (D) is a crosslinking agent that can react with the phenolic hydroxyl group of the component (A) or R 13 、R 14 、R 23 or R 24The alkoxy group represented by is a component that undergoes a condensation reaction and facilitates pattern formation, and further improves the strength of the cured product.

[0142] The crosslinking agent (component (D)) is preferably a resin having an Mw of 150 to 10,000, and particularly preferably a resin having an Mw of 200 to 3,000. An Mw of 150 or greater provides sufficient photocurability, while an Mw of 10,000 or less is preferred because it does not deteriorate the heat resistance of the composition after curing.

[0143] Furthermore, the cross-linking agent for the component (D) is preferably selected from the following nitrogen-containing compounds, such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds, each containing an average of two or more hydroxymethyl and / or alkoxymethyl groups in one molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds each containing an average of two or more hydroxymethyl or alkoxymethyl groups in one molecule; and epoxy compounds each containing an average of two or more epoxy groups in one molecule.

[0144] As said melamine compound, the melamine compound represented by following formula (D1) is mentioned.

[0145] [Chemical Formula 16]

[0146]

[0147] In formula (D1), R 201 ~R 206 Each is independently a hydroxymethyl group, an alkoxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, but at least one is a hydroxymethyl group or an alkoxymethyl group. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

[0148] Examples of the melamine compound represented by formula (D1) include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, and hexaethoxymethylmelamine.

[0149] 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 further alkoxylating the melamine monomer with an alcohol. The alcohol is preferably a lower alcohol, such as an alcohol having 1 to 4 carbon atoms.

[0150] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0151] Examples of the glycoluril compound include tetrakishydroxymethyl glycoluril and tetrakis(methoxymethyl) glycoluril.

[0152] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0153] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include melamine condensate modified with formaldehyde or formaldehyde-alcohol and urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0154] Examples of the modified melamine condensate include those obtained by subjecting the compound represented by the formula (D1) or its multimers (for example, oligomers such as dimers and trimers) to formaldehyde through addition condensation according to a conventional method to a desired molecular weight.

[0155] Examples of the formaldehyde- or formaldehyde-alcohol-modified urea condensate include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0156] The modified urea condensate can be obtained, for example, by hydroxymethylating a urea condensate of a desired molecular weight with formaldehyde according to a known method, or further alkoxylating the urea condensate with an alcohol.

[0157] Examples of the phenol compound having an average of two or more hydroxymethyl groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2′,6,6′-tetramethoxymethylbisphenol A.

[0158] Examples of the epoxy compound having an average of two or more epoxy groups in one molecule include bisphenol-type epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin, novolac-type epoxy resins such as phenol novolac-type epoxy resin and cresol novolac-type epoxy resin, trisphenol alkane-type epoxy resin, biphenyl-type epoxy resin, dicyclopentadiene-modified phenol novolac-type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthalene-ring-containing epoxy resin, glycidyl ester-type epoxy resin, alicyclic epoxy resin, and heterocyclic epoxy resin.

[0159] When the photosensitive resin composition of the present invention includes component (D), the content of component (D) is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of component (A). If the content is 0.5 parts by mass or greater, sufficient curability is achieved upon light irradiation. 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 effects of the present invention to be fully exhibited in the cured product. The crosslinking agent for component (D) can be used alone or in combination of two or more.

[0160] [(E) Solvent]

[0161] The solvent for the component (E) is not particularly limited as long as it can dissolve the components (A) to (D) and various additives described below, but an organic solvent is preferred because of its excellent solubility in the above components.

[0162] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentanone; 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, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents of these organic solvents, which have the best solubility for the photoacid generator.

[0163] From the viewpoint of compatibility with the photosensitive resin composition and viscosity, 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, relative to 100 parts by mass of the total of component (A), component (B), and component (C).

[0164] [(F) Quencher]

[0165] The quencher (component (F)) is preferably a compound that can suppress the diffusion rate of the acid generated by the photoacid generator within the photosensitive resin film. The addition of such a quencher can improve resolution, suppress sensitivity changes after exposure, reduce substrate and environmental dependence, and improve exposure latitude and pattern shape.

[0166] Examples of the quencher of the component (F) include aliphatic primary amines, aliphatic secondary amines or aliphatic tertiary amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives.

[0167] Examples of the aliphatic primary 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, hexadecylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine.

[0168] Examples of the aliphatic secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dihexadecylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine.

[0169] Examples of the aliphatic tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, trilaurylamine, trihexadecylamine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, and N,N,N',N'-tetramethyltetraethylenepentamine.

[0170] Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

[0171] 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, N,N-dimethyl-m-methylaniline, etc.), 4-methyltriphenylamine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives ( For example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (for example, oxazole, isoxazole, etc.), thiazole derivatives (for example, thiazole, isothiazole, etc.), imidazole derivatives (for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (for example, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (for example, pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methyl-2-pyrrolidone, etc.), imidazoline derivatives , imidazolidine derivatives, pyridine derivatives (e.g., pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinylpyridine, 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-cyanoquinoline, 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, etc.

[0172] Examples of the nitrogen-containing compounds having a carboxyl 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, methoxyalanine, etc.).

[0173] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

[0174] Examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2-quinolinediol, 1H-indol-3-ylmethanol 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-(2-hydroxyethyl) Pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidinyl-1,2-propanediol, 3-pyrrolidinyl-1,2-propanediol, 8-hydroxyjulolide, quinuclidine-3-ol, 3-tropineol, 1-methyl-2-pyrrolidineethanol, 1-hydroxyethylaziridine, N-(2-hydroxyethyl)phthalimide and N-(2-hydroxyethyl)isonicotinamide, etc.

[0175] Examples of the amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, and benzamide.

[0176] Examples of the imide derivatives include phthalimide, succinimide, and maleimide.

[0177] As the quencher of the component (F), a quencher represented by the following formula (F1) can also be used.

[0178] [Chemical Formula 17]

[0179]

[0180] In formula (F1), w is 1, 2 or 3. 301 is any one substituent selected from the substituents represented by the following formulae (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 hydroxyl group. 301 When 2 R 301 They can bond to each other and form a ring together with the nitrogen atom to which they are bonded. 301 When there are two or more R 302 When , they may be the same or different.

[0181] [Chemical Formula 18]

[0182]

[0183] In formulas (F2) to (F4), R 303 、R 305 and R 308 Each is independently a linear or branched alkanediyl group having 1 to 4 carbon atoms. 304 and R 307 Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may contain at least one selected from a hydroxyl group, an ether bond, an ester bond, and a lactone ring. 306 is a single bond, or a linear or branched alkanediyl group having 1 to 4 carbon atoms. 309 It is an alkyl group having 1 to 20 carbon atoms, which may contain at least one selected from the group consisting of a hydroxyl group, an ether bond, an ester bond, and a lactone ring.

[0184] 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-diazabicyclo[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, 1,4,10,13-tetraoxa hetero-7,16-diazabicyclooctadecane, 1-aza-12-crown-4-ether, 1-aza-15-crown-5-ether, 1-aza-18-crown-6-ether, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine, tris(2-pentanoyloxyethyl)amine, tris(2-pivaloyloxyethyl)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 yl]amine, tris[2-(tert-butoxycarbonylmethoxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethoxy)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, (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, 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-(methoxycarbonyl)ethyl]amine, 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, but are not limited to the above compounds.

[0185] The content of component (F) is 0 to 3 parts by mass per 100 parts by mass of component (A). When component (F) is included, it is preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass, from the perspective of sensitivity. Component (F) can be used alone or in combination of two or more.

[0186] [(G) Antioxidant]

[0187] By including an antioxidant as the component (G), it is possible to more easily achieve improved heat resistance and transparency of the photosensitive resin composition. Examples of the antioxidant as the component (G) include hindered phenol compounds, ammonia, aliphatic primary amines, and hindered amine compounds.

[0188] The hindered phenol-based compound is not particularly limited, but the hindered phenol-based compounds listed below are preferred. Examples thereof include 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-butylhydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (trade name: Nocrac M-17), 2,5-di-tert-amylhydroquinone (trade name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: IRGANOX 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'-butylenebis(3-methyl-6-tert-butylphenol) (trade name: ADKSTAB 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-methylcyclohexyl)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: ADK STAB AO-30), pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (trade name: ADK STAB 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-hydroxyphenylpropionamide) (trade name: IRGANOX 1098), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 259), 2,2-thiodiethyl bis[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), calcium bis(3,5-di-tert-butyl-4-hydroxybenzylethylphosphonate) / 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-butyldibenzo[d,f][1,3,2]dioxaphosphine (trade name: Sumilizer GP), etc.

[0189] Examples of the aliphatic primary 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, hexadecylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine.

[0190] The hindered amine compound is not particularly limited, but the hindered amine compounds listed below are preferred. Examples thereof include p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade name: 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-methacryloyloxy-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 condensate (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-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (trade name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN 123), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN 770), bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate (trade name: TINUVIN 144), bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate (trade name: TINUVIN 765), tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate (trade name: LA-52), mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62), mixed esters 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- Mixed esters of butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-63P), mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-68LD), 2-methyl-2-acrylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (trade name: ADK STAB LA-82), and 2-methyl-2-acrylic acid, 1,2,2,4,6-pentamethyl-4-piperidinyl ester (trade name: ADK STAB LA-87). ,

[0191] The content of the component (G) is not particularly limited. When the component (G) is contained, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention.

[0192] [Other additives]

[0193] In addition to the above-mentioned components, the photosensitive resin composition of the present invention may further contain other additives. Examples of other additives include surfactants commonly used to improve coating properties.

[0194] As the above-mentioned surfactant, a nonionic surfactant is preferred, for example, a fluorine-based surfactant can be listed, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide and fluorinated organosiloxane compounds can be listed. These surfactants can use commercially available products, for example, 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), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Among them, Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the component (A).

[0195] The photosensitive resin composition of the present invention may also contain a silane coupling agent as another additive. By including a silane coupling agent, the adhesion of the resin film obtained from the composition to the adherend can be further improved. As silane coupling agents, epoxy-containing silane coupling agents, aromatic group-containing aminosilane coupling agents, etc. can be listed. These silane coupling agents can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited. When the silane coupling agent is contained, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0196] The photosensitive resin composition of the present invention can be prepared by conventional methods, for example, by stirring and mixing the components, and then filtering the mixture using a filter as needed.

[0197] The photosensitive resin composition of the present invention has excellent dispersion stability in a varnish, suppresses aggregation in a film, and is useful as a material for optical members requiring shielding (optical member applications).

[0198] [Pattern Forming Method Using Photosensitive Resin Composition]

[0199] The pattern forming method using the photosensitive resin composition of the present invention comprises:

[0200] (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition of the present invention;

[0201] (ii) exposing the photosensitive resin film to light;

[0202] (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0203] 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-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 a portion of the substrate by ion sputtering or electroplating. Sometimes, a substrate having either one or both of grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm is used. The opening width and depth of the grooves or holes of the substrate can be measured using a scanning electron microscope.

[0204] Examples of methods for forming the photosensitive resin film of the present invention include coating the photosensitive resin composition of the present invention on the substrate by dipping, spin coating, roll coating, or the like, and optionally preheating (pre-baking: PB) the substrate to efficiently perform the photocuring reaction. Pre-heating can be performed at, for example, 40°C to 140°C for about 1 minute to 1 hour.

[0205] The coating amount of the photosensitive resin composition can be appropriately selected depending on the intended purpose, and is preferably an amount that gives a film thickness of 0.1 to 200 μm, more preferably an amount that gives a film thickness of 1 to 150 μm.

[0206] In order to improve the uniformity of the film thickness on the substrate surface, a solvent may be added dropwise to the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be added and its amount may be appropriately selected according to 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 may also be used.

[0207] Next, (ii) the photosensitive resin coating is exposed. Exposure is preferably performed using light with a wavelength of 1 to 600 nm, more preferably using light with a wavelength of 10 to 600 nm, and even more preferably using light with a wavelength of 190 to 500 nm. Examples of the light of the above-mentioned wavelength include light of various wavelengths generated by a radiation generating device, such as ultraviolet rays such as g-line, h-line, and i-line, and far ultraviolet rays (248 nm, 193 nm). Among them, light with a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is preferably 10 to 10,000 mJ / cm 2 .

[0208] Exposure can be performed through a photomask. The photomask can be, for example, a film with a desired pattern hollowed out. The material of the photomask is not particularly limited, but is preferably a material that blocks light of the aforementioned wavelengths. For example, a material such as chromium is suitable as a light-shielding film.

[0209] Furthermore, a post-exposure heat treatment (PEB) can be performed to improve development sensitivity. PEB is preferably performed at 40-150°C for 0.5-10 minutes. PEB crosslinks the exposed portions, forming an insolubilized pattern that is insoluble in the developer solvent.

[0210] After exposure or PEB, (iii) the pattern is formed by developing with a developer. Preferred developers include, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as PGME. However, solvents used in the photosensitive resin composition of the present invention can also be used. Conventional development methods can be used, such as immersing the patterned substrate in the developer. Subsequently, cleaning, rinsing, and drying are performed as needed to obtain a photosensitive resin film having the desired pattern.

[0211] Furthermore, it is preferred that (iv) an oven or a hot plate be used to post-cure the patterned photosensitive resin coating at 100 to 250°C, preferably at 150 to 220°C. If the post-curing temperature is 100 to 250°C, the cross-linking density of the photosensitive resin composition can be increased, and the residual volatile components can be removed, which is more preferred from the perspective of adhesion to the substrate, heat resistance and strength, electrical properties, and adhesive strength. The post-curing time is preferably 10 minutes to 10 hours, and more preferably 10 minutes to 3 hours. If the photosensitive resin composition of the present invention is used, even with a relatively low post-curing temperature of around 200°C, a coating with excellent various film properties can be obtained. The film thickness of the coating (cured coating) after post-curing is generally 1 to 200 μm, preferably 5 to 50 μm.

[0212] When patterning is not required, for example, when only a uniform photosensitive resin coating is desired, the coating can be formed by exposing the film to light of an appropriate wavelength without using a photomask in step (ii) of the patterning method.

[0213] [Photosensitive dry film]

[0214] The photosensitive dry film of the present invention comprises a support film, and a photosensitive resin coating film obtained from the photosensitive resin composition of the present invention is provided on the support film.

[0215] Because the photosensitive dry film (support film and photosensitive resin coating) is solid and the photosensitive resin coating contains no solvent, bubbles caused by solvent evaporation are prevented from remaining within the photosensitive resin coating or between it and the uneven substrate. Considering flatness, step coverage, and substrate stacking spacing on the uneven substrate, an optimal film thickness range exists. Therefore, the thickness of the photosensitive resin coating is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[0216] Furthermore, the viscosity and fluidity of the photosensitive resin coating are closely related. Within an appropriate viscosity range, the photosensitive resin coating exhibits optimal fluidity, allowing it to penetrate deep into narrow gaps and enhance adhesion to the substrate through resin softening. Therefore, from the perspective of fluidity, the viscosity of the photosensitive resin coating is preferably 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, and even more preferably 50 to 300 Pa·s at a temperature of 80 to 120°C. In the present invention, viscosity is measured using a rotational viscometer.

[0217] When the photosensitive dry film of the present invention is adhered to a substrate with irregularities (e.g., a substrate having either or both grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm), the photosensitive resin coating follows and wraps around the irregularities, achieving high flatness. In particular, the flexibility of the photosensitive resin coating of the present invention enables even higher flatness. Furthermore, by adhering the photosensitive resin coating to the substrate in a vacuum environment, the formation of gaps between them can be more effectively prevented.

[0218] Then, the photosensitive dry film of the present invention can be manufactured by coating the photosensitive resin composition of the present invention on a substrate (support film) and drying it to form a photosensitive resin coating. As the manufacturing device of the photosensitive dry film, a film coater (film coater) commonly used for manufacturing adhesive products can be used. As the film coater, for example, a comma coater (comma coater), a reverse comma coater (comma reverse coater), a multi-coater (multi coater), a die coater, a lip coater (lip coater), a reverse lip coater (lip reverse coater), a direct gravure coater (direct gravure coater), a flat gravure coater (offset gravure coater), a three-roll bottom reverse coater (3-roll bottom reverse coater), a four-roll bottom reverse coater (4-roll bottom reverse coater) etc. can be listed.

[0219] After unwinding a support film from the coating machine's unwinding shaft and passing it through the coating head of the coating machine, the photosensitive resin composition of the present invention is coated on the support film to a specified thickness. The composition is then passed through a hot air circulation oven at a specified temperature and time to dry on the support film, forming a photosensitive resin coating. A photosensitive dry film can be obtained. Furthermore, if necessary, the photosensitive dry film can be passed through a laminating roller under a specified pressure along with a protective film unwound from another unwinding shaft of the coating machine. After laminating the photosensitive resin coating on the support film and the protective film, the film is wound onto the take-up shaft of the coating machine to produce a photosensitive dry film with a protective film. The temperature is preferably 25-150°C, the time is preferably 1-100 minutes, and the pressure is preferably 0.01-5 MPa.

[0220] The support film may be a monolayer film composed of a single film or a multilayer film composed of a plurality of polymer films. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Polyethylene terephthalate is preferred due to its moderate flexibility, mechanical strength, and heat resistance. Furthermore, these films may be treated with various treatments, such as corona treatment or release agent coating. These films can be commercially available products, for example, Cerapeel WZ (RX), Cerapeel BX8 (R) (these are manufactured by TORAY ADVANCED FILM CO., LTD.), E7302, E7304 (these are manufactured by TOYOBO CO., LTD.), Purex G31, Purex G71T1 (these are manufactured by Teijin DuPont Films Japan Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (these are manufactured by NIPPA Co., Ltd.), etc.

[0221] As the protective film, the same film as the support film can be used, preferably polyethylene terephthalate and polyethylene having appropriate flexibility. These films can be commercially available products. Examples of polyethylene terephthalate include the commercially available polyethylene terephthalate films listed above, and examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE Film 0-Type (manufactured by NIPPA Co., Ltd.).

[0222] From the perspective of stability in the production of the photosensitive dry film and prevention of winding around a core and so-called curl, the thickness of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm.

[0223] [Pattern Formation Method Using Photosensitive Dry Film]

[0224] Patterning methods using photosensitive dry films include:

[0225] (i) a process of forming a photosensitive resin coating on a substrate using the photosensitive dry film of the present invention;

[0226] (ii) exposing the photosensitive resin film to light;

[0227] (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0228] First, in step (i) above, a photosensitive resin coating is formed on a substrate using a photosensitive dry film. Specifically, the photosensitive resin coating is formed by attaching the photosensitive dry film to the substrate. If a protective film is laminated on the photosensitive dry film, the protective film is removed from the photosensitive dry film before attaching the photosensitive resin coating to the substrate. This attachment can be performed using, for example, a film attaching device.

[0229] Examples of the substrate include those described in the pattern forming method using a photosensitive resin composition. A vacuum laminator is preferred as the 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 using laminating rollers at a specified pressure within a vacuum chamber at a specified vacuum level, on a workbench at a specified temperature. The temperature is preferably 60-120°C, the pressure is preferably 0-5.0 MPa, and the vacuum level is preferably 50-500 Pa.

[0230] To obtain a photosensitive resin coating of desired thickness, the film can be applied multiple times as needed. For example, the number of application times is about 1 to 10, and a photosensitive resin coating with a thickness of 10 to 1,000 μm, particularly about 100 to 500 μm, can be obtained.

[0231] In order to efficiently perform the photocuring reaction of the photosensitive resin film and improve the adhesion between the photosensitive resin film and the substrate, preheating (prebaking) may be performed as needed. The prebaking can be performed at 40 to 140° C. for about 1 minute to 1 hour.

[0232] 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 (iv) performing a post-curing treatment as needed, similar to the pattern forming method using the photosensitive resin composition. Furthermore, 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.

[0233] Example

[0234] Hereinafter, the present invention will be described in more detail with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples.

[0235] In the following synthesis examples, the molecular weight (Mw) of each silicone resin was measured by GPC using a TSKgel Super HZM-H (manufactured by TOSOH CORPORATION) as a chromatographic column, 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 a standard.

[0236] In the following Synthesis Examples 1-1 to 1-4, the silicone resin (polymer) used in the preparation of the photosensitive resin composition of Synthesis Examples 1 to 9 was synthesized. Compounds (S-1) to (S-6) used in the synthesis of the silicone resin are shown below.

[0237] [Chemical Formula 19]

[0238]

[0239] [1] Synthesis of polymers containing silicone skeletons

[0240] [Synthesis Example 1-1] Synthesis of silicone resin (1)

[0241] In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 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) were added, and then 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 67.9 g (0.35 mol) of compound (S-5) and 399.8 g (0.65 mol) of compound (S-6) were added dropwise over 1 hour. 1 = 8) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain an organosilicon resin (1). 1 H-NMR (manufactured by Bruker) confirmed 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.

[0242] [Synthesis Example 1-2] Synthesis of silicone resin (2)

[0243] In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 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) were added, and then 2,000 g of toluene was added, and the mixture was heated to 70°C. Then, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 54.2 g (0.30 mol) of compound (S-5) and 589.2 g (0.4 mol) of compound (S-6) were added dropwise over 1 hour. 1 = 38) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain an organosilicon resin (2). 1 H-NMR (manufactured by 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.

[0244] [Synthesis Example 1-3] Synthesis of silicone resin (3)

[0245] In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 185.5 g (0.70 mol) of compound (S-2) and 90.3 g (0.21 mol) of compound (S-4) were added, and then 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 155.2 g (0.80 mol) of compound (S-5) and 589.2 g (0.2 mol) of compound (S-6) (y) were added dropwise over 1 hour. 1 = 38) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain an organosilicon resin (3). 1 H-NMR (manufactured by 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.

[0246] [Synthesis Example 1-4] Synthesis of silicone resin (4)

[0247] In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 126.0 g (0.30 mol) 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) were added, and then 2,000 g of toluene was added, 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, and 67.9 g (0.35 mol) of compound (S-5) and 399.8 g (0.65 mol) of compound (S-6) were added dropwise over 1 hour. 1 = 8) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)). After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain an organosilicon resin (4). 1 H-NMR (manufactured by 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.

[0248] [2] Synthesis of acrylic resin

[0249] In the following Synthesis Examples 2-1 to 2-3, acrylic resins (polymers) used in the preparation of the photosensitive resin compositions of Comparative Examples 1 to 7 were synthesized.

[0250] [Synthesis Example 2-1] Synthesis of acrylic resin (1)

[0251] 1 g of 2,2'-azobisisobutyronitrile (AIBN), 70 g of PGMEA (propylene glycol methyl ether acetate), and 70 g of toluene were added to a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer. Subsequently, 55 g of acrylic acid and 56 g of methacrylic acid were added, and after thorough stirring under a nitrogen atmosphere, the temperature was raised to 80°C and stirred for 6 hours while maintaining the reaction temperature at 80°C ± 2°C to obtain a solution of acrylic resin (1). PGMEA was added to the resulting solution so that the concentration of acrylic resin (1) became 60% by mass. The molecular weight (Mw) of acrylic resin (1) was 28,000.

[0252] [Synthesis Example 2-2] Synthesis of acrylic resin (2)

[0253] 1 g of 2,2'-azobisisobutyronitrile (AIBN), 70 g of PGMEA (propylene glycol methyl ether acetate), and 70 g of toluene were added to a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer. Subsequently, 50 g of acrylic acid and 79 g of methyl acrylate were added, and after thorough stirring under a nitrogen atmosphere, the temperature was raised to 80°C. The reaction temperature was maintained at 80°C ± 2°C while stirring for 6 hours to obtain a solution of acrylic resin (2). PGMEA was added to the resulting solution so that the concentration of acrylic resin (2) became 60% by mass. The molecular weight (Mw) of acrylic resin (2) was 32,000.

[0254] [3] Preparation of photosensitive resin composition

[0255] [Examples 1 to 9, Comparative Examples 1 to 7]

[0256] The components were blended in the amounts listed in Tables 1 to 2, stirred, mixed, and dissolved at room temperature, and then microfiltered using a 1.0 μm Teflon (registered trademark) filter membrane to prepare photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7.

[0257] [Table 1]

[0258]

[0259] [Table 2]

[0260]

[0261] 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 described in Tables 1 and 2 are as follows.

[0262] B-1: SDO-14 (manufactured by ARIMOTO CHEMICAL CO., LTD.), maximum absorption wavelength: 758.5 nm (according to JIS K 0115:2020), melting point: 250°C

[0263] B-2: Macrolex Green G (manufactured by Bayer AG), with a maximum absorption wavelength of 690 nm

[0264] [Chemical Formula 20]

[0265]

[0266] B-3: Sumiplast Green G (manufactured by Sumika Chemtex Co., Ltd.), maximum absorption wavelength 645 nm

[0267] [Chemical Formula 21]

[0268]

[0269] PAG-1

[0270] [Chemical Formula 22]

[0271]

[0272] Photopolymerization initiator: Irgacure OXE01, manufactured by BASF Japan Ltd.

[0273] CL-1, CL-2

[0274] [Chemical Formula 23]

[0275]

[0276] F-1: CHIMASSORB 119FL (made by BASF)

[0277] F-2: IRGANOX 3114 (manufactured by BASF)

[0278] AM-1

[0279] [Chemical Formula 24]

[0280]

[0281] Carbon black: Acetylene black (HS-100 manufactured by Denka Company Limited: average primary particle size 45 nm)

[0282] [4] Preparation of photosensitive dry film

[0283] A die coater was used as a coating machine, and a polyethylene terephthalate film (thickness of 38 μm) was used as a support film. The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 were coated on the support film, respectively. Subsequently, the film was passed through a hot air circulation oven (length of 4 m) set at 100° C. for 5 minutes to dry it, thereby forming a photosensitive resin coating on the support film to obtain a photosensitive dry film. Using a laminating roller, a polyethylene film (thickness of 40 μm) was attached as a protective film from above the photosensitive resin coating at a pressure of 1 MPa to produce a photosensitive dry film with a protective film. The film thickness of each photosensitive resin coating is recorded in Tables 3 and 4. In addition, the film thickness was measured (μm) using an optical interferometer film thickness meter (manufactured by SCREEN Semiconductor Solutions Co., Ltd.).

[0284] [5] Evaluation of photosensitive resin coating

[0285] (1) Evaluation of pattern forming properties

[0286] For the above-mentioned photosensitive dry film with a protective film, the protective film is peeled off, and a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) is used to set the vacuum degree in the vacuum chamber to 80 Pa so that the photosensitive resin coating on the support film is tightly adhered to the silicone substrate with uneven surfaces. The temperature condition is set to 100°C. After returning to normal pressure, the substrate is taken out of the vacuum laminator and the support film is peeled off. Then, in order to improve the adhesion with the substrate, a hot plate is used to pre-bake at 110°C for 5 minutes. In order to form a line width / spacing (line-and-space) pattern and a contact hole pattern on the obtained photosensitive resin coating, exposure is performed using a contact aligner type exposure device through a mask at an exposure condition of 365nm. After exposure, a hot plate is used to perform PEB at 130°C for 5 minutes and cool, and the substrate is spray-developed for 300 seconds using PGMEA (propylene glycol methyl ether acetate) to form a pattern.

[0287] The photosensitive resin coating on the substrate patterned by the above method was post-cured in an oven at 180°C while being purged with nitrogen for 2 hours. The cross-sections of the formed contact hole patterns of 50μm, 40μm, 30μm, 20μm, 10μm, and 5μm were then observed using a scanning electron microscope (SEM). The diameter of the smallest hole pattern that penetrated the bottom of the film was defined as the limiting resolution. The verticality of the 40μm contact hole pattern was further evaluated based on the cross-sectional photographs obtained. A vertical pattern was rated as ◎, a slightly inverted tapered profile was rated as ○, an inverted tapered profile was rated as △, and a poor opening was rated as ×. The results are shown in Tables 3 and 4.

[0288] (2) Compatibility evaluation

[0289] The photosensitive resin compositions of Examples 1-9 and Comparative Examples 1-7 were visually inspected for precipitation after being allowed to stand at 23°C for 24 hours. A score of ⊚ indicated no precipitation even after 24 hours. A score of △ indicated no precipitation within 12 hours but precipitation occurred within 24 hours. A score of × indicated precipitation occurred within 12 hours. The results are shown in Tables 3 and 4.

[0290] (3) Evaluation of reliability (adhesion, crack resistance)

[0291] The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7 were applied to a silicon wafer using a spin coater to a thickness of 10 μm, and then dried by heating on a hot plate at 100° C. for 3 minutes to remove the solvent.

[0292] Using a SUSS MicroTec SE. Mask Aligner MA8, 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, without a mask, for 5 minutes at 140°C. The wafer was then immersed in PGMEA for 5 minutes. The remaining film was heated in a 190°C oven for 1 hour to obtain a photosensitive resin film.

[0293] The obtained wafer was cut using a dicing machine equipped with a dicing blade (DAD685 manufactured by DISCO CORPORATION, spindle speed: 40,000 rpm, cutting speed: 20 mm / second) to obtain a 10 mm × 10 mm square test piece. The obtained test pieces (10 pieces each time) were subjected to a thermal cycle test (kept at -25°C for 10 minutes and at 125°C for 10 minutes, repeated 1,000 times), and the state of the resin film peeling off from the wafer after the thermal cycle test and the presence or absence of cracks were confirmed using an optical microscope. The evaluation of no peeling or cracking at all was good, even if only one peeling occurred, it was evaluated as peeling, and even if only one crack occurred, it was evaluated as cracking. The results are shown in Tables 3 and 4.

[0294] (4) Evaluation of heat resistance

[0295] The pre-test mass of the test pieces produced for reliability evaluation was measured. The test pieces were then placed in an oven heated to 200°C for 1,000 hours. The test pieces were removed from the oven and their mass was measured. A mass change of less than 0.5% before and after the test was considered good, while a mass change of 0.5% or greater was considered poor. The results are shown in Tables 3 and 4.

[0296] (5) Light-shielding test

[0297] Without a mask, the entire surface of the photosensitive resin film formed by laminating the photosensitive dry film on the glass wafer was irradiated with light using a high-pressure mercury lamp (wavelength of 360nm) as a light source using a SUSS MicroTec SE. Then, PEB was performed and immersed in PGMEA. The remaining film after this operation was further heated in an oven at 190°C for 2 hours to obtain a cured film. For this film, the transmittance (unit: %) of visible light with a wavelength of 800nm or less was measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Corporation). The maximum transmittance at this time is shown in Tables 3 and 4.

[0298] (6) Membrane aggregates

[0299] A 1 m section was cut from any position of the prepared dry film and the presence of aggregates was checked using an optical microscope. Aggregates with a maximum diameter of less than 1 μm were rated as ◯, and aggregates with a maximum diameter of 1 μm or greater were rated as ×.

[0300] The evaluation results of the resin films obtained using the photosensitive resin compositions and dry films described in Tables 1 and 2 are shown in Tables 3 and 4, respectively.

[0301] [Table 3]

[0302]

[0303] [Table 4]

[0304]

[0305] As shown in Table 3, Examples 1 to 9 using the photosensitive resin composition of the present invention exhibited no film aggregation, exhibited good contact hole pattern shape, ultimate resolution, compatibility, reliability (adhesion, crack resistance), heat resistance, and light-shielding properties. In contrast, as shown in Table 4, Comparative Examples 1 to 7 exhibited inferior contact hole pattern shape, ultimate resolution, compatibility, reliability (adhesion, crack resistance), and heat resistance compared to the Examples.

[0306] The above results indicate that the photosensitive resin composition of the present invention has excellent dispersion stability in varnish, has no film aggregates, and can form a light-shielding cured product having good reliability (adhesion, crack resistance), heat resistance, and resolution.

[0307] This manual contains the following solutions:

[0308] [1]: A photosensitive resin composition, characterized in that it comprises (A) a polymer containing a silicone skeleton, (B) an anthraquinone dye and (C) a photoacid generator.

[0309] [2]: The photosensitive resin composition according to [1], wherein the polymer (A) containing a silicone skeleton comprises repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4):

[0310] [Chemical Formula 25]

[0311]

[0312] Where R 1 ~R 4 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms; m represents an integer from 1 to 600; a 1 ~a 4 and b 1 ~b 4 To satisfy 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 number; 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),

[0313] [Chemical Formula 26]

[0314]

[0315] In formula (X1), Z 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 11 and R 12 are each independently a hydrogen atom or a methyl group; R 13 and R 14 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; 1 and p 2 Each independently represents an integer from 0 to 7; q 1 and q 2 are each independently an integer from 0 to 2,

[0316] [Chemical Formula 27]

[0317]

[0318] In formula (X2), Z 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 21 and R 22 are each independently a hydrogen atom or a methyl group; R 23 and R 24 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; 1 and r 2 Each independently represents an integer from 0 to 7; s 1 and s 2 are each independently an integer from 0 to 2,

[0319] [Chemical Formula 28]

[0320]

[0321] 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 from 0 to 7,

[0322] [Chemical Formula 29]

[0323]

[0324] In formula (X4), R 41 and R 42 are each independently a hydrogen atom or a methyl group; R 43 and R 44 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms;1 and u 2 are each independently an integer from 0 to 7; and v is an integer from 0 to 600.

[0325] [3]: The photosensitive resin composition according to [1] or [2] above, characterized in that the photosensitive resin composition further comprises at least one of (D) a crosslinking agent, (E) a solvent, (F) a quencher, and (G) an antioxidant.

[0326] [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) anthraquinone dye.

[0327] [5]: The photosensitive resin composition according to any one of [1] to [4], characterized in that the maximum absorption wavelength of the anthraquinone dye (B) is 800 nm or less.

[0328] [6]: The photosensitive resin composition according to any one of [1] to [5], characterized in that the photosensitive resin composition is used for optical components.

[0329] [7]: A photosensitive resin coating, characterized in that it is obtained from the photosensitive resin composition described in any one of [1] to [6] above.

[0330] [8]: A photosensitive dry film, characterized in that it has a support film and a photosensitive resin coating as described in [7] on the support film.

[0331] [9]: A method for forming a pattern using a photosensitive resin composition, comprising:

[0332] (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition described in any one of [1] to [6] above;

[0333] (ii) exposing the photosensitive resin film to light;

[0334] (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0335]

[10] : A method for forming a pattern using a photosensitive dry film, comprising:

[0336] (i) a process of forming a photosensitive resin coating on a substrate using the photosensitive dry film described in [8] above;

[0337] (ii) exposing the photosensitive resin film to light;

[0338] (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern.

[0339]

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

[10] is characterized in that it further comprises: (iv) a step of post-curing the photosensitive resin film formed with a pattern by development at a temperature of 100~250°C.

[0340] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any technical solution having substantially the same structure and achieving the same technical effect as the technical concept described in the claims of the present invention is included within the technical scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: The invention comprises (A) a polymer containing an organic silicon skeleton, (B) an anthraquinone dye and (C) a photoacid generator.

2. The photosensitive resin composition according to claim 1, wherein The polymer (A) containing a silicone skeleton comprises repeating units represented by the following formulae (a1) to (a4) and (b1) to (b4): Where R 1 ~R 4 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms; m represents an integer from 1 to 600; a 1 ~a 4 and b 1 ~b 4 To satisfy 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 number; 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), In formula (X1), Z 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 11 and R 12 are each independently a hydrogen atom or a methyl group; R 13 and R 14 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; 1 and p 2 Each independently represents an integer from 0 to 7; q 1 and q 2 are each independently an integer from 0 to 2, In formula (X2), Z 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 21 and R 22 are each independently a hydrogen atom or a methyl group; R 23 and R 24 Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; 1 and r 2 Each independently represents an integer from 0 to 7; s 1 and s 2 are each independently an integer from 0 to 2, 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 from 0 to 7, In formula (X4), R 41 and R 42 are each independently a hydrogen atom or a methyl group; R 43 and R 44 Each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms; 1 and u 2 are each independently an integer from 0 to 7; and v is an integer from 0 to 600.

3. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition further includes at least one of (D) a cross-linking agent, (E) a solvent, (F) a quencher, and (G) an antioxidant.

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

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

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

7. A photosensitive resin coating, characterized in that: Obtained from the photosensitive resin composition according to claim 1.

8. A photosensitive dry film, characterized in that: The photosensitive resin film comprises a support film, and the photosensitive resin film according to claim 7 is provided on the support film.

9. A pattern forming method using a photosensitive resin composition, characterized in that: Include: (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) A step of developing the exposed photosensitive resin film using a developer to form a pattern.

10. A pattern forming method using a photosensitive dry film, characterized in that: Include: (i) forming a photosensitive resin coating on a substrate using the photosensitive dry film according to claim 8; (ii) exposing the photosensitive resin film to light; (iii) A step of developing the exposed photosensitive resin film using a developer to form a pattern.

11. The pattern forming method according to claim 9 or 10, characterized in that: The method further comprises: (iv) post-curing the photosensitive resin film having the pattern formed by the development at a temperature of 100 to 250° C.

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