Photosensitive resin composition, pattern forming method, cured film forming method, interlayer insulating film, and surface protective film

Abstract

The present invention relates to a photosensitive resin composition, a pattern forming method, a cured film forming method, an interlayer insulating film, and a surface protective film. The subject of the present invention is to provide a photosensitive resin composition, a pattern forming method using the aforementioned photosensitive resin composition, a cured film, and an electronic component having the aforementioned cured film. The solution to this subject is a photosensitive resin composition containing: (A) a resin, (B) a photosensitizer, (C) a surfactant containing a structural unit represented by the following average empirical formula (1), and (D) a solvent. (R1R2Y2SiO 1 / 2 )2(R3Y1SiO 2 / 2 ) l (R5R6SiO 2 / 2 ) n (R4SiO 3 / 2 ) m (1); wherein Y1 and Y2 are each independently a hydrogen atom, a methyl group, a phenyl group, or a group represented by the following formula (2), and at least one of Y1 and Y2 is a group represented by the following formula (2), and R1 to R6 may be the same or different and are each a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, l and n are each independently an integer of 1 to 100, and m is an integer of 0 to 100.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a pattern forming method, a cured film forming method, an interlayer insulating film, a surface protective film, and an electronic component. Background Art

[0002] With the miniaturization and high performance of various electronic devices such as personal computers, digital cameras, and mobile phones, the requirements for further miniaturization, thinning, and high density of semiconductor elements have rapidly increased. Along with this, the interlayer insulating film and the surface protective film of semiconductor elements require various film thicknesses from a thin film of 1 μm or less to a thick film of 10 μm or more depending on their uses, and there are cases where a cured film formed by exposing a photosensitive resin composition and curing it is used (Patent Document 1, Patent Document 2). In each film thickness, uniformity of the film thickness is required during coating of the photosensitive resin composition, but in these documents, only positive-type and negative-type photosensitive resin compositions using a fluorine-based surfactant are claimed, and there is no description regarding the uniformity of the film thickness.

[0003] Further, when forming a thick film of 10 μm or more, since the photosensitive resin composition has a high viscosity, it is likely to contain bubbles during coating, and problems of coating defects often occur due to these bubbles. Patent Document 3 describes a method for manufacturing a composition containing an alkali-soluble resin, a photoacid generator, a fluorine-based surfactant, and an organic solvent, and claims that by mixing the surfactant and the organic solvent first and then adding the alkali-soluble resin and the photoacid generator to the mixed solution, the dispersibility of the surfactant is improved and the shrinkage hole defects during coating are reduced. However, this document only evaluates a film thickness of less than 10 μm and there is no description regarding the defects due to bubbles during thick film formation. Thus, the film thickness uniformity and the reduction of defects during coating are often raised as problems, and improvement thereof is strongly desired.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] [Patent Document 1] International Publication No. 2015 / 060238

[0007] [Patent Document 2] International Publication No. 2015 / 060240

[0008] [Patent Document 3] International Publication No. 2011 / 152058 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] The present invention has been made in view of the above facts, and an object thereof is to provide a photosensitive resin composition having excellent film thickness uniformity during coating and reduced coating defects during formation of a thick film. The present invention further aims to provide a pattern forming method using the aforementioned photosensitive resin composition, a cured film obtained by curing the pattern, and an electronic component having the aforementioned cured film.

[0011] Solutions for Solving the Problems

[0012] In order to solve the above problems, the present invention provides a photosensitive resin composition containing:

[0013] (A) a resin,

[0014] (B) a photosensitizer,

[0015] (C) a surfactant containing a structural unit represented by the following average empirical formula (1), and

[0016] (D) a solvent.

[0017] [Chemical formula 1]

[0018] (R1R2Y2SiO 1 / 2 )2(R3Y1SiO 2 / 2 ) l (R5R6SiO 2 / 2 ) n (R4Sio 3 / 2 ) m (1)

[0019] In the formula, Y1 and Y2 are each independently a hydrogen atom, a methyl group, a phenyl group, or a group represented by the following general formula (2), and at least one of Y1 and Y2 is a group represented by the following general formula (2). R1 to R6 may be the same or different and are each a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. l and n are each independently an integer of 1 to 100, and m is an integer of 0 to 100.

[0020] [Chemical formula 2]

[0021]

[0022] In the formula, the dotted line represents a bond. R9, R 10 , and R 11 are each independently a linear or branched alkylene group having 2 to 10 carbon atoms. However, R 10 and R 11 are different. R 12 is a trivalent hydrocarbon group having 2 to 10 carbon atoms. R 13 represents having selected from (OR 10 ), (OR 11 ), (OR 12The structure of one or more repeating units in (), R 14 is a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl ether group having 1 to 10 carbon atoms, a linear or branched unsaturated alkyl ether group having 1 to 10 carbon atoms, or a linear or branched alkyl ester group having 1 to 10 carbon atoms. a is an integer from 1 to 50, b is an integer from 0 to 50, c is an integer from 0 to 50, and d is an integer from 1 to 20. -OR 10 -, -OR 11 -, -OR 12 (R 13 )- may also be random in order.

[0023] If it is such a photosensitive resin composition, the film thickness uniformity during coating is excellent and the coating defects during thick film formation are reduced.

[0024] Furthermore, in the general formula (2) above, a is preferably an integer from 10 to 30, b is preferably an integer from 10 to 30, and c is preferably an integer from 0 to 20.

[0025] If it is such a photosensitive resin composition, it can have sufficient solubility in solvents, and can achieve an appropriate balance with the siloxane structure, improving the film thickness uniformity during coating and the defoaming property during thick film formation.

[0026] Furthermore, R in the general formula (2) above 14 is preferably a linear or branched alkyl ester group having 1 to 10 carbon atoms.

[0027] If it is such a photosensitive resin composition, the effects of the present invention can be further improved.

[0028] Furthermore, it preferably further contains (E) a crosslinking agent selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of 2 or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are replaced with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are replaced with substituents represented by the following formula (E-1), and compounds containing 2 or more nitrogen atoms having glycidyl groups represented by the following formula (E-2).

[0029] [Chemical formula 3]

[0030]

[0031] In the formula, the dotted line represents a bond, and R f represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

[0032] If it is such a photosensitive resin composition, the strength of the cured product can be further increased.

[0033] Further, the aforementioned resin (A) is preferably selected from at least one of polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and resin containing a siloxane skeleton.

[0034] Such a resin is suitable as the resin (A).

[0035] Further, the weight average molecular weight of the resin is preferably 3,000 to 500,000.

[0036] If it is such a photosensitive resin composition, it is easy to form a film with a desired film thickness on a substrate, and the viscosity is also ideal.

[0037] Further, the aforementioned photosensitizer (B) is preferably a photoacid generator.

[0038] If it is such a photosensitive resin composition, for a positive photosensitive resin composition, even if an alkaline aqueous solution is used as the developer, since the unexposed portion is not soluble in the developer and the exposed portion is soluble in the developer, a good positive pattern can still be formed. For a negative photosensitive resin composition, by using the acid generated from the component (B) as a catalyst, the crosslinking group of the component (E) crosslinks with the resin of the component (A), and a good negative pattern can also be formed.

[0039] Further, the aforementioned photoacid generator may be a compound having a diazoquinone structure.

[0040] If it is such a photoacid generator, a positive pattern can be formed more efficiently in particular.

[0041] Further, the aforementioned photosensitizer (B) may be a photo radical initiator.

[0042] The photosensitive resin composition of the present invention may contain such a photo radical initiator.

[0043] Further, the present invention provides a pattern forming method, comprising the following steps:

[0044] (I) Coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive material film,

[0045] (II) Then, after heat treatment, exposing the photosensitive material film through a photomask with high-energy rays or electron beams having a wavelength of 190 to 500 nm,

[0046] (III) Developing using a developer of an alkaline aqueous solution or an organic solvent.

[0047] If it is such a pattern forming method, a film having a desired pattern can be obtained.

[0048] Further, between the aforementioned exposure step (II) and the aforementioned development step (III), a post-exposure heating step is preferably included.

[0049] By including such steps, the pattern forming method of the present invention can use the acid generated from the photoacid generator upon exposure as a catalyst, and promote the crosslinking reaction between the crosslinking groups of the crosslinking agent and the crosslinking reaction sites of the polymer.

[0050] Further, the present invention provides a method for forming a cured film, comprising the following steps:

[0051] The patterned film obtained by the pattern forming method is further heated at a temperature of 100 to 300 °C for post-curing.

[0052] If it is such a method for forming a cured film, the crosslinking density of the film of the photosensitive resin composition can be increased, and the remaining volatile components can be removed, which is ideal from the viewpoints of the adhesion to the substrate, heat resistance, strength, and electrical properties.

[0053] Further, the present invention provides an interlayer insulating film or a surface protective film, which is composed of a cured film of a photosensitive resin composition.

[0054] If it is such an interlayer insulating film or a surface protective film, the adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to drugs such as alkaline stripping solutions are excellent, and the reliability of the semiconductor element using it as a protective film is also excellent. In particular, cracks generated during the temperature cycle test can be prevented.

[0055] Further, the present invention provides an electronic component having the above interlayer insulating film or surface protective film.

[0056] If it is such an electronic component, since it has a protective film (interlayer insulating film or surface protective film) with heat resistance, chemical resistance, and insulation properties, it becomes an electronic component with excellent reliability.

[0057] Effects of the Invention

[0058] If the present invention is as described above, a photosensitive resin composition with excellent film thickness uniformity during coating and reduced coating defects during thick film formation can be provided. Moreover, a pattern forming method using the aforementioned photosensitive resin composition, a cured film obtained by hardening the pattern, and an electronic component having the aforementioned cured film can also be provided. Detailed Description

[0059] As described above, there is a need to develop a photosensitive resin composition with excellent film thickness uniformity during coating and reduced coating defects during thick film formation, a pattern forming method using the aforementioned photosensitive resin composition, a cured film obtained by hardening the pattern, and an electronic component having the cured film.

[0060] The present inventors have conducted in-depth studies to achieve the above-mentioned purpose and have found that by preparing a photosensitive resin composition containing (A) a resin, (B) a photosensitizer, (C) a surfactant comprising a nonionic organosiloxane compound having a polyoxyalkylene group in the side chain and / or at the end, and (D) a solvent, the film thickness uniformity during coating is excellent and coating defects during thick film formation can be reduced, thereby completing the present invention.

[0061] That is, the present invention is a photosensitive resin composition comprising:

[0062] (A) resin,

[0063] (B) photosensitizer,

[0064] (C) a surfactant containing a structural unit represented by the following average empirical formula (1), and

[0065] (D) Solvent.

[0066] [Chemistry 4]

[0067] (R1R2Y2SiO 1 / 2 )2(R3Y1SiO2 / 2) l (R5R6SiO 2 / 2 ) n (R4SiO 3 / 2 ) m (1)

[0068] In the formula, Y1 and Y2 are each independently a hydrogen atom, a methyl group, a phenyl group or a group represented by the following general formula (2), and at least one of Y1 and Y2 is a group represented by the following general formula (2), R1 to R6 may be the same or different and may be a monovalent hydrocarbon group having 1 to 20 carbon atoms which may also contain heteroatoms, l and n are each independently an integer of 1 to 100, and m is an integer of 0 to 100.

[0069] [Chemistry 5]

[0070]

[0071] In the formula, dotted lines represent bonds, R9, R 10 , R 11 are each independently a linear or branched alkylene group having 2 to 10 carbon atoms, but R 10 and R 11 Different, R 12 is a trivalent hydrocarbon group having 2 to 10 carbon atoms, R 13 Indicates a selected from (OR 10 )、(OR 11 )、(OR 12 ) in one or more repeating units, R14 is a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl ether group having 1 to 10 carbon atoms, a linear or branched unsaturated alkyl ether group having 1 to 10 carbon atoms, or a linear or branched alkyl ester group having 1 to 10 carbon atoms. a is an integer from 1 to 50, b is an integer from 0 to 50, c is an integer from 0 to 50, and d is an integer from 1 to 20. -OR 10 -, -OR 11 -, -OR 12 (R 13 )- can also be random in order.

[0072] If it is the photosensitive resin composition of the present invention, the film thickness uniformity during coating is excellent and coating defects during thick film formation can be reduced.

[0073] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0074] [(A) resin]

[0075] (A) The resin is the resin that forms the basis of the photosensitive resin composition of the present invention. Depending on whether it is a positive-type photosensitive resin composition or a negative-type photosensitive resin composition, it can be selected according to the mechanical properties, optical properties, etc. required for the cured film formed by the photosensitive resin composition using the aforementioned resin. It is preferably a resin selected from polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and resin containing a siloxane skeleton. One kind can be used or two or more kinds can be used in combination.

[0076] (Polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor)

[0077] The resin preferably contains at least one of the structural units represented by the following general formulas (3), (4), (5), and (7).

[0078] [Chemical formula 6]

[0079]

[0080] In the formula, X1 is a tetravalent organic group, and X2 is a divalent organic group.

[0081] [Chemical formula 7]

[0082]

[0083] In the formula, X3 is a divalent organic group, and X4 is a divalent organic group that is the same as or different from the aforementioned X2.

[0084] [Chemical formula 8]

[0085]

[0086] In the formula, X5 is a tetravalent organic group the same as or different from the aforementioned X1, X6 is a divalent organic group the same as or different from the aforementioned X2, and R a and R b are each independently a hydrogen atom, an organic group having 1 to 10 carbon atoms which may also contain heteroatoms and may have substituents, or an organic group represented by the following general formula (6).

[0087] [Chemical formula 9]

[0088]

[0089] In the formula, the dotted line represents a bond. R c is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R d and R e are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10.

[0090] [Chemical formula 10]

[0091]

[0092] In the formula, X7 is a divalent organic group the same as or different from the aforementioned X3, and X8 is a tetravalent organic group.

[0093] X1 in the above general formula (3) is a tetravalent organic group, and there is no limitation if it is a tetravalent organic group. It is preferably a tetravalent organic group of an alicyclic aliphatic group or an aromatic group having 4 to 40 carbon atoms or a tetravalent organic group containing a siloxane skeleton, and more preferably a tetravalent organic group represented by the following formula (8). Also, the structure of X1 can be one kind or a combination of two or more kinds.

[0094] [Chemical formula 11]

[0095]

[0096] In the formula, R 15 , R 16 each independently represent a methyl group or a phenyl group, q1 and q2 represent integers of 1 to 20, and the dotted line represents a bond.

[0097] X2 in the above general formula (3) is a divalent organic group, and there is no limitation if it is a divalent organic group, but it is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or an aliphatic group or a siloxane group without a cyclic structure. More preferably, X2 can be a structure represented by the following formula (9), (10), or (11). Also, the structure of X2 can be one kind or a combination of two or more kinds.

[0098] [Chemical formula 12]

[0099]

[0100] In the formula, q3 represents an integer from 1 to 20, s1 represents an integer from 1 to 40, s2 and s3 each independently represent an integer from 0 to 40, and the dotted line represents a bond.

[0101] [Chemical formula 13]

[0102]

[0103] In the formula, q4 represents an integer from 1 to 4, q 14 represents an integer from 1 to 20, R 17 represents a fluorine atom, a methyl group, an ethyl group, a propyl group, a n-butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a trifluoromethyl group. When q4 is 2 or more, R 17 can be the same or different, and the dotted line represents a bond.

[0104] [Chemical formula 14]

[0105]

[0106] In the formula, q5, q6, and q7 represent integers from 1 to 10, q8 represents an integer from 1 to 20, and the dotted line represents a bond.

[0107] If it is a resin containing the structural unit represented by the above general formula (3), the mechanical strength, adhesion to the substrate, and heat resistance of the cured film obtained by pattern formation can be improved, so it is more ideal. Also, the structural unit (3) does not need to undergo a ring-closure reaction during post-curing, and the curing reaction temperature can be relatively reduced, so it is more ideal.

[0108] X3 in the above general formula (4) is a divalent organic group, and there is no restriction if it is a divalent organic group. It is preferably a divalent organic group having an aliphatic long-chain structure, an alicyclic aliphatic group, or an aromatic group with 4 to 40 carbon atoms. It is more preferably a divalent organic group represented by the following formula (12). Also, the structure of X3 can be one kind or a combination of two or more kinds.

[0109] [Chemical formula 15]

[0110]

[0111] In the formula, R 18 are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, q9 is an integer from 1 to 30, and the dotted line represents a bond.

[0112] X4 in the above general formula (4) is a divalent organic group, which may be the same as or different from the above X2. If it is a divalent organic group, there is no restriction. It is preferably a divalent organic group having 6 to 40 carbon atoms and being a cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or an aliphatic group without a cyclic structure, or a siloxane group. More preferably, the structures represented by the above formulas (9), (10) or (11) can be cited. Further, the structure of X4 can be one kind or a combination of two or more kinds.

[0113] If it is a resin containing the structural unit represented by the above general formula (4), the mechanical properties such as the extensibility of the cured film obtained by pattern formation and the adhesion to the substrate can be improved, so it is more preferable.

[0114] X5 in the above general formula (5) is a tetravalent organic group, which may be the same as or different from the above X1. If it is a tetravalent organic group, there is no restriction. It is preferably a tetravalent organic group of an alicyclic aliphatic group or an aromatic group having 4 to 40 carbon atoms or a tetravalent organic group containing a siloxane skeleton, and more preferably a tetravalent organic group represented by the above formula (8). Further, the structure of X5 can be one kind or a combination of two or more kinds.

[0115] X6 in the above general formula (5) is a divalent organic group, which may be the same as or different from the above X2. If it is a divalent organic group, there is no restriction. It is preferably a divalent organic group having 6 to 40 carbon atoms and being a cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or an aliphatic group without a cyclic structure, or a siloxane group. More preferably, the structures represented by the above formulas (9), (10) or (11) can be cited. Further, the structure of X6 can be one kind or a combination of two or more kinds.

[0116] R in the above general formula (5) a and R b are each independently a hydrogen atom, an organic group having 1 to 10 carbon atoms and may contain a hetero atom therein or may be substituted with a halogen atom, or an organic group represented by the above general formula (6). Either one or both of R a and R b are preferably an organic group represented by the above general formula (6).

[0117] R in the above general formula (6) c is a hydrogen atom or an organic group having 1 to 3 carbon atoms. R d and R e are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10. R c is preferably a hydrogen atom or a methyl group. R d and R e are preferably hydrogen atoms, and m1 is preferably an integer of 2 to 5.

[0118] If this is the case, since the structural unit has a polymerizable unsaturated bonding group, by combining with a photo radical initiator described later, the radicals generated in the exposed portion during pattern formation act as initiators to carry out radical polymerization and have the characteristic of being insoluble in the developer. Therefore, a negative photosensitive resin composition can be provided without newly adding a crosslinking agent.

[0119] X7 in the above general formula (7) is a divalent organic group, which may be the same as or different from the above X3. There is no restriction if it is a divalent organic group. It is preferably a divalent organic group having an aliphatic long-chain structure, an alicyclic aliphatic group or an aromatic group with 4 to 40 carbon atoms. It is more preferably the divalent organic group represented by the above formula (12). Also, the structure of X7 can be one kind or a combination of two or more kinds.

[0120] X8 in the above general formula (7) is a tetravalent organic group. There is no restriction if it is a tetravalent organic group. It is preferably a divalent organic group with 6 to 40 carbon atoms, more preferably a cyclic organic group containing 1 to 4 aromatic rings or aliphatic rings having substituents, or an aliphatic group or a siloxane group without a cyclic structure. A more ideal X8 can be exemplified by the structure represented by the following formula (13). Also, the structure of X8 can be one kind or a combination of two or more kinds.

[0121] [Chemical formula 16]

[0122]

[0123] In the formula, q 10 、q 11 、and q 12 represent integers from 1 to 10, q 13 represents an integer from 1 to 20, and the dotted line represents a bond.

[0124] If the resin contains the structural unit represented by the above general formula (7), it can improve the mechanical strength, the adhesion to the substrate, and the heat resistance of the cured film obtained by pattern formation. Therefore, it is more ideal. Also, the structural unit (7) does not need to undergo a ring-closing reaction during post-curing, and the curing reaction temperature can be relatively reduced. Therefore, it is more ideal.

[0125] The ideal weight-average molecular weight of the above polyamide, polyamide-imide, polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor is preferably 3,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 7,000 to 50,000. If the weight-average molecular weight is 3,000 or more, the photosensitive resin composition formed by using the above resin as the base resin can be easily formed into a desired film thickness on the substrate. If the weight-average molecular weight is 500,000 or less, there is no concern that the viscosity of the photosensitive resin composition will become significantly high and film formation will be impossible. In addition, in the present invention, the weight-average molecular weight is a polystyrene conversion value determined by gel permeation chromatography (GPC).

[0126] (Resin containing a siloxane backbone)

[0127] The resin preferably contains a structural unit represented by the following general formula (14).

[0128] [Chemical formula 17]

[0129]

[0130] In the formula, R 19 ~R 22 may be the same or different and represent a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. l1 are each independently an integer of 1 to 100. e and f are positive numbers and g, h, i, and j are 0 or positive numbers. However, e + f + g + h + i + j = 1. W is an organic group represented by the following general formula (15), T is an organic group represented by the following general formula (16), and U is an organic group represented by the following general formula (17) and / or (18).

[0131] [Chemical formula 18]

[0132]

[0133] In the formula, Z is a divalent organic group selected from any one of the following formulas, and p1 is 0 or 1.

[0134] [Chemical formula 19]

[0135]

[0136] R 23 and R 24 are each an alkyl group or an alkoxy group having 1 to 4 carbon atoms, which may be different or the same. k is any one of 0, 1, and 2, and the dotted line represents a bond.

[0137] [Chemical formula 20]

[0138]

[0139] In the formula, V is a divalent organic group selected from any one of the following formulas, and p2 is 0 or 1.

[0140] [Chemical formula 21]

[0141]

[0142] R 25 and R 26 are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms, which may be different or the same. o is any one of 0, 1, and 2, and the dotted line represents a bond.

[0143] [Chemical formula 22]

[0144]

[0145] In the formula, R 27 and R 28 are each independently a hydrogen atom or a methyl group. n1 and n2 are each independently an integer from 0 to 7. R 29 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and an ester bond or an ether bond may be contained between the carbon atoms, and the dotted line represents a bond.

[0146] [Chemical formula 23]

[0147]

[0148] In the formula, R 30 and R 31 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom. n3 is an integer from 0 to 10, and the dotted line represents a bond.

[0149] In the above general formula (14), R 19 to R 22 may be the same or different, and are each a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom.

[0150] The above monovalent hydrocarbon group may be any of linear, branched, and cyclic, and specific examples thereof include: monovalent aliphatic hydrocarbon groups such as alkyl groups having 1 to 20 carbon atoms and alkenyl groups having 2 to 20 carbon atoms; monovalent aromatic hydrocarbon groups such as aryl groups having 6 to 20 carbon atoms and aralkyl groups having 7 to 20 carbon atoms.

[0151] Examples of the above alkyl group include: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, norbornyl, adamantyl, etc. Examples of the above alkenyl group include: vinyl, propenyl, butenyl, pentenyl, etc.

[0152] In addition, the monovalent aliphatic hydrocarbon group may also contain a heteroatom. Specifically, part or all of the hydrogen atoms of the monovalent aliphatic hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a carbonyl group, an ether bond, a thioether bond, etc. may be inserted between its carbon atoms. Examples of such a monovalent aliphatic hydrocarbon group containing a heteroatom include 2-oxocyclohexyl and the like.

[0153] Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, etc.

[0154] In addition, the monovalent aromatic hydrocarbon group may also contain a heteroatom. Specifically, part or all of the hydrogen atoms of the monovalent aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, etc.

[0155] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a cyclopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclobutoxy group, a n-pentyloxy group, a cyclopentyloxy group, a n-hexyloxy group, a cyclohexyloxy group, a n-heptyloxy group, a n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a norbornyloxy group, an adamantyloxy group, etc.

[0156] Examples of the alkylthio group having 1 to 10 carbon atoms include a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a cyclopropylthio group, a n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a cyclobutylthio group, a n-pentylthio group, a cyclopentylthio group, a n-hexylthio group, a cyclohexylthio group, a n-heptylthio group, a n-octylthio group, a n-nonylthio group, a n-decylthio group, a norbornylthio group, an adamantylthio group, etc.

[0157] Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2-ethylphenoxy group, a 3-ethylphenoxy group, a 4-ethylphenoxy group, a 4-tert-butylphenoxy group, a 4-butylphenoxy group, a dimethylphenoxy group, a naphthyloxy group, a biphenyloxy group, a terphenyloxy group, etc.

[0158] Examples of the arylthio group having 6 to 20 carbon atoms include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2-ethylphenylthio group, a 3-ethylphenylthio group, a 4-ethylphenylthio group, a 4-tert-butylphenylthio group, a 4-butylphenylthio group, a dimethylphenylthio group, a naphthylthio group, a biphenylthio group, a terphenylthio group, etc.

[0159] Examples of the aromatic hydrocarbon group substituted by these groups include: 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3-tert-butoxyphenyl, 4-tert-butoxyphenyl, 2-methoxy phenethyl, 3-methoxy phenethyl, 4-methoxy phenethyl, 2-ethoxy phenethyl, 3-ethoxy phenethyl, 4-ethoxy phenethyl, biphenylyloxy phenyl, biphenylthio phenyl, and the like.

[0160] The number of carbon atoms of the above-mentioned monovalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 8. Further, the number of carbon atoms of the above-mentioned monovalent aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10.

[0161] Among them, R 19 ~R 22 are preferably methyl, ethyl, n-propyl or phenyl, more preferably methyl or phenyl.

[0162] In the above general formula (14), l1 are each independently an integer of 1 to 100, preferably an integer of 1 to 50.

[0163] Further, from the viewpoints of adhesion to the substrate, electrical properties, reliability, and light resistance, in the above general formula (14), e and f are positive numbers and g, h, i, and j are 0 or positive numbers. At this time, it is preferably 0 < e ≤ 0.8, more preferably 0.2 ≤ e ≤ 0.8, and it is preferably 0 < f ≤ 0.8, more preferably 0.2 ≤ f ≤ 0.8, and it is preferably 0 ≤ g ≤ 0.3, more preferably 0 ≤ g ≤ 0.2, and it is preferably 0 ≤ h ≤ 0.3, more preferably 0 ≤ h ≤ 0.2, and it is preferably 0 < i ≤ 0.8, more preferably 0 < i ≤ 0.5, and it is preferably 0 < j ≤ 0.8, more preferably 0 < j ≤ 0.5. However, e + f + g + h + i + j = 1.

[0164] In the above general formula (15), R 23 and R 24 are each an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and may be different or the same. Specific examples of R 23 and R 24 include: methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, and the like.

[0165] In the above general formula (16), R 25 and R 26 are each an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and may be different or the same. Specific examples of R 25 and R 26 include: methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, and the like.

[0166] In the above general formula (17), R 27 and R 28Each is independently a hydrogen atom or a methyl group. n1 and n2 are each independently an integer from 0 to 7.

[0167] In the above general formula (17), R 29 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and an ester bond or an ether bond may also be contained between its carbon atoms. The above divalent hydrocarbon group may be any of linear, branched, and cyclic, and specific examples thereof include: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl and other alkanediyls. Further, an ester bond or an ether bond may be inserted between the carbon atoms of the above divalent hydrocarbon group. Among them, R 29 is preferably methylene or ethylene, and more preferably methylene.

[0168] In the above general formula (18), R 30 and R 31 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may also contain a heteroatom. The above alkyl groups may be the same as those described in the description of R 19 to R 22 . R 30 and R 31 are preferably a hydrogen atom or a methyl group.

[0169] In the above general formula (18), n3 is an integer from 0 to 10, and is preferably 0.

[0170] Regarding the weight average molecular weight of the resin containing a siloxane skeleton of the present invention, from the viewpoints of the compatibility and photocurability of the photocurable resin composition using the resin, and the mechanical properties of the cured product obtained from the above photocurable resin composition, it is preferably 3,000 to 500,000, and more preferably 5,000 to 100,000.

[0171] (A) The resin can be set as described above. Further, among such resins, when a polymerizable unsaturated bonding group is present in the structural unit, by combining with a photoinitiator described later, the free radicals generated in the exposed portion during pattern formation serve as initiators to carry out free radical polymerization and have the characteristic of being insoluble in the developer, so a negative photosensitive resin composition can be provided without newly adding a crosslinking agent. Further, by combining with a photosensitizer that generates an acid upon irradiation and increases the dissolution rate in an aqueous alkali solution and is a compound having a diazoquinone structure, a positive photosensitive resin composition can be provided. Further, by using the acid generated from a photoacid generator described later as a catalyst, and the crosslinking group of the following (E) component crosslinks with the resin of the (A) component, a negative photosensitive resin composition can be formed.

[0172] [(B) Photosensitizer]

[0173] (B) The photosensitizer is a substance that causes the resin to become soluble or insoluble in a solvent upon exposure to light. The following (B) component used to construct a positive photosensitive resin composition or a negative photosensitive resin composition can be used. In addition, one kind or two or more kinds of (B) components can be used. When two or more kinds are used, they may have different functions respectively. Further, the (B) component may be a compound that generates an acid upon light irradiation (photoacid generator).

[0174] (Positive photosensitive resin composition)

[0175] In the present invention, in order to construct a positive photosensitive resin composition, the (B) component is preferably a photosensitizer that generates an acid upon light irradiation and increases the dissolution rate in an aqueous alkali solution, and is a compound having a diazoquinone structure. Examples of the (B) component include compounds having a 1,2-diazonaphthoquinone sulfonyl group in the molecule.

[0176] Examples of the compound having a 1,2-diazonaphthoquinone sulfonyl group in the molecule include compounds having a 1,2-diazonaphthoquinone sulfonyl group in the molecule represented by the following general formula (19) or (20).

[0177] [Chemical formula 24]

[0178]

[0179] Specifically, the compound to which the above 1,2-diazonaphthoquinone sulfonyl group is to be introduced can preferably be used: trihydroxybenzophenone or tetrahydroxybenzophenone, a ballast molecular of a stabilizer represented by the following general formula (21) having a phenolic hydroxyl group, or a novolak resin having a weight average molecular weight of preferably 2,000 to 20,000 and more preferably 3,000 to 10,000 of a repeating unit represented by the following formula (26). That is, a compound in which a hydrogen atom of the phenolic hydroxyl group of the resin or compound having a phenolic hydroxyl group listed below is substituted with the above 1,2-diazonaphthoquinone sulfonyl group can preferably be used as the (B) component.

[0180] [Chemical formula 25]

[0181]

[0182] Here, R 101 ~R 106Each is independently a hydrogen atom, a methyl group, a group represented by the following formula (22), or a group represented by the following formula (23). w is an integer from 0 to 2, z is an integer from 0 to 2. When z is 0, w is 1 or 2. When z is 0 and w is 1, E is a hydrogen atom, a methyl group, or a group represented by the following formula (22). When z is 0 and w is 2, one of them is a methylene group or a group represented by the following formula (24), and the other is a hydrogen atom, a methyl group, or a group represented by the following formula (22). When z is 1, it is a methylene group or a group represented by the following formula (24). When z is 2 and w is 1, E is a methine group or a group represented by the following formula (25). When w is 2, one of the Es is a methylene group or a group represented by the following formula (24), and the other is a methine group or a group represented by the following formula (25).

[0183] [Chemical formula 26]

[0184]

[0185] In the formula, a1, a2, a3, a4, a5, a6, and a7 are each an integer from 0 to 3, provided that a1 + a2 ≤ 5, a3 + a4 ≤ 4, and a6 + a7 ≤ 3.

[0186] At this time, the low nuclear body (sedative molecule) of the above formula (21) preferably has 2 to 20 benzene rings, more preferably 2 to 10 benzene rings, still more preferably 3 to 6 benzene rings, and the ratio of the number of phenolic hydroxyl groups to the number of benzene rings is preferably 0.5 to 2.5, more preferably 0.7 to 2.0, still more preferably 0.8 to 1.5.

[0187] Specific examples of such a low nuclear body (sedative molecule) are as follows.

[0188] [Chemical formula 27]

[0189]

[0190] [Chemical formula 28]

[0191]

[0192] [Chemical formula 29]

[0193]

[0194] [Chemical formula 30]

[0195]

[0196] [Chemical formula 31]

[0197]

[0198] [Chemical formula 32]

[0199]

[0200] [Chemical formula 33]

[0201]

[0202] Among the above-exemplified low nucleophiles (sedative molecules), (B-3), (B-29), (B-33), (B-38), etc. can be desirably used. Compounds in which the hydrogen atoms of the phenolic hydroxyl groups of these sedative molecules are substituted with 1,2-diazonaphthoquinone sulfonyl groups can be desirably used as the component (B) of the photosensitive resin composition of the present invention.

[0203] [Chemical formula 34]

[0204]

[0205] In the formula, mm is an integer of 0 to 3.

[0206] The novolak resin having the repeating unit represented by the above formula (26) can be synthesized by condensing at least one phenolic compound represented by the following formula (27), specifically, o-cresol, m-cresol, p-cresol, 3,5-xylenol, etc. with aldehydes by a conventional method.

[0207] [Chemical formula 35]

[0208]

[0209] In the formula, mm is an integer of 0 to 3.

[0210] At this time, examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc., and formaldehyde is preferred.

[0211] In addition, the ratio of the phenolic compound represented by the above formula (27) to the aldehydes is preferably 0.2 to 2 in terms of molar ratio, and particularly preferably 0.3 to 2.

[0212] As a method for introducing 1,2-diazonaphthoquinone sulfonyl group into the compound to be introduced with 1,2-diazonaphthoquinone sulfonyl group, a dehydrochlorination condensation reaction of 1,2-diazonaphthoquinone sulfonyl chloride with phenolic hydroxyl group using a base catalyst is preferably used. When the sedative molecule represented by the above formula (21) is trihydroxybenzophenone or tetrahydroxybenzophenone, the ratio of the hydrogen atoms of the phenolic hydroxyl groups substituted with 1,2-diazonaphthoquinone sulfonyl groups is 10 to 100 mol%, preferably 50 to 100 mol%. When it is a novolak resin having the repeating unit represented by the above formula (26), the ratio of the hydrogen atoms of the phenolic hydroxyl groups substituted with 1,2-diazonaphthoquinone sulfonyl groups is 2 to 50 mol%, preferably 3 to 27 mol%.

[0213] The addition amount of component (B) is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of component (A). Also, one kind of component (B) can be used, or two or more kinds can be used in combination.

[0214] By blending such component (B), the solubility in an alkaline aqueous solution is inhibited due to the dissolution inhibitory property of component (B) before exposure, and the system becomes alkali-insoluble. During exposure, the photosensitizer of component (B) generates an acid by light and increases the dissolution rate in an alkaline aqueous solution, and the system becomes alkali-soluble.

[0215] That is, when an alkaline aqueous solution is used as the developer, the unexposed portion is insoluble in the developer, and the exposed portion is soluble in the developer, so a positive pattern can be formed.

[0216] (Negative photosensitive resin composition)

[0217] Also, in the present invention, in order to construct a negative photosensitive resin composition, component (B) is preferably a compound that generates an acid by light. By using the acid generated from component (B) as a catalyst, the crosslinking group of the following component (E) crosslinks with the resin of component (A), and a negative photosensitive resin composition can be obtained.

[0218] As component (B), as a photoacid generator, those that generate an acid by irradiation with light having a wavelength of 190 to 500 nm and the acid becomes a hardening catalyst can be used. Examples include: onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, sulfonic acid nitrobenzyl esters, sulfonic acid esters, sulfonic acid imide esters, sulfonic acid oxime esters, sulfonic acid imide esters, triazine derivatives, etc.

[0219] Examples of the above onium salts include compounds represented by the following general formula (28).

[0220] (R 32 ) j1 M + K - (28)

[0221] In the formula, R 32 represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, M + represents iodonium or sulfonium, K - represents a non-nucleophilic counter ion, and j1 represents 2 or 3.

[0222] The above R 32Among them, examples of the alkyl group include: methyl, ethyl, propyl, butyl, cyclohexyl, 2-oxocyclohexyl, norbornyl, adamantyl, etc. Examples of the aryl group include: phenyl; alkoxyphenyl such as o- or m- or p-methoxyphenyl, ethoxyphenyl, m- or p-tert-butoxyphenyl, etc.; alkylphenyl such as 2- or 3- or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, etc. Examples of the aralkyl group include various groups such as benzyl, phenethyl, etc.

[0223] K - Examples of the non-nucleophilic relative ions of include: halide ions such as chloride ion, bromide ion, etc.; fluoroalkylsulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, nonafluorobutanesulfonate ion, etc.; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, 1,2,3,4,5-pentafluorobenzenesulfonate ion, etc.; alkylsulfonate ions such as methanesulfonate ion, butanesulfonate ion, etc.

[0224] Examples of the diazomethane derivative include the compound represented by the following general formula (29).

[0225] [Chemical formula 36]

[0226]

[0227] In the formula, R 33 may be the same or different, and represents a linear or branched or cyclic alkyl or haloalkyl having 1 to 12 carbon atoms, an aryl or haloaryl having 6 to 12 carbon atoms, or an aralkyl having 7 to 12 carbon atoms.

[0228] Among the above-mentioned R 33 examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. Examples of the haloalkyl group include: trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, nonafluorobutyl, etc. Examples of the aryl group include: phenyl; alkoxyphenyl such as o- or m- or p-methoxyphenyl, ethoxyphenyl, m- or p-tert-butoxyphenyl, etc.; alkylphenyl such as 2- or 3- or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, etc. Examples of the haloaryl group include: fluorophenyl, chlorophenyl, 1,2,3,4,5-pentafluorophenyl, etc. Examples of the aralkyl group include: benzyl, phenethyl, etc.

[0229] Specific examples of such photoacid generators include: diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate and other onium salts; bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(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, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane and other diazomethane derivatives;Glyoxime derivatives such as bis - O - (p - toluenesulfonyl) - α - dimethyglyoxime, bis - O - (p - toluenesulfonyl) - α - diphenylglyoxime, bis - O - (p - toluenesulfonyl) - α - dicyclohexylglyoxime, bis - O - (p - toluenesulfonyl) - 2,3 - pentanedione glyoxime, bis - O - (p - toluenesulfonyl) - 2 - methyl - 3,4 - pentanedione glyoxime, bis - O - (n - butanesulfonyl) - α - dimethyglyoxime, bis - O - (n - butanesulfonyl) - α - diphenylglyoxime, bis - O - (n - butanesulfonyl) - α - dicyclohexylglyoxime, bis - O - (n - butanesulfonyl) - 2,3 - pentanedione glyoxime, bis - O - (n - butanesulfonyl) - 2 - methyl - 3,4 - pentanedione glyoxime, bis - O - (methanesulfonyl) - α - dimethyglyoxime, bis - O - (trifluoromethanesulfonyl) - α - dimethyglyoxime, bis - O - (1,1,1 - trifluoroethanesulfonyl) - α - dimethyglyoxime, bis - O - (tert - butanesulfonyl) - α - dimethyglyoxime, bis - O - (perfluorooctanesulfonyl) - α - dimethyglyoxime, bis - O - (cyclohexanesulfonyl) - α - dimethyglyoxime, bis - O - (benzenesulfonyl) - α - dimethyglyoxime, bis - O - (p - fluorobenzenesulfonyl) - α - dimethyglyoxime, bis - O - (p - tert - butylbenzenesulfonyl) - α - dimethyglyoxime, bis - O - (xylenesulfonyl) - α - dimethyglyoxime, bis - O - (camphorsulfonyl) - α - dimethyglyoxime; Sulfonic acid oxime ester derivatives such as α - (phenylsulfinylimino) - 4 - methylphenylacetonitrile; β - ketosulfone derivatives such as 2 - cyclohexylcarbonyl - 2 - (p - toluenesulfonyl)propane, 2 - isopropylcarbonyl - 2 - (p - toluenesulfonyl)propane; Disulfone derivatives such as diphenyl disulfone, dicyclohexyl disulfone; Sulfonic acid nitrobenzyl ester derivatives such as 2,6 - dinitrobenzyl p - toluenesulfonate, 2,4 - dinitrobenzyl p - toluenesulfonate; Sulfonic acid ester derivatives such as 1,2,3 - tris(methanesulfonyloxy)benzene, 1,2,3 - tris(trifluoromethanesulfonyloxy)benzene, 1,2,3 - tris(p - toluenesulfonyloxy)benzene; Sulfonic acid imide ester derivatives such as trifluoromethanesulfonic acid phthalimide ester, toluenesulfonic acid phthalimide ester, 5 - norbornene - 2,3 - dicarboximide trifluoromethanesulfonate, 5 - norbornene - 2,3 - dicarboximide toluenesulfonate, 5 - norbornene - 2,3 - dicarboximide n - butanesulfonate, N - trifluoromethanesulfonyloxynaphthalimide; Sulfonic acid imide ester derivatives such as (5 - (4 - methylphenyl)sulfonyloxyimino - 5H - thiophene - 2 - yliden) - (2 - methylphenyl)acetonitrile, (5 - (4 - (4 - methylphenylsulfonyloxy)phenyl)sulfonyloxyimino - 5H - thiophene - 2 - yliden) - (2 - methylphenyl)acetonitrile;Triazine derivatives such as 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine; 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane, etc. Among them, sulfonylimide ester derivatives, sulfonimide ester derivatives, sulfonic acid oxime ester derivatives, etc. can be preferably used. One or more than two kinds of the above-mentioned photoacid generators can be used.;

[0230] Regarding the blending amount of the photoacid generator as the component (B) above, from the viewpoints of the light absorption of the photoacid generator itself and the photocuring property under a thick film, in the negative photosensitive resin composition of the present invention, it is preferably 0.05 to 20 parts by mass, and particularly preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the component (A).

[0231] Also, in other forms of negative photosensitive resin compositions, the component (B) can be a photo radical initiator. By using such a component (B), the resin can be crosslinked and insolubilized. The photo radical initiator can be arbitrarily selected from known compounds used as photopolymerization initiators for UV curing. For example, as the photo radical initiator, preferably cited are: benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; 9-thioxanthone derivatives such as 9-thioxanthone, 2-methyl-9-thioxanthone, 2-isopropyl-9-thioxanthone, diethyl-9-thioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether; oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime; N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl peroxide; aromatic biimidazoles, etc., but not limited thereto. Also, they can be used alone or in combination of two or more. Among the above-mentioned photo radical initiators, oximes are particularly better from the viewpoint of photosensitivity.

[0232] The photoacid generator and the photo-radical initiator can be used separately or in combination as needed.

[0233] The blending amount of the component (B) is preferably 0.1 to 20 parts by mass, more preferably 2 to 15 parts by mass, based on 100 parts by mass of the resin of the component (A). By blending 0.1 part by mass or more of the component (B) based on 100 parts by mass of the component (A), the resulting negative photosensitive resin composition has excellent photosensitivity. On the other hand, by blending 20 parts by mass or less, the resulting negative photosensitive resin composition has excellent thick film hardening properties.

[0234] [(C) Surfactant]

[0235] The photosensitive resin composition of the present invention contains a surfactant having a structural unit represented by the following average empirical formula (1). By containing the structural unit represented by the following average empirical formula (1), in either the positive photosensitive resin composition or the negative photosensitive resin composition, the film thickness uniformity during coating is excellent and coating defects during thick film formation can be reduced.

[0236] [Chemical formula 37]

[0237] (R1R2Y2SiO 1 / 2 )2(R3Y1SiO 2 / 2 ) l (R5R6SiO 2 / 2 ) n (R q SiO3. / 2) m (1)

[0238] In the formula, Y1 and Y2 are each independently a hydrogen atom, a methyl group, a phenyl group, or a group represented by the following general formula (2), and at least one of Y1 and Y2 is a group represented by the following general formula (2). R1 to R6 may be the same or different and are each a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. l and n are each independently an integer of 1 to 100, and m is an integer of 0 to 100.

[0239] [Chemical formula 38]

[0240]

[0241] In the formula, the dotted line represents a bond. R9, R 10 , R 11 are each independently a linear or branched alkylene group having 2 to 10 carbon atoms. However, R 10 and R 11 are different. R 12 is a trivalent hydrocarbon group having 2 to 10 carbon atoms. R 13 represents having selected from (OR10 )、(OR 11 )、(OR 12 ) of one or more repeating unit structures, R 14 is a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl ether group having 1 to 10 carbon atoms, a linear or branched unsaturated alkyl ether group having 1 to 10 carbon atoms, or a linear or branched alkyl ester group having 1 to 10 carbon atoms. a is an integer from 1 to 50, b is an integer from 0 to 50, c is an integer from 0 to 50, and d is an integer from 1 to 20. -OR 10 -, -OR 11 -, -OR 12 (R 13 )- can also be random in order.

[0242] In the above average empirical formula (1), R1 to R6 can be the same or different from each other, and are monovalent hydrocarbon groups having 1 to 20 carbon atoms that may also contain heteroatoms. Specific examples of R1 to R6 can be listed as the same as those listed above as R 19 to R 22 in the general formula (14).

[0243] In the above general formula (2), R9, R 10 , R 11 are each independently a linear or branched alkylene group having 2 to 10 carbon atoms. However, R 10 and R 11 are different, R 12 is a trivalent hydrocarbon group having 2 to 10 carbon atoms, and R 13 represents a structure having one or more repeating units selected from (OR 10 ), (OR 11 ), (OR 12 ). R 14 is a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl ether group having 1 to 10 carbon atoms, a linear or branched unsaturated alkyl ether group having 1 to 10 carbon atoms, or a linear or branched alkyl ester group having 1 to 10 carbon atoms. R9, R 10 , R 11 are preferably linear or branched alkylene groups having 2 to 4 carbon atoms, and R 12 is preferably a trivalent hydrocarbon group having 2 to 4 carbon atoms.

[0244] In the above average empirical formula (1), l and n are each independently an integer of 1 to 100, m is an integer of 0 to 100, but l is preferably an integer of 1 to 50, more preferably an integer of 1 to 30, n is preferably an integer of 10 to 50, more preferably an integer of 10 to 30, and m is preferably an integer of 0 to 50, more preferably an integer of 0 to 30. When m is not 0, m is preferably an integer of 1 to 5. By setting l, m, and n within the above ranges, the film thickness uniformity during coating can be improved, and the defoaming property during thick film formation can be improved.

[0245] In the above general formula (2), a is an integer of 1 to 50, b is an integer of 0 to 50, c is an integer of 0 to 50, and d is an integer of 1 to 20, but a is preferably an integer of 10 to 30, b is preferably an integer of 10 to 30, and c is preferably an integer of 0 to 20. By setting a, b, and c within the above ranges, sufficient solubility in a solvent and an appropriate balance with the siloxane structure can be achieved, the film thickness uniformity during coating can be improved, and the defoaming property during thick film formation can be improved. When a, b, and c are greater than the upper limit value of the above range, the content ratio of the siloxane structure becomes small, so the defoaming property and the function as a surfactant are reduced. Also, when a, b, and c are less than the lower limit value of the above range, since the content ratio of the polyoxyalkylene becomes small, the solubility in a solvent may sometimes decrease.

[0246] Specific examples of the surfactant containing the structural unit represented by the above average empirical formula (1) include, but are not limited to, the compounds represented by the following formulas (C-1) to (C-15).

[0247] [Chemical formula 39]

[0248]

[0249] [Chemical formula 40]

[0250]

[0251] Among the dotted lines in the formula, the dotted line in the siloxane chain represents the bonding with (R1R2Y2SiO 1 / 2 ), (R3Y1SiO 2 / 2 ), (R5R6SiO 2 / 2 ), or (R4SiO 3 / 2 ), and the dotted line in the polyoxyalkylene chain represents the bonding with R 10 , R 11 , or R 12 .

[0252] The surfactant of component (C) has a hydrophobic siloxane chain and a polyoxyalkylene part that is hydrophilic in its side chain. By appropriately adjusting the combination and individual ratios of the respective units constituting the siloxane chain, the structure, position (terminal or side chain), average empirical formula (1), and substituents in the general formula (2) of the hydrophilic group represented by the general formula (2), it can have sufficient solubility in the solvent and an appropriate balance with the siloxane structure, can improve the film thickness uniformity during coating, and can improve the defoaming property during the formation of a thick film, resulting in a photosensitive resin composition with excellent film thickness uniformity during coating and reduced coating defects during the formation of a thick film.

[0253] [(E) Crosslinking agent]

[0254] The photosensitive resin composition of the present invention may contain, if necessary, an (E) crosslinking agent selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, phenolic compounds having an average of 2 or more hydroxymethyl or alkoxyhydroxymethyl groups in 1 molecule, compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with glycidyl groups, compounds in which the hydrogen atoms of the hydroxyl groups of polyhydric phenols are substituted with substituents represented by the following formula (E-1), and compounds containing 2 or more nitrogen atoms having glycidyl groups represented by the following formula (E-2).

[0255] [Chemical formula 41]

[0256]

[0257] In the formula, the dotted line represents a bond, and R f represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

[0258] Examples of the above-mentioned amino condensates modified with formaldehyde or formaldehyde-alcohol include melamine or melamine condensates modified with formaldehyde or formaldehyde-alcohol, or urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0259] The preparation of the above-mentioned melamine condensates modified with formaldehyde or formaldehyde-alcohol, for example, first modifies melamine monomers with formaldehyde for hydroxymethylation according to a known method, or further modifies it with alcohol for alkoxylation to prepare a modified melamine represented by the following general formula (30). In addition, the above-mentioned alcohol is a lower alcohol, and preferably an alcohol having 1 to 4 carbon atoms.

[0260] [Chemical formula 42]

[0261]

[0262] In the formula, R 34They may be the same or different and are hydroxymethyl, alkoxymethyl having an alkoxy group with 1 to 4 carbon atoms, or a hydrogen atom, and at least one of them is hydroxymethyl or the above alkoxymethyl.

[0263] The above R 34 Examples thereof may include: hydroxymethyl; alkoxymethyl such as methoxymethyl and ethoxymethyl; and a hydrogen atom, etc.

[0264] Specific examples of the modified melamine represented by the above general formula (30) may include: trimethoxymethylmonohydroxymethylmelamine, dimethoxymethylmonohydroxymethylmelamine, trihydroxymethylmelamine, hexahydroxymethylmelamine, hexamethoxymethylolmelamine, etc. Then, the modified melamine represented by the above general formula (30) or its polymer (for example, oligomers such as dimers and trimers) is subjected to addition condensation polymerization with formaldehyde according to a conventional method until a desired molecular weight is obtained, and a melamine condensate modified with formaldehyde or formaldehyde-alcohol can be obtained.

[0265] Also, the preparation of the above urea condensate modified with formaldehyde or formaldehyde-alcohol, for example, modifies a urea condensate with a desired molecular weight by hydroxymethylation with formaldehyde according to a known method, or further modifies it by alkoxylation with an alcohol.

[0266] Specific examples of the above urea condensate modified with formaldehyde or formaldehyde-alcohol may include, for example: methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate, etc.

[0267] In addition, one of these modified melamine condensates and modified urea condensates can be used, or two or more of them can be used in combination. Also, the above modified melamine can also be used as the component (E).

[0268] Then, examples of the phenolic compound having an average of 2 or more hydroxymethyl or alkoxymethylol (alkoxymethyl) in one molecule may include: (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2’,6,6’-tetramethoxymethylbisphenol A, compounds represented by the following formulas (E-3) to (E-7), etc.

[0269] [Chemical formula 43]

[0270]

[0271] In addition, one kind of the above crosslinking agent can be used, or two or more kinds can be used in combination.

[0272] On the other hand, examples of the compound in which the hydrogen atom of the hydroxyl group of the polyphenol is substituted with a glycidyl group include compounds obtained by reacting the hydroxyl groups of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Ideal examples of the compound in which the hydrogen atom of the hydroxyl group of the polyphenol is substituted with a glycidyl group include the compounds represented by the following formulas (E-8) to (E-14).

[0273] [Chemical formula 44]

[0274]

[0275] In the formula, the range of t is 2 ≤ t ≤ 3.

[0276] One or more of these compounds in which the hydroxyl group of the polyphenol is substituted with a glycidyloxy group (compounds in which the hydrogen atom of the hydroxyl group of the polyphenol is substituted with a glycidyl group) can be used as a crosslinking agent.

[0277] Examples of the compound in which the hydrogen atom of the hydroxyl group of the polyphenol is substituted with a substituent represented by the following formula (E-1) include those containing two or more of the substituents and represented by the following formula (E-15).

[0278] [Chemical formula 45]

[0279]

[0280] In the formula, the dotted line represents a bond.

[0281] [Chemical formula 46]

[0282]

[0283] In the formula, 1 ≤ u ≤ 3.

[0284] On the other hand, examples of the compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (E-2) include those represented by the following formula (E-16).

[0285] [Chemical formula 47]

[0286]

[0287] In the formula, the dotted line represents a bond, and R f represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

[0288] [Chemical formula 48]

[0289]

[0290] In the formula, G represents a linear, branched or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group.

[0291] Examples of the compound represented by the above formula (E-16) include compounds represented by the following formulas (E-17) to (E-20).

[0292] [Chemical Formula 49]

[0293]

[0294] On the other hand, as the compound containing two or more nitrogen atoms having glycidyl groups represented by the above formula (E-2), a compound represented by the following formula (E-21) can be preferably used.

[0295] [Chemical Formula 50]

[0296]

[0297] These compounds containing two or more nitrogen atoms having glycidyl groups represented by the above formula (E-2) can be used singly or in combination of two or more as a crosslinking agent.

[0298] In the case of the positive photosensitive resin composition of the present invention, the component (E) is a component that causes a crosslinking reaction during post-curing after pattern formation and further improves the strength of the cured product. Also, in the case of the negative photosensitive resin composition, the component (E) uses the acid generated from the component (B) as a catalyst, and the crosslinking group of the component (E) crosslinks with the resin of the component (A), thereby forming a negative pattern and further being a component that causes a crosslinking reaction during post-curing after pattern formation and further improves the strength of the cured product. Considering the viewpoints of photocurability and heat resistance, the weight average molecular weight of such a component (E) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0299] In the photosensitive resin composition of the present invention, the blending amount of the component (E) is preferably 0.5 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass, based on 100 parts by mass of the component (A).

[0300] [(D) Solvent]

[0301] The photosensitive resin composition of the present invention contains a (D) solvent. The solvent of the (D) component is contained in either a positive photosensitive resin composition or a negative photosensitive resin composition. If it can dissolve the (A) component, (B) component, (C) component, and also dissolve the (E) component when containing the (E) component, there is no particular limitation. Examples of the solvent include: ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoterbutyl ether acetate, γ-butyrolactone; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide. One or more of them can be used. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, N-methyl-2-pyrrolidone, or a mixed solvent thereof.

[0302] The blending amount of the (D) component is preferably 50 to 2,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on the total 100 parts by mass of the blending amounts of the (A) component, (B) component, (C) component, and also including the (E) component when containing the (E) component.

[0303] [Other Components]

[0304] Furthermore, in the photosensitive resin composition of the present invention, components other than the necessary (A) component, (B) component, (C) component, and (D) component may be further contained. Examples of other components include, in addition to the above-mentioned (E) component: (F) a compound that generates an acid upon heating, (G) an antioxidant, (H) a silane compound, (I) a basic compound, (J) a protective amine compound, (K) a dissolution inhibitor, (L) a free-radical polymerizable compound, etc.

[0305] [((F) Compound that Generates an Acid upon Heating)]

[0306] The compound that generates an acid upon heating of the (F) component may be added to thermally promote the crosslinking reaction between the (A) component and the (E) component in the post-curing step of heating at a temperature of 100 to 300 °C after the above-mentioned pattern formation.

[0307] Particularly with respect to the component (F), it is preferably a component that does not promote the hardening of the film and does not interfere with pattern formation until a pattern is formed by development. To achieve this purpose, the component (F) is preferably a compound that does not generate acid at the temperature in the step of removing the solvent and drying after coating the photosensitive resin composition, and starts to generate acid and promote the hardening of the pattern and the film of the positive photosensitive resin composition only through heat treatment after pattern formation. Specifically, it is preferably a compound that decomposes and generates acid through heat treatment at 100°C to 300°C, ideally at 150°C to 300°C. By containing such a component (F), the pattern and the film of the positive photosensitive resin composition can be changed into a pattern and a film in which the crosslinking and hardening reactions further proceed in the post-hardening step of heating at a temperature of 100 to 300°C applied after pattern formation. The component (F) can further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or film by further promoting the crosslinking and hardening reactions.

[0308] As the compound that preferably generates acid by heat, the compounds described in paragraphs

[0061] to

[0085] of Japanese Patent Laid-Open No. 2007-199653 can be used.

[0309] The blending amount of the compound that generates acid by heat is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, with respect to 100 parts by mass of the component (A) in the photosensitive resin composition of the present invention, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

[0310] ((G) Antioxidant)

[0311] By containing the antioxidant of the component (G), the oxidative degradation of the aliphatic group and phenolic hydroxyl group of the component (A) is inhibited. Also, by the rust prevention effect on metal materials, the oxidation of metals caused by external moisture, photoacid generators, thermal acid generators, etc., or the decrease in adhesion and peeling accompanying metal oxidation can be inhibited.

[0312] If specific examples of the antioxidant that can be used here are listed, it is preferably a hindered phenol antioxidant, a phosphorus antioxidant, a quinone antioxidant, or a sulfur antioxidant. However, it is not limited thereto. Also, these antioxidants can be used alone or in combination of two or more.

[0313] Among the specific examples of the above antioxidants, further examples of hindered phenol antioxidants include: pentaerythritol tetra[3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Ltd., IRGANOX 1010 (trade name)), thiodiethylene bis[3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate] (manufactured by BASF Japan Ltd., IRGANOX 1035 (trade name)), octadecyl 3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionate (manufactured by BASF Japan Ltd., IRGANOX 1076 (trade name)), octyl 3,5-di(tert-butyl)-4-hydroxyhydrocinnamate (manufactured by BASF Japan Ltd., IRGANOX 1135 (trade name)), 4,6-bis(octylthiomethyl)o-cresol (manufactured by BASF Japan Ltd., IRGANOX 1520L), Sumilizer GA80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB AO-20 (trade name, manufactured by ADEKA Corporation), ADK STAB AO-30 (trade name, manufactured by ADEKA Corporation), ADK STAB AO-40 (trade name, manufactured by ADEKA Corporation), ADK STAB AO-50 (trade name, manufactured by ADEKA Corporation), ADK STAB AO-60 (trade name, manufactured by ADEKA Corporation), ADK STAB AO-80 (trade name, manufactured by ADEKA Corporation), ADK STAB AO-330 (trade name, manufactured by ADEKA Corporation), hindered phenol antioxidants described in WO2017 / 188153A1, and the like.

[0314] Among the specific examples of the above antioxidants, further examples of phosphorus antioxidants include: triphenyl phosphite, tris(tolyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(nonylphenyl) phosphite, tris(octylphenyl) phosphite, tris[decyl poly(oxyethylene)] phosphite, tris(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tris(decyl) thiophosphite, tris(isodecyl) thio(phosphite), phenyl-bis(2-ethylhexyl) phosphite, phenyl-diisodecyl phosphite, tetradecyl poly(oxyethylene)-bis(ethylphenyl) phosphite, phenyl-dicyclohexyl phosphite, phenyl-diisooctyl phosphite, phenyl-di(tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl-diisodecyl phosphite, diphenyl-cyclohexylphenyl phosphite, diphenyl-(tridecyl) thiophosphite, and the like.

[0315] Among the specific examples of the above antioxidants, further examples of sulfur-based antioxidants include: ADK STAB AO-412S (manufactured by ADEKA Corporation, trade name), AO-503S (manufactured by ADEKA Corporation, trade name), Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd., trade name), etc.

[0316] Regarding sulfur-based antioxidants and phosphorus-based antioxidants, the effect of decomposing peroxides can be expected.

[0317] Furthermore, the content of the antioxidant in (G) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the resin of component (A). When the content is 0.1 part by mass or more, the adhesion to the metal material is improved and peeling is suppressed. Also, when the content is 10 parts by mass or less, the developability of the composition and the toughness of the cured film do not deteriorate.

[0318] ((H) Silane compound)

[0319] Regarding the silane compound of component (H), by containing the silane compound, not only can the adhesion to the metal material be improved, but also the peeling of the cured film in reliability tests such as thermal shock tests and high-temperature and high-humidity tests can be suppressed.

[0320] Any silane compound having an alkoxysilyl group can be used here. Also, ideal specific examples are as follows. Examples include: γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl-triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, triethoxysilylpropyl ethyl carbamate, 3-(triethoxysilyl)propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, the silane compound containing an amide group described in Japanese Patent No. 6414060, the silane compound containing a thiourea group described in WO2016 / 140024 and Japanese Patent No. 5987984, the silane compound containing a thiol group described in Japanese Patent No. 2017-044964, etc. However, it is not limited thereto. In addition, these silane compounds can be used alone or in combination of two or more.

[0321] Further, the content of the silane compound of (H) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 3 to 6 parts by mass with respect to 100 parts by mass of the resin of the component (A). If it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and if it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be more effectively suppressed. Further, when the content is 10 parts by mass or less, the developability of the composition is not deteriorated, and development residues are not caused.

[0322] ((I) basic compound)

[0323] Regarding the basic compound of the component (I), by containing the basic compound, the diffusion rate of the acid generated from the photoacid generator in the resist film can be suppressed. In the case of a negative photosensitive resin composition, by blending the above basic compound, the resolution can be improved, the sensitivity change after exposure can be suppressed, the substrate and environment dependence can be reduced, and the exposure latitude, pattern shape, etc. can be improved.

[0324] Examples of the above basic compound include primary, secondary, and tertiary aliphatic 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, imide derivatives, and compounds represented by the following general formula (31).

[0325] N(α) q (β) 3-q (31)

[0326] In the formula, q is 1, 2, or 3. The side chains α may be the same or different, and are any of the substituents represented by the following general formulas (32) to (34). The side chains β may be the same or different, and represent a hydrogen atom, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain an ether bond or a hydroxyl group. Further, the side chains α may also be bonded to each other to form a ring.

[0327] [Chemical formula 51]

[0328]

[0329] Here, R 300 、R 302 、R 305 are linear or branched alkylene groups having 1 to 4 carbon atoms, R 301 、R 304 are a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain one or more hydroxyl groups, ether bonds, ester bonds, or lactone rings. R 303 is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R 306is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain one or more hydroxyl groups, ether bonds, ester bonds, and lactone rings. In addition, * represents the bonding end.

[0330] Examples of primary aliphatic amines include: ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc.

[0331] Examples of secondary aliphatic amines include: dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di(sec-butyl)amine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, di(dodecyl)amine, di(hexadecyl)amine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, N,N-dimethyltetraethylenepentamine, etc.

[0332] Examples of tertiary aliphatic amines include: trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri(sec-butyl)amine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tri(dodecyl)amine, tri(hexadecyl)amine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, etc.

[0333] Examples of mixed amines include: dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, etc.

[0334] Examples of aromatic amines and heterocyclic amines are as follows: aniline derivatives (such as 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-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (such as oxazole, isoxazole, etc.), thiazole derivatives (such as thiazole, isothiazole, etc.), imidazole derivatives (such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (such as pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (such as pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (such as pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-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 (such as quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0335] Examples of nitrogen-containing compounds having a carboxyl group are as follows: aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (such as nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.).

[0336] Examples of nitrogen-containing compounds having a sulfonyl group are as follows: 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, etc.

[0337] Examples of nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include, for example: 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol 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, piperidine ethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidinyl-1,2-propanediol, 3-pyrrolidinyl-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidinoethanol, 1-aziridine ethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, and the like.

[0338] Examples of amide derivatives include, for example: formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, and the like.

[0339] Examples of imide derivatives include, for example: phthalimide, succinimide, maleimide, and the like.

[0340] Examples of the compound represented by the above general formula (31) 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-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)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, tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, 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, β-(diethylamino)-δ-valerolactone, but not limited thereto. One or more of the above basic compounds can be used.,

[0341] In view of sensitivity, the blending amount of the above basic compound in the photosensitive resin composition of the present invention is preferably 0 to 3 parts by mass, and particularly preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the component (A).

[0342] ((J) protecting amine compound)

[0343] The photosensitive resin composition of the present invention may contain a protected amine compound as the component (J). When the crosslinking agent of the component (E) has high reactivity, if an amine compound is directly added, there is a concern that the component (E) and the amine compound react at room temperature, and the viscosity of the composition increases over time, resulting in deteriorated storage stability. On the other hand, if it is an amine compound in which the basic group is protected by a protecting group, it does not react with the crosslinking agent of the component (E) at room temperature, so the storage stability of the photosensitive resin composition over time can be improved. Also, since the base is generated only upon heating, it can become a catalyst for the ring-closure reaction of the imide precursor, which is one of the components (A), or can become a catalyst for the crosslinking reaction between the resin of the component (A) and the crosslinking agent of the component (E), and effectively promote the crosslinking reaction.

[0344] As for the protected amine compound of the component (J), any nitrogen-containing organic compound in which a group that can be deprotected by heat or an acid is bonded to a nitrogen atom is acceptable. In particular, if it has a urethane structure represented by the following general formula (35) or (36), there are no particular restrictions.

[0345] [Chemical formula 52]

[0346]

[0347] Here, in the formula, R 35 、R 36 、R 37 and R 38 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R 39 and R 40 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a monocyclic group having substituents formed by bonding to each other, or a polycyclic group having substituents formed by bonding to each other, provided that the total number of carbon atoms in the formula is 10 or less.

[0348] Also, R 41represents an alkyl group having 1 to 12 carbon atoms which may also have substituents, a cycloalkyl group having 3 to 12 carbon atoms which may also have substituents, an alkenyl group having 2 to 12 carbon atoms which may also have substituents, an alkynyl group having 2 to 12 carbon atoms which may also have substituents, an aryl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an aralkyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, or a heterocyclic group which may also have substituents; provided that, the total number of carbon atoms constituting R 41 is set to 12 or less. Regarding the substituents which the above groups may also have, any one may be used according to the purpose.

[0349] Specific examples of the above formulas (35) and (36) are as follows. For example: N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(isopropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(isopropoxycarbonyl)diisopropylamine, N-(isopropoxycarbonyl)pyrrolidine, N-(isopropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(isopropoxycarbonyl)azetidine, N-(1-ethylpropoxycarbonyl)-2,6-dimethylpiperidine, N-(1-ethylpropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-ethylpropoxycarbonyl)diisopropylamine, N-(1-ethylpropoxycarbonyl)pyrrolidine, N-(1-ethylpropoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)azetidine, N-(1-propylbutoxycarbonyl)-2,6-dimethylpiperidine, N-(1-propylbutoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-propylbutoxycarbonyl)diisopropylamine, N-(1-propylbutoxycarbonyl)pyrrolidine, N-(1-propylbutoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-propylbutoxycarbonyl)azetidine, N-(cyclopentyloxycarbonyl)-2,6-dimethylpiperidine, N-(cyclopentyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclopentyloxycarbonyl)diisopropylamine, N-(cyclopentyloxycarbonyl)pyrrolidine, N-(cyclopentyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(cyclopentyloxycarbonyl)azetidine, N-(cyclohexyloxycarbonyl)-2,6-dimethylpiperidine, N-(cyclohexyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclohexyloxycarbonyl)diisopropylamine, N-(cyclohexyloxycarbonyl)pyrrolidine, N-(cyclohexyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(cyclohexyloxycarbonyl)azetidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(tert-butoxycarbonyl)diisopropylamine, N-(tert-butoxycarbonyl)pyrrolidine, N-(tert-butoxycarbonyl)-2,5-dimethylpyrrolidine, N-(tert-butoxycarbonyl)azetidine, N-(benzyloxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(benzyloxycarbonyl)diisopropylamine, N-(benzyloxycarbonyl)pyrrolidine, N-(benzyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(benzyloxycarbonyl)azetidine, 1,4-bis(N,N'-diisopropylaminocarbonyloxy)cyclohexane, imidazole compounds described in Japanese Patent Publication No. 5609815, etc.

[0350] The protected amine compound of this embodiment is particularly preferably one that decomposes 100% at 200°C or lower. Thereby, the alkali compound can be generated more effectively during thermosetting, and the imidization of the polyimide precursor, which is one of the components (A), or the crosslinking reaction between the crosslinking agent of the component (E) and the resin of the component (A) can be promoted. The boiling point of the alkali and other decomposition products obtained by heating the protected amine compound at 1 atmosphere (0.1 MPa) should be 200°C or lower. This is because by setting it to 200°C or lower, the decomposition products can be volatilized from the coating film by low-temperature treatment. There is no particular limitation on the lower limit of the boiling point of the decomposition products at 1 atmosphere. From the viewpoint of the simplicity of the synthesis of the protected amine compound, those with a boiling point of -150°C or higher are preferably used.

[0351] In addition, one kind of the protected amine compound can be used alone or two or more kinds can be used in combination. The blending amount is 0 to 10 parts by mass relative to 100 parts by mass of the resin of the component (A). When blending, 0.01 to 10 parts by mass, particularly 0.01 to 5 parts by mass, are preferably mixed. If the blending amount is 10 parts by mass or less, the alkali solubility of the composition will not be reduced, and the lithography patterning characteristics will not deteriorate.

[0352] ((K) dissolution inhibitor)

[0353] The photosensitive resin composition of the present invention may contain a dissolution inhibitor as the component (K). Examples of the dissolution inhibitor include compounds having a weight average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule, and compounds in which the hydrogen atoms of the phenolic hydroxyl groups are replaced by acid-labile groups in an overall average proportion of 0 to 100 mol%, or compounds having a carboxyl group in the molecule, and compounds in which the hydrogen atoms of the carboxyl group are replaced by acid-labile groups in an overall average proportion of 50 to 100 mol%.

[0354] In addition, the substitution rate of the hydrogen atoms of the phenolic hydroxyl groups replaced by acid-labile groups is 0 mol% or more, preferably 30 mol% or more, on average, based on the entire phenolic hydroxyl groups. The upper limit is 100 mol%, and 80 mol% is more preferable. The substitution rate of the hydrogen atoms of the carboxyl group replaced by acid-labile groups is 50 mol% or more, preferably 70 mol% or more, on average, based on the entire carboxyl group. The upper limit is 100 mol%.

[0355] At this time, the compound having two or more phenolic hydroxyl groups or the compound having a carboxyl group is preferably represented by the following formulas (K1) to (K14).

[0356] [Chemical formula 53]

[0357]

[0358] However, in the above formulas, R 201, R 202 each represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R 203 represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R 204 represents -(CH2) i1 -(where i1 represents an integer from 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R 205 represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R 206 represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or a phenyl or naphthyl group substituted with a hydroxyl group respectively. R 208 represents a hydrogen atom or a hydroxyl group. v1 is an integer from 0 to 2, and v2 is 0 or 1. w1 and h1 are 0 or 1. t1, u1, t2, u2, t3, u3 respectively satisfy t1 + u1 = 8, t2 + u2 = 5, t3 + u3 = 4, and are the numbers for each phenyl skeleton to have at least 1 hydroxyl group. aa is a number for adjusting the molecular weight of the compounds of formula (K8) and (K9) to 100 to 1,000.

[0359] The blending amount of the dissolution inhibitor is preferably 0 to 50 parts by mass, more preferably 5 to 50 parts by mass, still more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the resin of component (A), and can be used alone or in combination of two or more. If the blending amount is 0 parts by mass or more, the resolution will be improved, and if it is 50 parts by mass or less, there will be no film loss of the pattern and the resolution will not decrease.

[0360] ((L) radical polymerizable compound)

[0361] The photosensitive resin composition of the present invention may contain a radical polymerizable compound of component (L). By combining with the polyimide precursor represented by the general formula (5) of the above component (A) and a photo radical initiator, a negative photosensitive resin composition can be obtained. For such a composition, due to the radicals generated by exposure, the radical polymerizable compounds of component (L) will crosslink with each other, or when any one or both of R a and R b is a radical polymerizable group represented by the above general formula (6), the resin of component (A) and the radical polymerizable compound will crosslink, whereby a good negative pattern can be obtained. Considering that the radical polymerizable compound of component (L) functions as a crosslinking agent in this way, it is preferably a compound having 2 or more radical polymerizable unsaturated bonding groups in 1 molecule.

[0362] The compound having two or more radically polymerizable unsaturated bonding groups in the molecule is preferably a (meth)acrylic acid-based compound, for example, preferably: ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate (the number of each ethylene glycol unit is 2 to 20), polyethylene glycol dimethacrylate (the number of each ethylene glycol unit is 2 to 20), poly(1,2-propanediol) diacrylate, poly(1,2-propanediol) dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, pentaerythritol tetraacrylate, glycerol diacrylate, glycerol dimethacrylate, methylenebisacrylamide, N-hydroxymethylacrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, N,N'-bis(2-methacryloyloxyethyl)urea, etc., but not limited thereto.

[0363] The component (L) is preferably blended in an amount of 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, relative to 100 parts by mass of the component (A). In the range of 1 to 100 parts by mass, the desired effects can be fully obtained without having an adverse effect on the developability. In addition, one kind of compound can be used as the copolymerizable monomer, or a plurality of kinds can be used in combination.

[0364] (Pattern forming method)

[0365] Then, a pattern forming method using the photosensitive resin composition of the present invention will be described.

[0366] In the photosensitive resin composition of the present invention, in order to form a pattern, it can be carried out by a known photolithography technique. For example, on a silicon wafer or a SiO2 substrate, a SiN substrate, or a substrate having a pattern such as copper wiring formed thereon, the photosensitive resin composition is coated by a spin coating method (spin coating method), and pre-baked under the conditions of 80 to 130 °C for about 50 to 600 seconds to form a photosensitive film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, more preferably 5 to 20 μm.

[0367] In the spin coating method, about 5 mL of the photosensitive resin composition is dispensed onto a silicon substrate, and then the substrate is rotated to coat the photosensitive resin composition on the substrate. At this time, by adjusting the rotation speed, the film thickness of the photosensitive material film on the substrate can be easily adjusted. Subsequently, the residual solvent can be removed by pre-baking.

[0368] Then, a mask for forming a target pattern is placed over the photosensitive material film, and high-energy rays with wavelengths of 190 to 500 nm, such as i-rays and g-rays, or an electron beam are irradiated to make the exposure dose about 1 to 5,000 mJ / cm 2 , preferably about 100 to 2,000 mJ / cm 2 .

[0369] Then, if necessary, post-exposure heating treatment (post-exposure bake (PEB)) can be performed on a hot plate at 60 to 150 °C for 1 to 10 minutes, preferably at 80 to 120 °C for 1 to 5 minutes. By doing so, the acid generated from the photoacid generator due to exposure can be used as a catalyst to promote the cross-linking reaction between the cross-linking groups of the cross-linking agent and the cross-linking reaction sites of the polymer.

[0370] Subsequently, development is carried out. Depending on the type of the resin of the component (A) in the photosensitive resin composition of the present invention, either alkali development using an aqueous alkali solution or organic solvent development can be selected.

[0371] An ideal aqueous alkali solution for alkali development can be, for example, a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH). Development can be carried out by using common methods such as the spray method and the immersion method, by immersing in the developer solution, etc. Subsequently, washing, rinsing, drying, etc. are carried out as needed, and a resist film with a desired pattern can be obtained.

[0372] On the other hand, an ideal organic solvent for organic solvent development can be the above-mentioned solvent used when preparing the photosensitive resin composition of the present invention. For example, it is preferably a ketone such as cyclohexanone and cyclopentanone, and more preferably a glycol such as propylene glycol monomethyl ether. Development can be carried out by using common methods such as the spray method and the immersion method, by immersing in the developer solution, etc. Subsequently, washing, rinsing, drying, etc. are carried out as needed, and a resist film with a desired pattern can be obtained.

[0373] (Hardened film forming method)

[0374] Furthermore, by heating and post-curing the film of the formed pattern obtained by the above-described pattern forming method using an oven or a hot plate at a temperature of 100 to 300°C, preferably 150 to 300°C, and more preferably 180 to 250°C, a cured film can be formed. When the post-curing temperature is 100 to 300°C, the crosslinking density of the film of the photosensitive resin composition can be increased, and residual volatile components can be removed, which is ideal in terms of the adhesion to the substrate, heat resistance, strength, and electrical properties. Moreover, the post-curing time can be set from 10 minutes to 10 hours.

[0375] Regarding the above-formed pattern, it is used for the purpose of a protective film covering wirings, circuits, substrates, etc. These formed patterns and the protective film have excellent insulation properties, and at the same time, they exhibit excellent adhesion on a metal layer such as Cu of the wiring or circuit to be coated, on a metal electrode existing on the substrate, or on an insulating substrate such as SiN existing in the wiring or circuit to be coated. Moreover, in a state where it has the corresponding mechanical strength as a protective film, the resolution ability for forming fine patterns can be greatly improved.

[0376] (Cured film)

[0377] The cured film obtained in this way has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to alkaline stripping solutions, etc. The reliability of the semiconductor device using it as a protective film is also excellent. In particular, it can prevent cracks from occurring during the temperature cycle test, and can be ideally used as a protective film (interlayer insulating film or surface protective film) for electrical and electronic components, semiconductor devices, etc.

[0378] That is, the present invention provides an interlayer insulating film or a surface protective film composed of a cured film obtained by curing the above-described photosensitive resin composition.

[0379] Regarding the above protective film, considering its heat resistance, chemical resistance, and insulation properties, it is effective in insulating films for semiconductor devices including re-wiring applications, insulating films for multi-layer printed circuit boards, solder resist films, cover film applications, etc.

[0380] In addition, the present invention provides an electronic component having the above interlayer insulating film or the above surface protective film.

[0381] Such an electronic component has a protective film (interlayer insulating film or surface protective film) having heat resistance, chemical resistance, and insulation properties, and thus has excellent reliability.

[0382] Specific examples of such electronic components include: semiconductor integrated circuit components such as IC (Integrated Circuit) and LSI (Large-Scale Integrated Circuit); optoelectronic semiconductor components such as LED (Light Emitting Diode), PD (Photo Diode), CCD (Charged-Coupled Device), and CMOS (Complementary Metal-Oxide Semiconductor); sensor components such as current sensor components or magnetic sensor components; and various electronic components such as MEMS (Micro electromechanical systems) components, which are micro machines formed by a microelectromechanical mechanism on the surface of a semiconductor substrate.

[0383] Examples

[0384] Hereinafter, the present invention will be specifically described by way of synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0385] I. Synthesis of Resin

[0386] In the following synthesis examples, the chemical structural formulas and names of the compounds used are as follows.

[0387] [Chemical Formula 54]

[0388]

[0389] [Chemical Formula 55]

[0390]

[0391] [Synthesis Example 1] Synthesis of Polyimide Resin (A1)

[0392] In a 1 L flask equipped with a stirrer and a thermometer, 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.6 mmol) of 4-aminophenol (PAP), and 125 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, a solution prepared by dissolving 26.7 g (86.2 mmol) of 3,3’,4,4’-oxydiphthalic dianhydride (s-ODPA) in 270 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. After the addition was completed, the mixture was stirred at room temperature for 3 hours. Thereafter, 40 g of xylene was added to the reaction solution, and while removing the water generated at 170 °C from the system, heating under reflux was carried out for 3 hours. After cooling to room temperature, the reaction solution was added dropwise to 2 L of ultrapure water with stirring, the precipitate was separated by filtration, washed appropriately with water, and dried under reduced pressure at 40 °C for 48 hours to obtain polyimide resin (A1). After measuring the molecular weight of this polymer by GPC, the weight-average molecular weight in terms of polystyrene was 35,000.

[0393] [Synthesis Example 2] Synthesis of polyimide resin (A2)

[0394] In Synthesis Example 1, 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was replaced with 21.2 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP). Except for this, polyimide resin (A2) was obtained with the same formulation. After measuring the molecular weight of this polymer by GPC, the weight-average molecular weight in terms of polystyrene was 34,000.

[0395] [Synthesis Example 3] Synthesis of polyamideimide resin (A3)

[0396] In a 500 mL flask equipped with a stirrer and a thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, a solution prepared by dissolving 19.0 g (61.4 mmol) of 3,3’,4,4’-oxydiphthalic dianhydride (s-ODPA) in 192 g of N-methyl-2-pyrrolidone was added dropwise at room temperature. After the addition was completed, the mixture was stirred at room temperature for 3 hours. Thereafter, 40 g of xylene was added to the reaction solution, and the mixture was heated under reflux for 3 hours while removing the water generated at 170 °C from the system. After cooling to room temperature, 3.2 g (41.0 mmol) of pyridine was added, and 4.9 g (20.5 mmol) of sebacoyl dichloride (DC-1) was added dropwise while maintaining the temperature at 5 °C or lower. After the addition was completed, the temperature was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water with stirring. The precipitate was separated by filtration, washed appropriately, and dried under reduced pressure at 40 °C for 48 hours to obtain a polyamideimide resin (A3). After measuring the molecular weight of the polymer by GPC, the weight-average molecular weight in terms of polystyrene was 35,000.

[0397] [Synthesis Example 4] Synthesis of polyamide resin (A4)

[0398] In a 500 mL flask equipped with a stirrer and a thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, 13.0 g (163.8 mmol) of pyridine was added, and 19.6 g (81.9 mmol) of sebacoyl dichloride (DC-1) was added dropwise while maintaining the temperature at 5 °C or lower. After the addition was completed, the temperature was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water with stirring. The precipitate was separated by filtration, washed appropriately, and dried under reduced pressure at 40 °C for 48 hours to obtain a polyamide resin (A4). After measuring the molecular weight of the polymer by GPC, the weight-average molecular weight in terms of polystyrene was 38,000.

[0399] [Synthesis Example 5] Synthesis of tetracarboxylic acid diester compound (X-1)

[0400] In a 3 L flask equipped with a stirrer and a thermometer, 100 g (322 mmol) of 3,3’,4,4’-oxydiphthalic dianhydride (s-ODPA), 65.2 g (644 mmol) of triethylamine, 39.3 g (322 mmol) of N,N-dimethyl-4-aminopyridine, and 400 g of γ-butyrolactone were added. While stirring at room temperature, 83.8 g (644 mmol) of 2-hydroxyethyl methacrylate (HEMA) was added dropwise. Then, the mixture was stirred at room temperature for 24 hours. Thereafter, 370 g of a 10% aqueous hydrochloric acid solution was added dropwise under ice cooling to stop the reaction. 800 g of 4-methyl-2-pentanone was added to the reaction solution, and the organic layer was separated and extracted. Then, it was washed 6 times with 600 g of water. The solvent of the obtained organic layer was distilled off to obtain 180 g of a tetracarboxylic acid diester compound (X-1).

[0401] [Synthesis Example 6] Synthesis of Polyimide Precursor (A5)

[0402] In a 1 L flask equipped with a stirrer and a thermometer, 57.1 g (100 mmol) of (X-1) and 228 g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Then, while maintaining the reaction solution temperature at 10°C or lower under ice cooling, 24.4 g (205 mmol) of thionyl chloride was added dropwise. After the addition was completed, the mixture was stirred under ice cooling for 2 hours. Then, while maintaining the reaction solution temperature at 10°C or lower under ice cooling, a solution prepared by dissolving 34.8 g (95 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 1.1 g (10 mmol) of 4-aminophenol (PAP), and 32.4 g (410 mmol) of pyridine in 144 g of N-methyl-2-pyrrolidone was added dropwise. After the addition was completed, the temperature was returned to room temperature, and the reaction solution was added dropwise to 3 L of water with stirring. The precipitate was separated by filtration, washed appropriately with water, and then dried under reduced pressure at 40°C for 48 hours to obtain a polyimide precursor (A5). After measuring the molecular weight of this polymer by GPC, the weight-average molecular weight in terms of polystyrene was 36,000.

[0403] [Synthesis Example 7] Synthesis of Polyimide Resin (A6)

[0404] In a 1 L flask equipped with a stirrer and a thermometer, 27.5 g (75 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 5.8 g (20 mmol) of 1,3-bis(3-aminophenoxy)benzene (APB), 1.1 g (10 mmol) of 4-aminophenol (PAP), and 138 g of γ-butyrolactone were added and dissolved by stirring at room temperature. Then, a solution prepared by dissolving 12.4 g (40 mmol) of 3,3’,4,4’-oxydiphthalic dianhydride (s-ODPA) and 110.5 g of an acid anhydride-modified silicone (DAN-1) in 492 g of γ-butyrolactone was added dropwise at room temperature. After the addition was completed, the mixture was stirred at room temperature for 3 hours. Thereafter, 40 g of xylene was added to the reaction solution, and the mixture was heated under reflux for 3 hours while removing the water generated at 170 °C from the system. After cooling to room temperature, 1.7 g (22.5 mmol) of glycidol was added to the polyimide solution, and the mixture was heated at 120 °C for 3 hours. After cooling to room temperature, the reaction solution was added dropwise to 4 L of ultrapure water with stirring, the precipitated product was separated by filtration, washed appropriately with water, and dried under reduced pressure at 40 °C for 48 hours to obtain a polyimide resin (A6). After measuring the molecular weight of the polymer by GPC, the weight-average molecular weight in terms of polystyrene was 20,000.

[0405] [Synthesis Example 8] Synthesis of Resin (A7) Containing a Siloxane Skeleton

[0406] In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, and a reflux condenser, 624 g (1.45 mol) of compound (S-1) was dissolved in 2,500 g of toluene, and then 261.2 g (0.62 mol) of compound (S-2), 1,214.4 g (0.40 mol) of compound (S-7), and 13.3 g (0.10 mol) of compound (S-6) were added, and the mixture was heated to 60 °C. Thereafter, 3.5 g of a carbon-supported platinum catalyst (5 mass%) was added. After confirming that the internal reaction temperature rose to 65 - 67 °C, the temperature was further raised to 90 °C over 3 hours, then cooled again to 60 °C, and 3.5 g of a carbon-supported platinum catalyst (5 mass%) was added. 285.2 g (1.47 mol) of compound (S-5) was added dropwise to the flask over 1 hour. At this time, the temperature in the flask rose to 65 - 67 °C. After completion of the dropwise addition, the mixture was further aged at 90 °C for 3 hours, cooled to room temperature, and 2,800 g of methyl isobutyl ketone was added. The reaction solution was pressure-filtered using a filter to remove the platinum catalyst. Further, 1,300 g of pure water was added to the obtained resin solution containing a siloxane skeleton, and the mixture was stirred and allowed to stand for liquid separation to remove the lower aqueous layer. This liquid separation and water washing operation was repeated 6 times. The solvent in the resin solution containing a siloxane skeleton was distilled off under reduced pressure to obtain a resin (A7) containing a siloxane skeleton. After measuring the molecular weight of the polymer by GPC, the weight-average molecular weight in terms of polystyrene was 31,000.

[0407] [Synthesis Example 9] Synthesis of Resin (A8) Containing a Siloxane Skeleton

[0408] In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, and a reflux condenser, 26.5 g (0.10 mol) of compound (S-4), 108.9 g (0.90 mol) of compound (S-3), 151.3 g (0.05 mol) of compound (S-7), and 2,000 g of toluene were added, and the mixture was heated to 60 °C. Thereafter, 1.0 g of a carbon-supported platinum catalyst (5 mass%) was added. After confirming that the internal reaction temperature had risen to 63 - 65 °C, the mixture was further heated to 90 °C over 3 hours, cooled again to 60 °C, and 1.0 g of a carbon-supported platinum catalyst (5 mass%) was added. 184.3 g (0.95 mol) of compound (S-5) was added dropwise to the flask over 1 hour. At this time, the temperature in the flask rose to 65 - 67 °C. After completion of the dropwise addition, the mixture was further aged at 90 °C for 3 hours, cooled to room temperature, and 2,000 g of methyl isobutyl ketone was added. The reaction solution was pressure-filtered using a filter to remove the platinum catalyst. Further, 1,000 g of pure water was added to the resulting resin solution containing a siloxane backbone, and the mixture was stirred and allowed to stand for liquid separation to remove the lower aqueous layer. This liquid separation and water washing operation was repeated 6 times. The solvent in the resin solution containing a siloxane backbone was distilled off under reduced pressure to obtain a resin (A8) containing a siloxane backbone. After measuring the molecular weight of the polymer by GPC, the weight-average molecular weight in terms of polystyrene was 15,000.

[0409] II. Preparation of Photosensitive Resin Composition

[0410] Using the polymers synthesized in Synthesis Examples 1 - 9 above as base resins, a resin composition at 30 mass% in terms of resin was prepared with the compositions and blending amounts shown in Table 1. Thereafter, after stirring, mixing, and dissolving, it was precisely filtered using a 0.5 μm filter made of Teflon (registered trademark) to obtain a photosensitive resin composition. In the table, PGMEA for the solvent represents propylene glycol monomethyl ether acetate, GBL represents γ-butyrolactone, and CPn represents cyclopentanone.

[0411] [Table 1]

[0412]

[0413]

[0414] In addition, in Table 1, the details of each component are as described below.

[0415] (Component (B))

[0416] · B1

[0417] [Chemical Formula 56]

[0418]

[0419] In the formula, Q represents a 1,2-naphthoquinone diazide sulfonyl group or a hydrogen atom represented by the following formula (37), and 90% of Q is substituted with a 1,2-naphthoquinone diazide sulfonyl group represented by the following formula (37).

[0420] [Chemical formula 57]

[0421]

[0422] ·B2: N-1919 manufactured by ADEKA Corporation

[0423] ·B3

[0424] [Chemical formula 58]

[0425]

[0426] ·B4

[0427] [Chemical formula 59]

[0428]

[0429] Component (C)

[0430] [Chemical formula 60]

[0431]

[0432] C-20: FC-430 (perfluorooctane sulfonic acid derivative) manufactured by Sumitomo 3M Co., Ltd.

[0433] Component (E)

[0434] ·E1

[0435] [Chemical formula 61]

[0436]

[0437] ·E2: EP4000L manufactured by ADEKA Corporation

[0438] ·E3

[0439] [Chemical formula 62]

[0440]

[0441] Component (L)

[0442] ·L1: Diethylene glycol diacrylate

[0443] Component (I)

[0444] ·I1

[0445] [Chemical formula 63]

[0446]

[0447] III. Pattern Formation

[0448] After dispensing 5 mL of the above photosensitive resin compositions 1 to 14 and comparative photosensitive resin compositions 1 to 3 onto an 8-inch silicon substrate, the substrate was rotated, i.e., spin coating was used, and coating was performed such that the film thickness after post-hardening heating applied after pattern formation became 10 μm. That is, considering the case where the film thickness would decrease in the post-hardening step in advance, the rotation speed during coating was adjusted so that the final film thickness after post-hardening became 10 μm. Then, pre-baking was performed on a hot plate at 100 °C for 2 minutes.

[0449] The film thickness of the obtained coated film was measured at 29 locations at intervals of 6 mm in the diameter direction of the substrate using a film thickness meter RE-3100 manufactured by Dainippon Screen Co., Ltd., and the average of the film thickness and the variation in the film thickness as coating uniformity were expressed as a range in Table 2.

[0450] Also, the results of measuring the number of defects of 100 nm or more in the obtained coated film using a defect inspection apparatus Surfscan SP2 manufactured by KLA-Tencor Corporation are shown in Table 2.

[0451] Then, i-ray exposure and pattern formation were performed using an i-ray stepper NSR-2205i11 manufactured by Nikon Corporation. In pattern formation, a mask for positive patterns and a mask for negative patterns were appropriately combined according to the photosensitive resin composition used. The mask had a pattern capable of forming holes with a 20-μm pattern arranged in a 1:1 aspect ratio, and was capable of forming a hole pattern with a pitch of 10 μm from 50 μm to 20 μm, a pitch of 5 μm from 20 μm to 10 μm, and a pitch of 1 μm from 10 μm to 1 μm.

[0452] Then, for those who performed the heating step (post-exposure bake), it was performed under the conditions shown in Table 2 below.

[0453] In the development step, a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developer for the aqueous alkali solution, or cyclopentanone (CPn) was used as the developer for the organic solvent. The results are shown in Table 2. When using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH), immersion development was performed 3 times for 1 minute, and then rinsing with ultrapure water was performed. When using cyclopentanone (CPn), immersion development was performed 2 times for 1 minute, and then rinsing was performed with isopropyl alcohol.

[0454] Then, post-hardening was performed on the obtained substrate pattern in an oven while purging with nitrogen at 200 °C for 2 hours.

[0455] Then, each substrate was cut in such a way as to observe the shape of the hole pattern, and the shape of the 10-μm hole pattern was observed using a scanning electron microscope (SEM).

[0456] In addition, the pattern shape of the holes was evaluated based on the following criteria, and the evaluation results are shown in Table 2.

[0457] Good: Those in which the holes were observed to be rectangular or in a forward-tapered shape (a shape in which the size of the upper part of the hole is larger than the size of the bottom part).

[0458] Poor: Those in which an inverse-tapered shape (a shape in which the size of the upper part of the hole is smaller than the size of the bottom part), an overhanging shape (a shape in which the upper part of the hole is overhanging), significant film loss, or residues were observed at the bottom of the holes.

[0459] [Table 2]

[0460]

[0461] As shown in Table 2, the photosensitive resin composition of the present invention exhibited good pattern shapes in both positive and negative patterns, and in either alkaline aqueous solution development or organic solvent development. Also, compared with the comparative example using a known fluorine-based surfactant, it was confirmed that the film thickness range of the present invention was small, the film thickness uniformity was excellent, and the number of coating defects was also reduced.

[0462] In addition, the present invention is not limited to the above-described embodiments. The above-described embodiments are for illustration, and those having a configuration substantially the same as the technical idea described in the claims of the present invention and exhibiting the same effects are all intended to be included within the technical scope of the present invention.

Claims

1. A photosensitive resin composition, characterized by containing: (A) A resin selected from at least one of polyamide, polyamideimide, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and a resin containing a siloxane skeleton, (B) A photosensitizer, (C) A surfactant containing a structural unit represented by the following average empirical formula (1), and (D) A solvent; (R1R2Y2SiO 1 / 2 )2(R3Y1SiO 2 / 2 ) l (R5R6SiO 2 / 2 ) n (R4SiO 3 / 2 ) m (1) In the formula, Y1 and Y2 are each independently a hydrogen atom, a methyl group, a phenyl group, or a group represented by the following general formula (2), and at least one of Y1 and Y2 is a group represented by the following general formula (2). R1 to R6 may be the same or different and are each a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. l and n are each independently an integer of 1 to 100, and m is an integer of 0 to 100; In the formula, the dotted line represents a bond, and R9, R 10 , R 11 are each independently a linear or branched alkylene group having 2 to 10 carbon atoms. However, R 10 and R 11 are different, R 12 is a trivalent hydrocarbon group having 2 to 10 carbon atoms, R 13 represents a structure having one or more repeating units selected from (OR 10 ), (OR 11 ), (OR 12 ), R 14 is a linear or branched alkyl ester group having 2 to 10 carbon atoms, a is an integer of 1 to 50, b is an integer of 0 to 50, c is an integer of 0 to 50, d is an integer of 1 to 20; -OR 10 -, -OR 11 -, -OR 12 (R 13 )- may also be in a random order.

2. The photosensitive resin composition according to claim 1, wherein, In the general formula (2), a is an integer of 10 to 30, b is an integer of 10 to 30, and c is an integer of 0 to 20.

3. The photosensitive resin composition according to claim 1 or 2, further containing: (E) A crosslinking agent selected from an amino condensate modified with formaldehyde or formaldehyde - alcohol, a phenolic compound having an average of 2 or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule, a compound in which the hydrogen atom of the hydroxyl group of a polyphenol is substituted with an epoxypropyl group, a compound in which the hydrogen atom of the hydroxyl group of a polyphenol is substituted with a substituent represented by the following formula (E - 1), and a compound containing 2 or more nitrogen atoms having an epoxypropyl group represented by the following formula (E - 2); In the formula, the dotted line represents a bond, and R f represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

4. The photosensitive resin composition according to claim 1, wherein, The weight - average molecular weight of the resin is 3,000 to 500,000.

5. The photosensitive resin composition according to claim 1 or 2, wherein, The (B) photosensitizer is a photoacid generator.

6. The photosensitive resin composition according to claim 5, wherein The photoacid generator is a compound having a diazoquinone structure.

7. The photosensitive resin composition according to claim 1 or 2, wherein The (B) photosensitizer is a photo - radical initiator.

8. A pattern forming method, characterized by comprising the following steps: (I) Coating the photosensitive resin composition according to any one of claims 1 to 7 on a substrate to form a photosensitive film, (II) Then, after heat treatment, exposing the photosensitive film to high - energy rays or an electron beam with a wavelength of 190 to 500 nm through a photomask, (III) Developing with a developer of an alkaline aqueous solution or an organic solvent.

9. The pattern forming method according to claim 8, wherein, Between the exposure step (II) and the development step (III), a post - exposure heating step is included.

10. A method for forming a cured film, characterized by comprising the following steps: Further heating and post - curing the film with a formed pattern obtained by the pattern forming method according to claim 8 or 9 at a temperature of 100 to 300 °C.

11. An interlayer insulating film, characterized by: Being composed of a cured film of the photosensitive resin composition according to any one of claims 1 to 7.

12. A surface protective film, characterized by: Being composed of a cured film of the photosensitive resin composition according to any one of claims 1 to 7.

13. An electronic component, characterized by: Having the interlayer insulating film according to claim 11 or the surface protective film according to claim 12.

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