Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern

Abstract

The purpose of the present disclosure is to provide: a photosensitive resin composition which has high adhesiveness and high sensitivity while maintaining high resolution; a photosensitive resin laminate; a method for forming a resist pattern; and a method for producing a conductor pattern. A photosensitive resin composition according to the present disclosure comprises (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, (C) a polymerization initiator, and (D) a polymerization inhibitor. The (D) polymerization inhibitor contains, with respect to the total amount of solid content of the photosensitive resin composition, 0.002-0.3 mass% of a compound that has a Mol LogP of 2.35 or less and that has an aromatic ring in which 2 or more hydrogen atoms are substituted with a group represented by XH (X represents at least one selected from O, NH, and NR', and R' represents at least one selected from the group consisting of alkyl groups having 1-20 carbon atoms, carbonyl groups having 1-20 carbon atoms, carboxy groups having 1-20 carbon atoms, and sulfonyl groups having 1-20 carbon atoms).

Description

Photosensitive resin composition, photosensitive resin laminate, and method for forming a resist pattern

[0001] This disclosure relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern, etc.

[0002] Printed circuit boards are generally manufactured by photolithography. Photolithography is a technique that forms a photosensitive resin layer on a substrate, and then exposes and develops the resin layer to form a resist pattern. Using this technique, a desired wiring pattern can be formed on the substrate by first forming a conductor pattern through etching or plating, and then removing the resist pattern from the substrate.

[0003] To manufacture printed circuit boards, a "photosensitive resin laminate" (also called a "dry film resist") is often used, in which a photosensitive resin layer is laminated on a support. There are known examples of photosensitive resin compositions for obtaining such photosensitive resin laminates, and examples of such known examples include the following Patent Documents 1 and 2.

[0004] Patent Document 1 aims to provide a photosensitive resin composition that exhibits excellent adhesion to copper surfaces and can form a stable resist film that is not affected by changes over time after coating or lamination. The disclosure describes the study of a photosensitive resin composition comprising a carboxylic acid compound and one or more heterocyclic compounds selected from the group consisting of triazoles, tetrazoles, and imidazoles.

[0005] Patent Document 2 aims to provide a photosensitive resin composition that exhibits excellent adhesion to copper, low development residue, and excellent plating adhesion. The disclosure describes the study of a photosensitive resin composition comprising a compound having an acidic group with an acid dissociation constant (pKa) of -5 or more and containing a total of three or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms in two or more aromatic rings.

[0006] International Publication No. 2008 / 015754, Japanese Patent Publication No. 2023-136935

[0007] Wildman, SA; Crippen, GM, Prediction of Physicochemical Parameters by Atomic Contributions, Journal of Chemical Information and Computer Sciences, 1999, 39, 868-873.

[0008] There is a growing demand for miniaturization, increased density, and improved productivity in electronic devices. In particular, to further enhance the image quality of resist patterns, there is a strong need for good adhesion to the substrate and high resolution when the photosensitive resin layer is thin. Simultaneously, there is a strong demand for photosensitive resin materials with high exposure sensitivity to reduce the required exposure amount in the exposure process. However, conventional technology has room for improvement in achieving high adhesion and high exposure sensitivity while maintaining high resolution.

[0009] Therefore, the object of this disclosure is to provide a photosensitive resin composition, a photosensitive resin laminate, a method for forming a resist pattern, and a method for manufacturing a conductor pattern that maintain high resolution, high adhesion, and high sensitivity.

[0010] One aspect of the present invention is listed below. [1] A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor; wherein the (D) polymerization inhibitor contains 0.002 to 0.3% by mass of a compound having an aromatic ring in which two or more hydrogen atoms are substituted with a group represented by XH (wherein X is at least one selected from O, NH, and NR', and R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms), and having a MolLogP of 2.35 or less, with respect to the total solid content of the photosensitive resin composition. [2] The photosensitive resin composition according to item 1, wherein at least one of the groups represented by XH is a hydroxyl group. [3] A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor, wherein the polymerization inhibitor (D) is represented by the following formula (1) and has a MolLogP of 2.35 or less (D １ A photosensitive resin composition containing 0.002 to 0.3% by mass of the compound relative to the total solid content of the photosensitive resin composition. {In formula (1), X is at least one selected from O, NH, and NR', R is at least one selected from the group consisting of a halogen atom; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a carboxyl group; or an alkyl group having 1 to 10 carbon atoms, R' is at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms, a is an integer of 1 or more, b is an integer of 0 or more, and the sum of a and b is an integer between 2 and 5.} [4] The above (D １ ) A photosensitive resin composition according to item 3, wherein a is 2 or more in the compound. [5] The (D １) A photosensitive resin composition according to item 3 or 4, wherein a is 2 in the compound. [6] The (D １ ) A photosensitive resin composition according to any one of items 3 to 5, wherein b is 1 or more in the compound. [7] The (D １ ) A photosensitive resin composition according to any one of items 3 to 6, wherein X is an oxygen atom (O) in the compound. [8] The (D １ ) A photosensitive resin composition according to any one of items 3 to 7, wherein in the compound, R is a carboxyl group. [9] A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor; wherein the (D) polymerization inhibitor contains 0.002 to 0.3% by mass of a compound having an aromatic ring in which three or more hydrogen atoms are substituted with a group represented by XH (wherein X is at least one selected from O, NH, and NR', and R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms) with respect to the total solid content of the photosensitive resin composition.

[10] A photosensitive resin composition according to item 9, wherein at least one of the groups represented by XH is a hydroxyl group.

[11] A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor; wherein the polymerization inhibitor (D) is represented by the following formula (1), and in the formula (1), a is 2 or more (D ２ A photosensitive resin composition containing 0.002 to 0.3% by mass of the compound relative to the total solid content of the photosensitive resin composition. {In formula (1), X is at least one selected from O, NH, and NR'; R represents at least one selected from the group consisting of: a halogen atom; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a carboxy group; or a carboxyalkyl group in which the alkyl group has 1 to 10 carbon atoms; R' represents at least one selected from the group consisting of: an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxy group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms; a represents an integer of 2 or more, b represents an integer of 0 or more, and the sum of a and b is an integer of 2 or more and 5 or less.}

[12] The (D ２ ) compound, wherein b is 1 or more, the photosensitive resin composition according to item 11.

[13] The (D ２ ) compound, wherein X is an oxygen atom (O), the photosensitive resin composition according to item 11 or 12.

[14] The (D ２ ) compound, wherein R is a carboxy group, the photosensitive resin composition according to any one of items 11 to 13.

[15] The photosensitive resin composition according to any one of items 1 to 14, wherein the (C) polymerization initiator comprises at least one of a hexaarylbiimidazole compound or an acridine compound.

[16] The photosensitive resin composition according to any one of items 1 to 15, wherein the (C) polymerization initiator is contained in an amount of 4.0% by mass or more based on the total solid content of the photosensitive resin composition.

[17] The (D) polymerization inhibitor is a thermal polymerization inhibitor further containing a nitrogen atom, (D ３

[18] A photosensitive resin composition according to any one of items 1 to 16, wherein the (C) polymerization initiator contains at least one of a hexaarylbiimidazole compound or an acridine compound, and the ratio of the content of the (D) polymerization inhibitor to the (C) polymerization initiator is in the range of 1:50 to 1:1500, according to any one of items 1 to 17.

[19] A photosensitive resin composition according to any one of items 1 to 18, wherein the (B) compound having an ethylenically unsaturated bond contains a compound having a bisphenol A skeleton.

[20] A photosensitive resin composition according to any one of items 1 to 19, wherein the (A) alkali-soluble polymer contains constituent units derived from the following components: (a-1) (meth)acrylic acid; and (a-2) compounds having aromatic hydrocarbon groups.

[21] The photosensitive resin composition according to any one of items 1 to 20, wherein the alkali-soluble polymer (A) contains constituent units derived from the following components: (a-1) (meth)acrylic acid; (a-2) compounds having aromatic hydrocarbon groups; and (a-3) hydroxyalkyl (meth)acrylate.

[22] The polymerization inhibitor (D) is at least one compound selected from the group consisting of a compound represented by formula (1) having a MolLogP greater than 2.35; phenothiazine; phenothiazine derivatives; phenoxazine; and phenoxazine derivatives. ４ ) A photosensitive resin composition according to any one of items 3 to 8, 11 to 14, further comprising the compound.

[23] The (D) polymerization inhibitor, the (D １ ) compound, or the (D ２ ) The total content d1 (mass%) of the compound and the (D ４ ) A photosensitive resin composition according to item 22, wherein the ratio d1:d2 of the total compound content d2 (mass%) is in the range of 5:1 to 1:5.

[24] A photosensitive resin laminate comprising a temporary support layer and a photosensitive resin layer made of the photosensitive resin composition according to any one of items 1 to 23.

[25] A photosensitive resin laminate according to item 24, further comprising a protective layer.

[26] A method for forming a resist pattern using the photosensitive resin laminate according to item 24.

[0011] According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive resin laminate, a method for forming a resist pattern, and a method for manufacturing a conductor pattern that maintain high resolution, high adhesion, and high sensitivity.

[0012] A plan view showing the configuration of the drawing pattern related to this embodiment. A plan view showing the configuration of the drawing pattern related to this embodiment. A plan view showing the configuration of the drawing pattern related to this embodiment.

[0013] Embodiments of this disclosure will be described below. This disclosure is not limited to these embodiments and can be implemented in various ways within the scope of its gist.

[0014] In this specification, if there are multiple structures represented by the same reference numeral in the same formula, unless otherwise specified, each structure may be selected independently and may be identical or different from one another. Similarly, if there are multiple structures represented by the same reference numeral in different formulas, unless otherwise specified, each structure may be selected independently and may be identical or different from one another.

[0015] Furthermore, in this specification, the upper or lower limits in the stepped numerical ranges may be replaced with the upper or lower limits in the corresponding other stepped numerical ranges, and may also be replaced with the corresponding values ​​described in the examples.

[0016] Furthermore, in this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic," "(meth)acrylate" means "acrylate" and / or "methacrylate," and "(meth)acryloyl" means "acryloyl" and / or "methacryloyl." A "(meth)acryloyl group compound" is referred to, for example, as a "(meth)acrylate compound."

[0017] Furthermore, within this specification, the term "process" is included not only in the case of an independent process, but also in cases where it cannot be clearly distinguished from other processes, as long as the function of that process is achieved. In the drawings, the scale, shape, and length may be exaggerated for the sake of clarity.

[0018] Furthermore, in this specification, "solids" in a photosensitive resin composition refers to the components of the photosensitive resin composition other than the solvent. The measurement methods for the physical properties and parameters described herein refer to the methods described in the examples.

[0019] Furthermore, unless otherwise specified in this specification, "adhesion" refers to the adhesion performance of the resist pattern to the substrate; "resolution" refers to the resolution performance of the resist pattern; "developability" also refers to the developability of the photosensitive resin layer (resist); and "sensitivity" refers to the exposure sensitivity of the photosensitive resin layer (resist).

[0020] [First Embodiment] [Photosensitive Resin Composition] In one embodiment, the photosensitive resin composition of the present disclosure comprises the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor. Furthermore, the (D) polymerization inhibitor contains, in an amount of 0.002 to 0.3% by mass of the total solid content of the photosensitive resin composition, a compound having an aromatic ring in which two or more hydrogen atoms are substituted with a group represented by XH (wherein X is at least one selected from O, NH, and NR', and R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms), and having a MolLogP of 2.35 or less.

[0021] In this disclosure, the above-mentioned (A) alkali-soluble polymer, etc., is described as "component (A)," etc. Optionally, the photosensitive resin composition may further contain components other than components (A) to (D), such as (E) a hydrogen donor, antioxidant, stabilizer, base dye, sensitizer, and solvent, and each component and / or the raw material for each component may be used alone or in combination of two or more.

[0022] The photosensitive resin composition of this disclosure contains the above compound in an amount of 0.002 to 0.3% by mass relative to the total solid content of the photosensitive resin composition. As a result, the photosensitive resin composition of this disclosure maintains high resolution while exhibiting high adhesion and high exposure sensitivity. The inventors speculate on the reason for this as follows.

[0023] This disclosure reveals that the above-mentioned compound having an aromatic ring in which two or more hydrogen atoms are substituted with a group represented by XH has a higher number of alkyl radicals captured per molecule compared to existing polymerization inhibitors which are aromatic compounds in which one hydrogen atom is substituted, and therefore can suppress the progress of excessive polymerization reactions. At the same time, by adjusting the MolLogP value to a suitable range, it is possible to significantly obtain the effect as a polymerization inhibitor.

[0024] In this disclosure, MolLogP is a calculated value of the octanol / water partition coefficient (LogP) obtained by classifying each atom in a molecule into a predetermined atomic type according to the atomic contribution method proposed by Wildman et al., and then adding the contribution values ​​of each atomic type according to the number of atoms. In more detail: "Wildman SA; Crippen. GMJ Chem. Inf. Comput. Sci. 1999, 39, 5, 868-873"; "Broto, P. et al., Eur. J. Med. Chem. 1984, 19, 71."; "Ghose, AK; Crippen, GMJ Comput. Chem. 1986, 4, 565."; "Ghose, A. K.; Crippen, GMJ Chem. Inf. Comput. Sci. 1987, 27, 21."; "Ghose, A K. et al., J. Comput. Chem. 1988, 9, 80."; "Viswanadhan, V. et al., J. Chem. Inf. Comput. Sci. 1989, 29, This is an index value indicating lipophilicity calculated using the calculation method shown in "163-172." and "Ghose, AK et al., J. Phys. Chem. B 1998, 102, 3762.". The higher the MolLogP value, the more easily it blends in organic solvents. On the other hand, polymerization inhibitors with excessively high MolLogP values ​​do not diffuse adequately in the solvent and have low compatibility with components (A) and (B) contained in the photosensitive resin composition, meaning they do not diffuse sufficiently into the photosensitive resin composition. If the polymerization inhibitor does not diffuse sufficiently into the photosensitive resin composition, it is thought that it will not adequately capture excess radicals in the polymerization reaction. In other words, the photosensitive resin composition of this disclosure contains 0.002 to 0.3% by mass of the above compound in component (D), which has an aromatic ring in which two or more hydrogen atoms are substituted with a group represented by XH, and has a MolLogP of 2.35 or less. This allows the compound to be sufficiently diffused into the photosensitive resin composition as a polymerization inhibitor and to obtain an inhibitory effect on polymerization reactions by capturing excess alkyl radicals.

[0025] (A) Component: Alkali-soluble polymer Component (A) is a binder polymer obtained by copolymerizing monomers having ethylenically unsaturated bonds, which are one or more constituent units as described below.

[0026] (A) Component (A) preferably has a carboxyl group from the viewpoint of exhibiting suitable alkali solubility.

[0027] (A) The acid value of component (A) is preferably 200 mg KOH / g or less, from the viewpoint of suppressing swelling in the developing process of the photosensitive resin composition or photosensitive resin laminate and further improving adhesion.

[0028] The acid value can be calculated by accurately weighing approximately 1 g of the sample, dissolving it in 100 mL of acetone, and then performing a neutralization titration with a 1 mol / L potassium hydroxide solution. The acid value (mgKOH / g) is then calculated based on the volume of potassium hydroxide solution added using the following formula: Acid value (mgKOH / g) = 56.1 × {Volume of 1 mol / L potassium hydroxide solution added (mL)} / {Mass of accurately weighed sample (g)}. The neutralization titration can be performed, for example, using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

[0029] The lower limit of the acid value of component (A) is not limited, but based on the calculation method described above, it may be greater than 0 mg KOH / g, or 50 mg KOH / g or more, 60 mg KOH / g or more, 80 mg KOH / g or more, etc. The acid value of component (A) is controlled by the content of compounds having an acid group among the compounds (a-1) to (a-4) described below.

[0030] Component (A) is preferably composed of multiple types of constituent units from the viewpoint of achieving both high adhesion and high resolution, more preferably having constituent units derived from (a-1) and (a-2) below, and even more preferably having all constituent units derived from (a-1) to (a-3) below: (a-1) (meth)acrylic acid; (a-2) compounds having aromatic hydrocarbon groups; and (a-3) hydroxyalkyl (meth)acrylate. Component (A) may further contain component (a-4) described later.

[0031] The above compound (a-1) is (meth)acrylic acid. From the viewpoint of achieving both high adhesion and high resolution, the content of the constituent units derived from (a-1) is preferably 10 to 30% by mass, and more preferably 20 to 27% by mass, relative to the total mass of component (A).

[0032] Examples of the above (a-2) compound include styrene and / or styrene derivatives, benzyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, and 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate. Examples of styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer. In particular, from the viewpoint of easily achieving the effects of this disclosure or being suitable for forming a conductive pattern, the above (A) component preferably contains benzyl (meth)acrylate and / or styrene as the (a-2) compound, and more preferably contains styrene. From the viewpoint of achieving both high adhesion and high resolution, the content of the constituent units derived from above (a-2) is preferably 20 to 80% by mass, and more preferably 35 to 80% by mass, relative to the total mass of component (A). When component (A) contains styrene as compound (a-2), it is preferable that the content of constituent units derived from styrene is 35% by mass or more relative to the total mass of component (A).

[0033] The above (a-3) compound is a hydroxyalkyl (meth)acrylate. From the viewpoint of achieving both high adhesion and high resolution, the content of the constituent units derived from (a-3) is preferably 1 to 40% by mass, and more preferably 4 to 35% by mass, relative to the total mass of component (A).

[0034] Examples of the above (a-4) compounds include compounds having acid groups such as fumaric acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semi-ester, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, iso Examples include bornyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, vinyl alcohol esters (e.g., vinyl acetate), (meth)acrylonitrile, etc. The content of the constituent units derived from the above (a-4) compounds may be 0 to 20% by mass relative to the total mass of component (A).

[0035] If the above component (A) contains multiple types of binder polymers, the proportion of each constituent unit means the weighted average of the copolymerization ratios of each constituent unit, weighted by the content ratio of each binder polymer. Similarly, each value described for component (A) (e.g., weight-average molecular weight, polydispersity, etc.) also means the weighted average of the content ratio of each binder polymer.

[0036] The weight-average molecular weight (Mw) of component (A) is preferably 5,000 to 600,000, more preferably 10,000 to 200,000, even more preferably 10,000 to 100,000, and particularly preferably 15,000 to 55,000. A weight-average molecular weight (Mw) of component (A) of 5,000 or more makes it easier to maintain a uniform thickness of the photosensitive resin laminate and to ensure resistance to developing solutions. A weight-average molecular weight (Mw) of component (A) of 600,000 or less makes it easier to ensure flexibility and developability of the photosensitive resin laminate. Furthermore, from the viewpoint of improving resolution, the weight-average molecular weight (Mw) of component (A) is preferably 10,000 to 35,000, and more preferably 15,000 to 25,000.

[0037] The polydispersity of component (A) {weight-average molecular weight of component (A) (Mw) / number-average molecular weight of component (A) (Mn)} is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0038] (A) The content of component (A) is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 5 to 60% by mass, relative to the solid content of the photosensitive resin composition. When the content of component (A) is 1% by mass or more, excellent adhesion and fine line strength are easily achieved. When the content of component (A) is 80% by mass or less, resistance to developing solutions is easily ensured.

[0039] <Synthesis of Component (A)> Component (A) can be synthesized by diluting monomers, which are one or more constituent units as described above, with a solvent such as acetone, methyl ethyl ketone, and isopropanol, mixing appropriate amounts of radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile into the solution, and then heating and stirring. In some cases, component (A) can be synthesized by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust to the desired concentration. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods. Furthermore, synthesis may be carried out by living radical polymerization.

[0040] (B) Component: Photopolymerizable compound having an ethylenically unsaturated bond Component (B) is a photopolymerizable compound having an ethylenically unsaturated bond, for example, a compound having one or more ethylenically unsaturated bonds in one molecule. Component (B) may contain multiple different compounds. Furthermore, from the viewpoint of adhesion and resolution, component (B) preferably contains a compound having a bisphenol A skeleton.

[0041] The ethylenically unsaturated bond in component (B) functions as a photopolymerizable bond. The compound having such an ethylenically unsaturated bond may be a compound containing a photopolymerizable functional group, for example, a compound containing a (meth)acryloyl group.

[0042] Regarding component (B), having "n" photopolymerizable functional groups in one molecule is sometimes referred to as "n-functional." For example, a compound having n (meth)acryloyl groups is sometimes referred to as an n-functional (meth)acrylate compound. For example, with respect to component (B), having one, two, three, four, five, or six photopolymerizable functional groups in one molecule is sometimes referred to as "monofunctional (or monofunctional)," "difunctional," "trifunctional," "tetrafunctional," "pentafunctional," or "hexafunctional," respectively.

[0043] Examples of bifunctional (meth)acrylate compounds include alkyl di(meth)acrylates, 1,3-bis(meth)acryloyloxy-2-propanol, polyalkylene glycol di(meth)acrylates, tricyclodecanol di(meth)acrylates, ethoxylated (hydrogenated) bisphenol A di(meth)acrylates, propoxylated (hydrogenated) bisphenol A di(meth)acrylates, and tetramethylene glycoxified (hydrogenated) bisphenol A di(meth)acrylates.

[0044] Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, polypropylene di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. Furthermore, the polyalkylene glycol di(meth)acrylate may be a compound having multiple alkylene groups, consisting of ethylene groups, propylene groups, and tetramethylene groups. Examples of such compounds include a polyalkylene glycol di(meth)acrylate obtained by adding an average of three ethylene oxides to each end of a polypropylene glycol containing an average of 12 propion oxides; and a di(meth)acrylate obtained by adding an average of six propylene oxides to each end of six ethylene oxides.

[0045] In this specification, the average number of alkylene oxides such as ethylene oxide and propylene oxide can be understood to be determined by number averaging, and for reference, catalog values ​​can be referred to within a range that does not deviate from the above values.

[0046] Furthermore, as a bifunctional (meth)acrylate compound, the following general formula (I): (In the formula, R １ Each is independently a hydrogen atom or a methyl group, and X １ O and Y １ Compounds having a bisphenol A skeleton, represented as follows: O is independently an oxyethylene group or an oxypropylene group, m1, m2, n1 and n2 are independently integers from 0 to 40, m1 + m2 is from 1 to 40, and n1 + n2 is from 0 to 20.

[0047] Furthermore, examples of bifunctional (meth)acrylate compounds include: di(meth)acrylates of polyalkylene glycols obtained by adding an average of 2 propylene oxides to each end of bisphenol A, which has an average of 6 ethylene oxides at each end; di(meth)acrylates of polyalkylene glycols obtained by adding an average of 4 propylene oxides to each end of bisphenol A, which has an average of 2 ethylene oxides at each end; di(meth)acrylates of polyalkylene glycols obtained by adding an average of 2 propylene oxides to each end of bisphenol A, which has an average of 4 ethylene oxides at each end; di(meth)acrylates of polyethylene glycols obtained by adding an average of 5 ethylene oxides to each end of bisphenol A; and di(meth)acrylates of polyethylene glycols obtained by adding an average of 5 ethylene oxides to each end of 9,9-bis(4-hydroxyphenyl)fluorene. Examples include polyethylene glycol di(meth)acrylate obtained by adding an average of two ethylene oxide groups to each end of bisphenol A; polyethylene glycol di(meth)acrylate obtained by adding an average of one ethylene oxide group to each end of bisphenol A; and so on.

[0048] Examples of trifunctional or more (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin penta(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0049] Furthermore, examples of trifunctional or more (meth)acrylate compounds include compounds obtained by forming a (meth)acrylate from an alcohol having three or more groups in which alkylene oxide groups can be added as a central skeleton, to which alkylene oxide groups such as ethylene oxide groups, propylene oxide groups, or butylene oxide groups are added, and (meth)acrylic acid. Examples of such compounds include trimethylolpropane alkylene oxide-modified tri(meth)acrylate, glycerin alkylene oxide-modified tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, alkylene oxide-modified diglycerin tetra(meth)acrylate, alkylene oxide-modified triglycerin penta(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified isocyanuric acid tri(meth)acrylate. The alkylene oxide group is preferably an ethylene oxide group, a propylene oxide group, or a butylene oxide group.

[0050] As a trifunctional or more (meth)acrylate compound, from the viewpoint of excellent developability, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate and / or alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate may be included.

[0051] An example of a (meth)acrylate compound with three or more functions is a compound with a polyglycerin backbone, as shown in the general formula (VI): {In the formula, k, l, and m are each an integer between 0 and 30, and n is an integer between 2 and 20, R １ , R ２ , and R ３ Each of these independently represents either a hydrogen atom or a methyl group, and R ４ , R ５ , and R ６Each of these is an alkylene group having 1 to 10 carbon atoms, as shown in formula (VII): [In the formula, R ７ and R ８ Each of these is an alkylene group having 1 to 10 carbon atoms. The group represented by ] and the following formula (VIII): [In the formula, R ９ This is an alkylene group having 1 to 10 carbon atoms. It is one selected from the group consisting of groups represented by ]. Examples of compounds represented by} include

[0052] An example of a trifunctional (meth)acrylate compound is the following general formula (II), which has a trimethylolpropane backbone: {In the formula, n １ , n ２ , and n ３ Each of these is an integer between 1 and 25, where n is independent. １ +n ２ +n ３ R is an integer between 3 and 75. １ , R ２ , and R ３ Each of these is independently either a methyl group or a hydrogen atom. Examples of compounds represented by} include:

[0053] Furthermore, an example of a trifunctional (meth)acrylate compound is the following general formula (III), which has glycerin as its backbone: Examples of compounds represented by the formula {wherein Y independently represents an alkylene group, R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 200} include:

[0054] An example of a tetrafunctional (meth)acrylate compound is one with a pentaerythritol backbone, as shown in the general formula (IV): {In the formula, n １ , n ２ , n ３ , and n ４ Each of these independently represents an integer from 1 to 25, and n １ +n ２ +n ３ +n ４ is an integer between 4 and 100, and R １ , R ２, R ３ , and R ４ Each of these independently represents a methyl group or a hydrogen atom, R ５ , R ６ , R ７ , and R ８ Each of these independently represents an alkylene group, R ５ , R ６ , R ７ , and R ８ If there are multiple instances of each, then the multiple R ５ , R ６ , R ７ , and R ８ Compounds represented by} may be identical or different from each other.

[0055] An example of a hexafunctional (meth)acrylate compound is the following general formula (V), which has dipentaerythritol as its backbone: Examples of compounds represented by {wherein R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 30} include compounds represented by the formula (V). In general formula (V), n may be 0, that is, the ethylene oxide moiety may not be present.

[0056] Examples of (B) components with three or more functionalities that can be specifically used include: tri(meth)acrylate obtained by adding an average of 21 ethylene oxide units to trimethylolpropane; tetra(meth)acrylate obtained by adding an average of 9 ethylene oxide units to pentaerythritol; tetra(meth)acrylate obtained by adding an average of 9 ethylene oxide units to diglycerin; polyethylene glycol hexa(meth)acrylate obtained by adding 13 ethylene oxide units to dipentaerythritol; hexa(meth)acrylate obtained by adding an average of 21 ethylene oxide units to tetraglycerin; and so on. The abbreviations "EO" and "PO" mean ethylene oxide and propionate oxide, respectively.

[0057] From the viewpoint of adhesion and resolution, component (B) preferably contains a photopolymerizable compound containing an aromatic ring. The content of the photopolymerizable compound containing an aromatic ring is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more, based on the total amount of component (B).

[0058] From the viewpoint of further improving adhesion, it is preferable that the content of a compound having four or more (meth)acryloyl groups in one molecule of component (B) is 40% by mass or more; it is preferable that component (B) contains a compound having five or more (meth)acryloyl groups in one molecule.

[0059] (B) The content of component (B) is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the solid content of the photosensitive resin composition, from the viewpoint of excellent sensitivity and conformability.

[0060] (Content of various components) From the viewpoint of easily achieving the effects of this disclosure, or from the viewpoint of suitability for forming a conductive pattern, the total content of component (A) and component (B) in the photosensitive resin composition is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the solid content of the photosensitive resin composition.

[0061] (C) Component: Polymerization initiator Component (C) is a polymerization initiator. The polymerization initiator generates radicals in response to active light emitted from the exposure light source, thereby promoting the polymerization of compounds having ethylenically unsaturated bonds.

[0062] The content of component (C) is preferably 4.0% by mass or more based on the total mass of the photosensitive resin composition. This makes it easier to obtain sufficient sensitivity, so that light can be sufficiently transmitted to the bottom of the photosensitive resin layer even with a small amount of exposure, and consequently, good resolution and adhesion can be easily achieved. The content of component (C) may be 30% by mass or less, or 20% by mass or less, based on the solid content of the photosensitive resin composition.

[0063] Examples of component (C) include biimidazole compounds such as hexaarylbiimidazole compounds and dimers of 2,4,5-triarylimidazole, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, and acridine compounds, as well as ester compounds of N-aryl amino acids and halogen compounds. Component (C) preferably contains at least one of a hexaarylbiimidazole compound or an acridine compound. This is because the presence of a heteroaromatic ring gives it a relatively long radical lifetime, making it easier to control polymerization reactions as an initiator.

[0064] Biimidazole compounds are compounds having a biimidazole structure, and hexaarylbiimidazole compounds are preferred. Examples of hexaarylbiimidazole compounds include rofin dimers, i.e., dimers of 2,4,5-triarylimidazole.

[0065] Dimers of 2,4,5-triarylimidazole include the dimer of 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), the dimer of 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole, the dimer of 2-(p-methoxyphenyl)-4,5-diphenylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl Nylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methylphenyl) Toxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3 -Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,Examples include 5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.

[0066] From the viewpoint of high sensitivity, resolution, and adhesion, it is preferable that component (C) contains a hexaarylbiimidazole compound, more preferably a rofin dimer, and even more preferably a dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole.

[0067] When component (C) contains a hexaarylbiimidazole compound, the content of the hexaarylbiimidazole compound may be 4.0% by mass or more, preferably 5.0% by mass or more, more preferably 5.3% by mass or more, and even more preferably 5.5% by mass or more, based on the total solid content of the photosensitive resin composition. When component (C) contains a hexaarylbiimidazole compound, the content of the hexaarylbiimidazole compound may be 10.0% by mass or less, based on the total solid content of the photosensitive resin composition.

[0068] (C) When component contains an acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred as the acridine compound in terms of sensitivity and resolution.

[0069] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

[0070] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0071] Examples of aromatic ketone compounds include benzophenone. Dialkylbenzophenone falls under the category of "other sensitizers" in (E) sensitizers, which will be discussed later.

[0072] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by BASF: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0073] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available acylphosphine oxide compounds include Lucilin TPO (manufactured by BASF) and Irgacure-819 (manufactured by BASF).

[0074] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

[0075] Examples of dialkylketal compounds include benzyldimethylketal and benzyldiethylketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorthioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0076] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by BASF).

[0077] Examples of ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0078] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diallylodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0079] (D) Component: Polymerization inhibitor The photosensitive resin composition of this disclosure contains the above compound as component (D) as a polymerization inhibitor. In this disclosure, by including the above compound, the polymerization inhibitor present near the exposed and unexposed areas suppresses the reaction in the unexposed area, contributing to the provision of a photosensitive resin composition with high adhesion and high sensitivity while maintaining high resolution.

[0080] Preferred embodiments of component (D) are described below. The following preferred embodiments may be combined.

[0081] Component (D) preferably contains a phenol inhibitor having at least one hydroxyl group. That is, at least one of the two or more XH groups in the compound is a hydroxyl group. The hydroxyl group may be a phenolic hydroxyl group.

[0082] Component (D) in this disclosure is preferably represented by the following formula (1), wherein MolLogP is 2.35 or less (D １ The compound is contained in an amount of 0.002 to 0.3% by mass relative to the total solid content of the photosensitive resin composition. {In formula (1), X is at least one selected from O, NH, and NR', R represents at least one selected from the group consisting of a halogen atom; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a carboxyl group; or an alkyl group having 1 to 10 carbon atoms, R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms, a represents an integer of 1 or more, b represents an integer of 0 or more, and the sum of a and b is an integer between 2 and 5.}

[0083] Polymerization inhibitors containing an appropriate amount of a phenol compound having one or more XH groups in formula (1), or having two or more XH groups, are considered to have an advantage in adjusting the radicals suitable for polymerization reactions because they capture a larger number of alkyl radicals per molecule compared to existing monovalent phenol inhibitors, and are more efficient at capturing excess radicals for the required polymerization reaction.

[0084] Component (D) in the photosensitive resin composition of the present disclosure is preferably a compound represented by the above formula (1), wherein a in formula (1) is an integer of 2 or more (hereinafter referred to as (D) ２ The photosensitive resin composition contains 0.002 to 0.3% by mass of a compound (referred to as a compound) relative to the total solid content.

[0085] The above (D ２ A polymerization inhibitor containing an appropriate amount of the compound (D) is considered to have a higher number of alkyl radicals captured per molecule compared to existing phenol inhibitors, making it easier to capture excess radicals for the required polymerization reaction and thus advantageous in adjusting the radicals suitable for the polymerization reaction. Therefore, the above (D) ２ A photosensitive resin composition containing an appropriate amount of the compound exhibits improved adhesion and exposure sensitivity compared to existing photosensitive resin compositions, while maintaining high resolution.

[0086] In the above component (D), it is preferable that it be hydrophobic from the viewpoint of the diffusibility of the polymerization inhibitor, and therefore, MolLogP is 0 or greater. More preferably, the lower limit of MolLogP may be greater than 0, 0.1 or greater, or 0.5 or greater, and the upper limit is 2.3 or less, 2.2 or less, 2.1 or less, or 2.0 or less.

[0087] The value of a in formula (1) above is an integer of 1 or more, preferably an integer of 2 or more from the viewpoint of suitably capturing alkyl radicals, and more preferably 2. The functional group XH containing X in formula (1) above may be substituted at the ortho position and / or the para position.

[0088] In the above component (D), from the viewpoint of adjusting MolLogP to a suitable range and improving the diffusibility of the polymerization inhibitor, it is preferable to include a compound in formula (1) where the value of b is an integer of 1 or more.

[0089] From the viewpoint of suitably capturing alkyl radicals in component (D) above, it is preferable that the compound has a functional group in which X in formula (1) is represented by an oxygen atom (O), and / or a functional group in which R in formula (1) is represented by a carboxyl group. Compounds having the above functional groups are more advantageous in capturing radicals and contribute to improved adhesion.

[0090] In the above (D) component, １ Preferably, the compounds include, for example, the following: pyrogallol; 4-methylpyrogallol; 4-tert-butylpyrogallol; gallic acid; propyl gallate; 4-bromocatechol; 4-acetocatechol; methyl 3,4-dihydroxybenzoate; methylhydroquinone; chlorohydroquinone; and 4-amino-2-chlorophenol. These can be used individually or in combination of two or more.

[0091] In the above (D) component, １ The compound content is in the range of 0.002 to 0.3% by mass, preferably in the range of 0.003 to 0.2% by mass, relative to the total solid content of the photosensitive resin composition.

[0092] In the above (D) component,２ The compounds preferably include compounds having a skeleton derived from pyrogallol or gallic acid, and preferably include, for example, the following compounds: pyrogallol; 4-methylpyrogallol; 4-tert-butylpyrogallol; gallic acid; propyl gallate. These can be used individually or in combination of two or more.

[0093] In the above (D) component, ２ The compound content is in the range of 0.002 to 0.3% by mass, preferably in the range of 0.003 to 0.2% by mass, relative to the total solid content of the photosensitive resin composition.

[0094] From the viewpoint of improving adhesion, it is more preferable that component (D) above contains at least one compound selected from pyrogallol; 4-methylpyrogallol; 4-tert-butylpyrogallol; gallic acid; propyl gallate.

[0095] In the above component (D), preferably, from the viewpoint of thermal stability, it is a thermal polymerization inhibitor having a nitrogen atom (D ３ ) further contains the above (D ３ Examples of such compounds include nitroso compounds, nitrosamines, amines, nitrogen radical compounds, and piperidyl methacrylate.

[0096] The above (D ３Among the compounds, nitroso compounds include 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, N,N-diethyl-N-nitrosoaniline, and 5-nitroso-8-quinolinol; nitrosamines include N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodipropylamine, N-nitrosodibutylamine, N-nitrosodiethanolamine, N-nitrosodiisopropanolamine, N-nitroso-N-methylaniline, N-nitrosodiphenylamine, and nitrosophenylhydroxyamine aluminum salts (e.g., aluminum salts with 3 moles of nitrosophenylhydroxylamine added, N-nitroso-N-phenylhydroxylamine ammonium salt, etc.); amines include N-1-methylheptyl-N'-phenyl-p-phenylenediamine and N-isopropyl-N'-phenyl-p-phenylenediamine; Examples of nitrogen radical compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl benzoate free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-(2-chloroacetamide)-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical; Examples of piperidyl methacrylates include 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate.

[0097] In the above component (D), from the viewpoint of further improving resolution, a compound comprising at least one selected from the group consisting of a compound represented by the above formula (1) and having a MolLogP greater than 2.35; phenothiazine; phenothiazine derivatives; phenoxazine; and phenoxazine derivatives (hereinafter referred to as (D) ４Preferably, the above (D) component contains the above (D １ ) compound, or the above (D ２ ) Total compound content d1 (mass%) and (D ４ ) The ratio d1:d2 of the total compound content d2 (mass%) is in the range of 5:1 to 1:5 (D ４ ) contains the above (D ４ Component (D), which contains an appropriate amount of the compound, contributes to further improving the resolution of the photosensitive resin composition.

[0098] Examples of compounds represented by the above formula (1) and having a MolLogP of greater than 2.35 include tert-butylcatechol.

[0099] (D) component, (D ４ In addition to the compounds mentioned above, the following compounds may also be included: For example, p-methoxyphenol, hydroquinone, naphthylamine, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], etc. These can be used individually or in combination of two or more.

[0100] The content of component (D) is preferably in the range of 0.002 to 0.3% by mass relative to the total solid content of the photosensitive resin composition. Furthermore, from the viewpoint of improving sensitivity and adhesion, the mass ratio of the content of component (D) to component (C) (total mass including the sensitizer if one is included) is preferably in the range of 1:50 to 1:1500. The effect of improving sensitivity and adhesion when the mass ratio of the content of component (D) to component (C) (total mass including the sensitizer if one is included) is in the range of 1:50 to 1:1500 is more pronounced when at least one of a hexaarylbiimidazole compound or an acridine compound is included as the polymerization initiator (C). The reason for this is not clear, but since hexaarylbiimidazole compounds and acridine compounds have heteroaromatic rings, it is presumed that their MolLogP values ​​are similar to those of component (D) having the configuration of this disclosure, and that their diffusion behavior in the photosensitive resin composition is similar. Therefore, with respect to the heteroaromatic ring radicals that are generated, component (D) having the configuration of this disclosure is within the above range relative to the polymerization initiator, making it easier to suitably capture excess heteroaromatic ring radicals and act suitably as a polymerization inhibitor.

[0101] (E) Components: The photosensitive resin composition may optionally contain other components (hydrogen donors, base dyes, sensitizers, antioxidants, stabilizers, plasticizers, solvents, etc.).

[0102] While this disclosure does not wish to be bound by theory, it has been found that the combined use of component (C) and a hydrogen donor is involved in the hydrogen abstraction reaction from the hydrogen donor by the radical of the polymerization initiator, and that improvements in sensitivity and crosslink density can be expected by controlling the reaction rate.

[0103] The mass ratio of the hydrogen donor component content to the (C) component content (i.e., the mass of hydrogen donor content / the mass of (C) polymerization initiator content) is preferably 0.07 or higher, more preferably 0.09 or higher, and even more preferably 0.13 or higher, from the viewpoint of improving sensitivity and crosslinking density. The effect of the photosensitive resin laminate of this disclosure is not intended to be constrained by theory, but as described above, it is thought to be due to increasing the rate of hydrogen abstraction reaction from the hydrogen donor by the radicals of the polymerization initiator. Therefore, increasing the amount of hydrogen donor increases the initial concentration of the reaction, improves reactivity, and consequently improves sensitivity and crosslinking density. Accordingly, it was found that the degree of improvement in effect correlates more with controlling the mass ratio (mass of hydrogen donor content / mass of (C) polymerization initiator content) than with controlling the content of the hydrogen donor component alone. The mass ratio of the hydrogen donor component content to the (C) component content (i.e., the mass of the hydrogen donor / the mass of the (C) polymerization initiator) may be, for example, 0.50 or less.

[0104] The hydrogen donor is not particularly limited, but for example, leucocrystal violet may be used.

[0105] Examples of base dyes include Basic Green 1 [CAS number (same below): 633-03-4] (e.g., Aizen Diamond Green GH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Malachite Green [CAS number 569-64-2], Tris(4-dimethylamino-2-methylphenyl)methane [Leucomalachite Green], Fuchsine [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue) Examples include BOH (trade name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc. Among these, Basic Green 1 is preferred from the viewpoint of improving colorability, hue stability, and exposure contrast. These can be used individually or in combination of two or more.

[0106] The base dye content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and even more preferably 0.01 to 0.1% by mass. From the viewpoint of obtaining good colorability, the base dye content is preferably above the lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive layer, it is preferably below the upper limit.

[0107] As a sensitizer, sensitizing compounds other than the above-mentioned component (C) may be used, such as anthracene compounds, triarylamine compounds, dialkylbenzophenone compounds, oxazole compounds, pyrazoline compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, and coumarin derivatives. Among these, dialkylbenzophenone compounds, pyrazoline compounds, anthracene compounds, and coumarin derivatives are preferred.

[0108] Examples of anthracene compounds include anthracene and anthracene derivatives, of which anthracene derivatives include, for example, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and 10-phenyl-9-anthraceneboronic acid. Among these, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid are preferred from the viewpoint of sensitizing effect.

[0109] Examples of triarylamine compounds include compounds having a triphenylamine skeleton, and specifically, for example, triphenylamine.

[0110] Examples of dialkylbenzophenone compounds include Michlaz ketone [4,4'-bis(dimethylamino)benzophenone], 4-methoxy-4'-dimethylaminobenzophenone, and 4,4'-bis(diethylamino)benzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of sensitizing effect.

[0111] Examples of oxazole compounds include oxazolone (2-phenyl-4-ethoxymethyleneoxazole-5(4H)-one).

[0112] Examples of pyrazoline compounds include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is preferred from the viewpoint of sensitizing effect.

[0113] The coumarin derivative can be any compound having a coumarin skeleton, such as 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinoridine-11-one (also known as "coumarin 102").

[0114] From the viewpoint of sensitivity, the sensitizer content is preferably 0.01 to 0.6% by mass (e.g., 0.01 to 0.60% by mass), more preferably 0.1 to 0.6% by mass (e.g., 0.10 to 0.60% by mass), and even more preferably 0.1 to 0.4% by mass (e.g., 0.10 to 0.40% by mass), relative to the solid content of the photosensitive resin composition. In addition, one or more of these selected sensitizers may be used.

[0115] Examples of antioxidants include triphenyl phosphite (e.g., manufactured by ADEKA, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA, trade name: 2112), tris(mononylphenyl) phosphite (e.g., manufactured by ADEKA, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA, trade name: 329K). These can be used individually or in combination of two or more.

[0116] The antioxidant content is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, relative to the total solid content mass of the photosensitive resin composition. From the viewpoint of exhibiting good hue stability of the resist pattern and improving the sensitivity of the photosensitive layer, the antioxidant content is preferably above the lower limit. On the other hand, from the viewpoint of exhibiting good hue stability while suppressing the color development of the resist pattern and improving adhesion, it is preferably below the upper limit.

[0117] Stabilizers can be used to improve the thermal stability of the photosensitive resin composition. Examples of stabilizers include at least one alkylene oxide compound having a glycidyl group and a benzotriazole compound. These can be used individually or in combination of two or more.

[0118] Examples of plasticizers include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether; phthalate esters of diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, etc.

[0119] The plasticizer content is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, relative to the solid content of the photosensitive resin composition. When this percentage is 1% by mass or more, it is easier to suppress delays in development time and to impart flexibility to the cured film. When this percentage is 50% by mass or less, it tends to suppress insufficient curing and edge fusing.

[0120] (Solvent) The photosensitive resin layer is formed by applying a coating solution, in which the photosensitive resin composition is dispersed in a solvent, to a temporary support layer or to any intermediate layer applied to the temporary support layer, and then drying it. The resulting photosensitive resin layer may contain residual solvent.

[0121] Examples of solvents include ketones, such as methyl ethyl ketone; alcohols, such as methanol, ethanol, and isopropanol; and toluene. Acetone is also an example of a solvent. The solvent content remaining in the photosensitive resin layer is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less, relative to the solid content of the photosensitive resin composition.

[0122] [Second Embodiment] [Photosensitive Resin Composition] The photosensitive resin composition according to the second embodiment contains components (A) to (C) described in the first embodiment. In addition, as (D) polymerization inhibitor, the photosensitive resin composition contains 0.002 to 0.3% by mass of a compound having an aromatic ring in which three or more hydrogen atoms are substituted with a group represented by XH (wherein X is at least one selected from O, NH, and NR', and R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms) with respect to the total solid content of the photosensitive resin composition.

[0123] The photosensitive resin composition according to this disclosure contains, as component (D), a compound having an aromatic ring in which three or more hydrogen atoms are substituted with a group represented by XH, within the range of the above values, thereby improving the number of alkyl radicals captured per molecule and the diffusivity of the polymerization inhibitor in the photosensitive resin composition. Therefore, it is possible to obtain an inhibitory effect on polymerization reactions by capturing excess alkyl radicals, and as a result, high adhesion and high exposure sensitivity are achieved while maintaining the high resolution of the resulting photosensitive resin composition. Furthermore, in the polymerization inhibitor having the above configuration, the aromatic ring functions as a hydrophobic part and the group represented by XH functions as a hydrophilic part, making it easy to adjust the MolLogP value described in the first embodiment to a suitable range.

[0124] The features and preferred embodiments of the first and second embodiments described above may be combined or interchangeable. Furthermore, common configurations and preferred configurations of the first and second embodiments are described below.

[0125] [Photosensitive resin laminate] The photosensitive resin laminate of the present disclosure comprises a temporary support layer and a photosensitive resin layer containing the photosensitive resin composition described above, wherein the photosensitive resin composition contains the following components: (A) binder polymer; (B) photopolymerizable compound having an ethylenically unsaturated bond; (C) polymerization initiator; (D) polymerization inhibitor. Preferred embodiments of each component are as described in the above-described photosensitive resin composition.

[0126] The photosensitive resin layer of the photosensitive resin laminate of the present disclosure preferably has a MolLogP of 2.35 or less in component (D) and / or contains a compound comprising formula (1) (where a is 1 or more, or a is an integer of 2 or more).

[0127] The photosensitive resin laminates of this disclosure are suitably used in the manufacture of conductor patterns. For example, the photosensitive resin laminates of this disclosure can be suitably used in the manufacture of printed circuit boards; lead frames for mounting IC chips; metal foils such as metal masks; packages such as ball grid arrays (BGAs) and chip-size packages (CSPs); tape substrates such as chip-on-film (COF) and tape-automated bonding (TAB); semiconductor bumps; and partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields.

[0128] If desired, the photosensitive resin laminate may consist only of a temporary support layer and a photosensitive resin layer, or it may include a protective layer such as a protective film in addition to the temporary support layer and the photosensitive resin layer. The photosensitive resin laminate may have a protective layer on the side of the temporary support layer opposite to the photosensitive resin layer. In this case, a photosensitive resin laminate having a temporary support layer, a photosensitive resin layer, and a protective layer is provided.

[0129] A photosensitive resin laminate may have layers other than the temporary support layer, the photosensitive resin layer, and the protective layer (other layers). Examples of other layers include an "intermediate layer" placed between the temporary support layer and the photosensitive resin layer, and / or between the photosensitive resin layer and the protective layer. For example, a photosensitive resin laminate having an intermediate layer between the temporary support layer and the photosensitive resin layer is manufactured by applying a coating liquid to the intermediate layer on the temporary support layer to form a coating film, and then drying the coating film to obtain the photosensitive resin layer. Another example of other layers is a "release layer" placed on the side of the protective layer opposite to the photosensitive resin layer.

[0130] The temporary support layer, the photosensitive resin layer, and / or protective layer may each consist of a single layer or multiple layers. If they consist of multiple layers, their total thickness may be treated as the thickness of that layer.

[0131] The photosensitive resin laminate may be in the form of a long length. The long photosensitive resin laminate may be in the form of a roll wound around a core.

[0132] Each component of the photosensitive resin laminate of this disclosure is described below.

[0133] [Temporary Support Layer] The temporary support layer is a layer for supporting the photosensitive resin layer, and may be in the form of a substrate or film for supporting the photosensitive resin layer. The film for supporting the photosensitive resin layer is also called a "support film". The temporary support layer may be in the form of a layer for supporting the photosensitive resin layer, and it is preferable that it is transparent to the extent that it can transmit exposure light (active light) emitted from the exposure light source. The temporary support layer is peeled off from the photosensitive resin layer before the exposure process in which the photosensitive resin layer is exposed, or before the development process in which the photosensitive resin layer is developed.

[0134] Suitable substrates for use as a temporary support layer, particularly transparent substrates, include synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Of these, polyethylene terephthalate (PET) is preferred as a temporary support layer because it possesses moderate flexibility and strength. The temporary support layer may be stretched as needed.

[0135] The absorbance of the temporary support layer at a wavelength of 365 nm is preferably 0.3 or less, more preferably 0.2 or less, even more preferably 0.1 or less, and most preferably 0.08 (for example, 0.080) or less. The above absorbance may be 0 or greater.

[0136] It is preferable to use a film with few internal foreign matter, such as a high-quality film, as the temporary support layer. Examples of high-quality films include PET films synthesized using a Ti-based catalyst, PET films with small lubricant diameters and low lubricant content, PET films containing lubricant on only one side, thin-film PET films, PET films with smoothing treatment applied to at least one side, and PET films with roughening treatment such as plasma treatment applied to at least one side. By using a high-quality film as the temporary support layer, exposure light is less likely to be blocked by internal foreign matter in the temporary support layer, making it easier to irradiate the photosensitive resin layer with exposure light, and as a result, resolution is more easily improved.

[0137] The thickness of the temporary support layer is preferably 5 to 25 μm, and more preferably 6 to 20 μm. By adjusting the thickness of the temporary support layer within this range, it is easier to reduce the number of internal foreign matter, and therefore easier to prevent a decrease in resolution. In addition, it is easier to ensure the strength of the temporary support layer, and therefore easier to prevent wrinkles from forming in the photosensitive resin layer during the manufacturing process of the photosensitive resin laminate and / or when laminating the photosensitive resin layer to the substrate.

[0138] The haze of the temporary support layer is preferably 0.01 to 1.5%, more preferably 0.01 to 1.2%, and even more preferably 0.01 to 0.95%, from the viewpoint of improving the parallelism of the exposure light irradiated onto the photosensitive resin layer and obtaining good resolution.

[0139] [Protective Layer] The protective layer is a layer for protecting the photosensitive resin layer, and is often in the form of a film, also called a "protective film." The protective layer has appropriate adhesion to the photosensitive resin layer. When the adhesion between the photosensitive resin layer and the protective layer is sufficiently smaller than the adhesion between the photosensitive resin layer and the temporary support layer, the protective layer can be easily peeled off the photosensitive resin layer. The photosensitive resin layer exposed by peeling off the protective layer is laminated onto the substrate in the lamination process described later.

[0140] Examples of protective layers include polyethylene film, polypropylene film, oriented polypropylene film, biaxially oriented polypropylene film, and polyester film. Specifically, examples of protective layers include Alphan® EM-501, E-200, E-200C3, E-201F, FG-201, MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Trefan® KW37, 2578, 2548, 2500, YM17S, Therapiel® PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, SY (all manufactured by Toray Industries, Inc.), GF-18, GF-818, GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0141] The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 15 to 50 μm. This makes it easier to ensure the marketability and handling of the photosensitive resin laminate, and also makes it easier to wind (roll) the photosensitive resin laminate of this disclosure to realize a roll-shaped wound body.

[0142] The protective layer may have a release layer on its surface, in which case the protective layer is easily peeled off from the photosensitive resin layer. The compounds constituting this type of release layer are classified, for example, into silicone compounds and non-silicone compounds.

[0143] Examples of silicone compounds include: condensation reaction type silicone resins obtained by reacting terminally silanol polydimethylsiloxane with polymethylhydrogen siloxane or polymethylmethoxysiloxane; addition reaction type silicone resins obtained by reacting dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogen siloxane; UV-curable or electron-beam-curable silicone resins obtained by curing acrylic silicone and epoxy group-containing silicone with ultraviolet light or electron beams; modified silicone resins such as epoxy-modified silicone resin (silicone epoxy), polyester-modified silicone resin (silicone polyester), acrylic-modified silicone resin (silicone acrylic), phenol-modified silicone resin (silicone phenol), alkyd-modified silicone resin (silicone alkyd), and melamine-modified silicone resin (silicone melamine); and the like.

[0144] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0145] Examples of protective layers with a release layer include polyester films with a release layer, specifically the "X2NY" release film manufactured by Toyobo Film Solutions Co., Ltd.

[0146] The thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm. This may result in advantages such as a good appearance of the coating film, easier curing of the coating film, and easier securing of sufficient release properties.

[0147] [Intermediate Layer] The photosensitive resin laminate of the present disclosure may have an intermediate layer between the temporary support layer and the photosensitive resin layer. That is, the photosensitive resin laminate of the present disclosure may have a laminated structure in which the temporary support layer, the intermediate layer, and the photosensitive resin layer described above are sequentially laminated, or a laminated structure in which the temporary support layer, the intermediate layer, the photosensitive resin layer, and the protective film are sequentially laminated.

[0148] The photosensitive resin laminate, having an intermediate layer in its laminated structure, allows for exposure after the temporary support layer has been removed, and also reduces rattle of the resist pattern's sidewalls caused by scratches or foreign matter in the temporary support layer. Furthermore, by having an intermediate layer, the photosensitive resin laminate can be imbued with any desired functionality, such as oxygen barrier properties, and thus can exhibit such functionality even after the temporary support layer has been removed.

[0149] The laminated structure of a photosensitive resin laminate having an intermediate layer can be formed by arranging the intermediate layer between the temporary support layer and the photosensitive resin layer in the photosensitive resin laminate described above; or it can be formed by peeling the temporary support layer from the photosensitive resin laminate described above to remove the photosensitive resin layer, and then sequentially laminating the temporary support layer, the intermediate layer, and the photosensitive resin layer. The arrangement or lamination of the intermediate layer can be carried out by coating the resin composition constituting the intermediate layer onto the support or the photosensitive resin layer.

[0150] As described above, the intermediate layer is preferably an oxygen barrier layer and / or a water-soluble resin layer, and more preferably a water-soluble resin layer, from the viewpoint of ensuring exposure performance and functionality even after the temporary support layer has been peeled off from the photosensitive resin laminate.

[0151] The water-soluble resin layer as an intermediate layer is given by the following general formula (2): {In the formula, R １ and R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is -CH ２ CH ２ O-unit and / or -CH ２ CH (CH ３ It is preferable to include a compound represented by} which contains one or more single or repeating structures including an O-unit. By including the compound represented by the above general formula (2) in the water-soluble resin, the tackiness of the intermediate layer can be reduced and the bleeding of the compound itself can be suppressed.

[0152] The water-soluble resin layer, which serves as an intermediate layer, preferably contains polyvinyl alcohol (PVA). Including PVA in the water-soluble resin constituting the water-soluble resin layer can improve oxygen barrier properties. It is more preferable that the water-soluble resin layer contains 50% to 100% by mass of PVA, based on the mass of the water-soluble resin layer. Including 50% by mass or more of PVA in the water-soluble resin layer can further improve oxygen barrier properties.

[0153] The thickness of the water-soluble resin layer as an intermediate layer is preferably 1 μm to 8 μm. By making the water-soluble resin layer 1 μm or thicker, the stability of the water-soluble resin layer can be ensured after the temporary support layer is peeled off. On the other hand, by making the thickness of the water-soluble resin layer 8 μm or less, developability can be ensured.

[0154] [Method for producing a photosensitive resin laminate] A further aspect of the present disclosure is a method for producing a photosensitive resin laminate. Such a method may include, for example, the following steps: applying the photosensitive resin composition described above onto a temporary support layer to form a coating film; and drying the coating film to obtain a photosensitive resin layer.

[0155] The process of forming a coating film may include the following steps: a step of obtaining a coating solution by dissolving a photosensitive resin composition in a solvent, and a step of applying the coating solution to a temporary support layer. The coating solution can be prepared by mixing a photosensitive resin composition with a solvent that dissolves the composition. Examples of solvents include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, and isopropyl alcohol; and so on. The photosensitive resin composition and solvent may be mixed so that the viscosity of the coating solution is 500 to 4000 mPa·sec at 25°C.

[0156] A known method can be used to apply the coating liquid to the temporary support layer, for example, by using a bar coater or a roll coater. A coating film is obtained by applying the coating liquid to the temporary support layer. Drying of the coating film can be carried out using a known dryer and under known conditions (drying temperature and drying time).

[0157] Furthermore, the preferred details (composition, content, various ratios, etc.) described in the section on photosensitive resin laminates above may also be applied to the method for manufacturing photosensitive resin laminates.

[0158] [Method for forming a resist pattern] A further aspect of the present disclosure is a resist pattern obtained using the above-mentioned photosensitive resin laminate and a method for forming the resist pattern. Such a method includes the following steps: a step of laminating the photosensitive resin layer of the above-mentioned photosensitive resin laminate onto a substrate (lamination step); a step of exposing the photosensitive resin layer laminated onto the substrate (exposure step); and a step of removing the unexposed portion of the photosensitive resin layer using an alkaline aqueous solution (development step). A resist pattern is formed by going through these steps.

[0159] [Lamination Process] In the lamination process, the photosensitive resin layer of the photosensitive resin laminate is laminated onto the substrate. Specifically, the lamination process includes the steps of: exposing the photosensitive resin layer by peeling off the protective layer from the photosensitive resin laminate; and laminating the photosensitive resin layer onto the substrate so that the exposed photosensitive resin layer is in contact with the substrate. In the lamination process, a predetermined laminator device may be used, in which case the photosensitive resin layer may be heat-pressed onto the surface of the substrate.

[0160] Examples of substrate materials include metals and / or insulators, such as copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is, for example, 40°C to 160°C. Heat bonding can be performed by using a laminator device equipped with rolls, or by repeatedly passing the laminate of the substrate and photosensitive resin layer through the rolls several times. Heat bonding may be performed under reduced pressure if desired. When laminating the photosensitive resin laminate onto the substrate, the laminated surface on the substrate may be smoothed as necessary. From the viewpoint of optimizing the exposure process after peeling off the temporary support layer or support film, the substrate is preferably a metal plate or a metal-coated insulator.

[0161] [Exposure Process] In the exposure process, the photosensitive resin layer laminated on the substrate is exposed. Specifically, in the exposure process, the photosensitive resin layer is exposed using an exposure machine. Exposure can be performed before peeling off the temporary support layer from the photosensitive resin laminate, or it can be performed after peeling off the temporary support layer or support film. In the exposure process, when exposure is performed via a photomask, the exposure amount may be determined by the illuminance of the light source and the exposure time, or it may be measured using a light meter.

[0162] In the exposure process, direct imaging exposure may be performed. In direct imaging exposure, the photosensitive resin layer is exposed directly by a writing device without using a photomask. As the light source at this time, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm is used. If the writing pattern is controlled by a computer, the exposure amount may be determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0163] In the exposure process, the method of irradiating with exposure light is preferably at least one method selected from projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, with projection exposure or direct imaging exposure being more preferred.

[0164] The exposure step may include a step of heating the substrate and the photosensitive resin layer after exposure (post-exposure heating step) after the exposure and before the development step. In this heating step, the heating temperature is preferably about 30 to about 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. Performing the heating step makes it easier to achieve excellent resolution and adhesion. Heating may be performed using an infrared or far-infrared heating furnace, hot air, a constant temperature bath, a hot plate, a hot air dryer, an infrared dryer, and a hot roll, etc.

[0165] The elapsed time from the exposure process to the heating process, or more precisely, the time from when exposure is completed (i.e., when exposure is stopped) to when heating begins, is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds. The time from when heating begins to when heating is stopped is preferably 1 to 120 seconds, and more preferably 5 to 60 seconds.

[0166] [Developing Step] In the developing step, an alkaline aqueous solution is used to remove unexposed portions of the photosensitive resin layer. Thereby, a resist pattern is obtained. In the case where a temporary support layer or a support film is laminated on the photosensitive resin layer, the above developing step may be performed after peeling off the temporary support layer or the support film.

[0167] As the alkaline aqueous solution for the developer, Na ２ CO ３ , K ２ CO ３ , and aqueous solutions such as tetramethylammonium hydroxide are preferred. The alkaline aqueous solution is selected according to the properties of the photosensitive resin layer. For example, an aqueous solution of Na ２ CO ３ with a concentration of 0.2 to 2% by mass is used. The developer may contain a surfactant and / or an antifoaming agent, and may also contain a small amount of an organic solvent or the like to promote development. In the developing step, the temperature of the developer is preferably kept constant within the range of 20°C to 40°C.

[0168] The developing step preferably includes, after development, a step of washing the substrate and the resist pattern with water (water washing step). The water washing step facilitates removal of the developer remaining on the substrate and the resist pattern. Examples of water for washing used in the water washing step include pure water and industrial water. From the viewpoint of excellent resolution and from the viewpoint of easily forming a resist pattern with high rectangularity, a polyvalent metal salt with a concentration of 0.001 to 1% by mass may be mixed into the water for washing according to the properties of the photosensitive resin layer. Examples of the polyvalent metal salt include MgSO ４ and the like. In the water washing step, the temperature of the washing water is preferably kept constant within the range of 20°C to 40°C.

[0169] The developing process may include a step of heating the substrate and the formed resist pattern (post-developing heating step) after the above-mentioned developing, or after the above-mentioned developing and washing with water. In this heating step, the heating temperature is preferably 60°C to 300°C. Performing this heating step makes it easier to improve the chemical resistance of the resist pattern. Heating may be carried out using an infrared or far-infrared heating furnace, or by hot air, etc.

[0170] Regarding the order of the steps described above, it is preferable from the viewpoint of optimizing the exposure process after peeling off the support film to perform the following steps: laminating the photosensitive resin laminate onto the surface of a metal plate or metal-coated insulator, peeling off the temporary support layer from the photosensitive resin laminate, exposing it to ultraviolet light, and then removing the unexposed areas by developing.

[0171] [Method for Manufacturing Conductor Patterns] A further aspect of the present disclosure is a method for manufacturing a conductor pattern using the above-described photosensitive resin laminate. Such a method includes, for example, the following steps: a step of obtaining a substrate on which a resist pattern is formed (a step of manufacturing a substrate with a resist pattern); a step of performing an etching or plating treatment on the substrate on which the resist pattern is formed, and then forming a conductor pattern (a step of forming a conductor pattern); and a step of peeling the resist pattern from the substrate on which the conductor pattern is formed (a step of peeling).

[0172] [Process for manufacturing a substrate with a resist pattern] In the process for manufacturing a substrate with a resist pattern, a substrate on which a resist pattern has been formed is obtained. In this process, the section on "Method for forming a resist pattern" above can be referred to, thereby obtaining a substrate with a resist pattern.

[0173] [Conductor Pattern Formation Process] In the conductor pattern formation process, an etching or plating process is performed on the substrate on which the resist pattern has been formed, and then a conductor pattern is formed. Specifically, in the conductor pattern formation process, a conductor pattern is formed on the surface (for example, the copper surface) of the substrate (as described above, for example, a metal plate and a metal film insulating plate) exposed by development, using a known etching method or plating method.

[0174] Etching is performed, for example, by spraying an etching solution onto the resist pattern and the substrate surface. Examples of etching methods include acid etching and alkaline etching. Examples of etching solutions include aqueous hydrochloric acid solution, aqueous ferric chloride solution, or mixtures thereof.

[0175] Plating is performed by developing (removing) the exposed substrate portion according to known plating methods, and then applying metal plating (for example, metal plating with copper sulfate plating solution) or solder plating to that portion.

[0176] [Peeling Process] In the peeling process, the resist pattern is peeled off from the substrate on which the conductor pattern is formed. By removing the resist pattern from the substrate, a wiring board (e.g., a printed circuit board) having the desired conductor pattern is obtained.

[0177] In the stripping process, the resist pattern is removed from the substrate using an aqueous solution (stripping solution) that is more alkaline than the developer. Examples of the stripping solution include an aqueous solution of NaOH or KOH with a concentration of 2 to 5% by mass, and an aqueous solution of an organic amine. The stripping solution may contain a small amount of water-soluble solvent. Examples of water-soluble solvents include alcohol. The temperature of the stripping solution in the stripping process is preferably in the range of 40°C to 70°C. The stripping time may be set as appropriate.

[0178] The present invention is not limited to the embodiments described above, and can be implemented with various modifications within the scope of its gist.

[0179] Examples and comparative examples are described below. However, this disclosure is not limited to the following examples. With respect to the examples and comparative examples, various manufacturing, measurement, and evaluation methods were carried out as follows.

[0180] [Preparation of the photosensitive resin composition solution] [Synthesis of component (A)] The monomer (copolymer component) in component A shown in Table 1 was mixed with 3.0 parts by mass of azobisisobutyronitrile in the amounts (unit: parts by mass) shown in Table 1 to obtain solution (a). A mixture of 200 g of methyl ethyl ketone and 100 g of ethanol was placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube. The mixture was stirred while blowing nitrogen gas into the flask, and the temperature of the mixture in the flask was raised to 80°C. 300 g of solution (a) was added to the mixture in the flask dropwise over 4 hours at a constant dropping rate, and then stirred at 80°C for 2 hours.

[0181] Next, solution (b) was obtained by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol. 50 g of solution (b) was added dropwise to the mixture in the flask over 10 minutes at a constant dropping rate, and then stirred at 80°C for 3 hours. The mixture in the flask was then further heated to 90°C over 30 minutes, and then kept at 90°C for 2 hours. After that, stirring was stopped, and the mixture in the flask was cooled to room temperature (25°C). This yielded solutions containing components (A-1) to (A-12) as alkali-soluble polymers, respectively.

[0182] [Preparation of Photosensitive Resin Laminates: Examples 1-33, Comparative Examples 1-4] A 16 μm thick polyethylene terephthalate film (Toray Industries, Ltd., "16FS30") was used as a support film. The above coating liquid was applied to its surface using a bar coater according to the compositions and proportions listed in Tables 1 and 2, and then dried in a 95°C dryer for 1.5 minutes. This formed a photosensitive resin layer on the support film, obtaining a photosensitive resin laminate. In this example, a 33 μm thick polyethylene film (Tamapoly Co., Ltd., product name "GF-858"), a 22 μm thick polyester film with a release layer (Toyobo Film Solutions Co., Ltd., product name "X2NY"), or an 18 μm thick biaxially oriented polypropylene film (Oji F-Tex Co., Ltd., product name "E-200C3") was laminated on the side opposite the support film of the photosensitive resin layer as a protective film, and this was treated as a photosensitive resin laminate.

[0183] [Formation of resist pattern] <Surface preparation of substrate> A copper-clad laminate with a total thickness of 0.4 mm was prepared by laminating rolled copper foil with a thickness of 18 μm. Then, this surface was treated with 10 mass% H ２ SO ４ The copper-clad laminate was washed with an aqueous solution, and then with pure water. After washing, the copper-clad laminate was preheated to 50°C.

[0184] <Lamination> While peeling off the protective film from the photosensitive resin laminate, the copper-clad laminate, preheated to 50°C, was laminated using a hot roll laminator (Taisei Laminator Co., Ltd., VA-700SH) at a roll temperature of 105°C so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate. This obtained an evaluation substrate. The air pressure during lamination was set to 0.35 MPa and the lamination speed was set to 1.5 m / min.

[0185] <Exposure> Two hours after lamination, the substrate was exposed to a projection exposure machine (UX-2003SM-AGG01, manufactured by Ushio Inc.) at a wavelength of 365 nm using a predetermined projection mask pattern.

[0186] <Heating> After 1 minute following exposure, the substrate was heated to a roll temperature of 105°C by passing it through a hot roll laminator (VA-700SH, manufactured by Taisei Laminator Co., Ltd.). Here, the air pressure during lamination was set to 0.35 MPa and the lamination speed was set to 3.0 m / min.

[0187] <Developing> The support film was peeled off the substrate. Then, using an alkaline developer (Fuji Kiko Co., Ltd., dry film developer), 1% by mass of Na was used at 30°C. ２ CO ３ An aqueous solution was sprayed onto the photosensitive resin layer for a predetermined period of time, thereby performing development. The spraying time was set to twice the minimum development time, and the washing time after development (water rinsing by spraying) was also set to twice the minimum development time. In this case, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was treated as the minimum development time. From the above, a substrate with a resist pattern (evaluation substrate) was obtained.

[0188] [Fabrication of Conductor Patterns] Using the evaluation substrate obtained above, a conductor pattern was fabricated by a conventional method.

[0189] [Evaluation and Measurement] [Calculation of MolLogP] The MolLogP of each component (D) was calculated using RDKit, an open-source cheminformatics software. [Mw Weight-Average Molecular Weight] For each solution, the weight-average molecular weight of component (A) was derived by using gel permeation chromatography (GPC) and converting it using a calibration curve for standard polystyrene. The GPC conditions are as follows: (GPC conditions) Pump: JASCO PU-980 Columns: Two in total, Shodex KF-80Y / KF-806M Eluent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 2.05 mL / min Detector: JASCO RI-1530

[0190] A coating liquid (a preparation liquid of a photosensitive resin composition) was obtained by stirring and mixing the components shown in the table below {the numbers for each component indicate the blending amount (parts by mass) as solid content}, and ethanol measured to obtain a solid content concentration of 60%, such that the blending amount of each component as solid content was the value shown in the table below.

[0191] [Sensitivity (optimal exposure dose: mJ / cm ２ )] A drawing pattern with a line width (L) / space width (S) (hereinafter abbreviated as "L / S") of 8 / 8 (unit: μm) was prepared. Then, the above exposure step, heating step and development step were performed using this drawing pattern to form a pattern on an evaluation substrate. Then, the exposure dose at which the line width of the formed pattern is closest to 8 μm (10 mJ / cm ２ intervals) (unit: mJ / cm ２ ) was derived. A smaller value of this exposure dose (optimal exposure dose) was treated as higher sensitivity. The line width of the pattern was measured based on an observation image obtained at a magnification of 100 times using an optical microscope. In addition, in the evaluations of adhesiveness (x / x), adhesiveness (x / 200), and resolution (3x / x) described later, the exposure dose during exposure was set to the optimal exposure dose.

[0192] FIG. 1 is a plan view showing a configuration example of a mask pattern for this evaluation. In the figure, in a region 100 of the photomask, a region that transmits exposure light is indicated by reference numeral 10 (transmission region 10), and a region that does not transmit exposure light is indicated by reference numeral 1 (light shielding region 1). In the figure, the light shielding region 1 is indicated by hatching.

[0193] The transmission regions 10 each have a predetermined width and extend along the x direction, and a plurality of such transmission regions 10 are arranged at predetermined intervals in the width direction (y direction). In this example, since unexposed portions of the photosensitive resin layer are removed through the above development step, it is expected that a resist pattern having L / S corresponding to the width (L: line) of the transmission region 10 and the width (S: space) of the light shielding region 1 will theoretically be formed based on the drawing pattern in the figure.

[0194] [Adhesion (x / x)] The evaluation was performed using a photomask having a drawing pattern where the line width (L) / space width (S) is x / x {x = 1 to 20 (varying at 0.5 μm intervals)} (unit: μm). That is, the evaluation substrate obtained through the above surface preparation and lamination process was exposed to the photomask at the optimal exposure level. Subsequently, a resist pattern with a line length of 7 mm was formed by going through the above heating process and the above development process.

[0195] Figure 1 is a plan view showing an example of the configuration of a drawing pattern for this evaluation. In the figure, in region 100A of the photomask, the exposed region is indicated by reference numeral 10, and the unexposed region (shaded region) is indicated by reference numeral 1. Based on the drawing pattern in Figure 1, it is theoretically expected that a resist pattern with L / S corresponding to the width of the unexposed region 1 (S: space) and the width of the exposed region 10 (L: line) will be formed.

[0196] When the obtained resist pattern was observed with an optical microscope at 100x magnification, the minimum line width at which the line portions (exposed areas) were formed without meandering or chipping was determined as the "adhesion line width (unit: μm)". A smaller value indicates better adhesion.

[0197] [Adhesion (x / 200)] The evaluation was performed using a drawing pattern where the line width (L) / space width (S) was x / 200 {x = 1 to 20 (varying in 0.5 μm increments)} (unit: μm). That is, a resist pattern was formed by exposure with the optimal exposure amount, followed by the heating and developing processes described above.

[0198] Figure 2 is a plan view showing an example of a mask pattern configuration for this evaluation. In the figure, in region 100A of the photomask, the exposed region is indicated by reference numeral 10, and the unexposed region (shaded region) is indicated by reference numeral 1. In region 100A shown in Figure 2, the L / S value is different from that of region 100 shown in Figure 1. Based on the drawing pattern in Figure 2, it is theoretically expected that a resist pattern with L / S corresponding to the width of the unexposed region 1 (S: space) and the width of the exposed region 10 (L: line) will be formed.

[0199] When the obtained resist pattern was observed with an optical microscope at 100x magnification, the minimum line width at which the line portions (exposed areas) were formed without meandering or chipping was determined as the "adhesion line width (unit: μm)". A smaller value indicates better adhesion.

[0200] [Resolution (3x / x)] Evaluation was performed using a drawing pattern with a line width (L) / space width (S) of 3x / x {x = 1 to 20 (varying at 0.5 μm intervals)} (unit: μm). That is, a resist pattern was formed by exposure with the optimal exposure amount, followed by the heating and developing processes described above.

[0201] Figure 3 is a plan view showing an example of a mask pattern configuration. In the figure, in the drawing area 100, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. The unexposed area 1 has a predetermined width and extends in the X direction, and multiple such unexposed areas 1 are arranged in the width direction (Y direction) at predetermined intervals. Theoretically, by exposing the photosensitive resin layer based on the drawing pattern in Figure 1, it is expected that a resist pattern with L / S corresponding to the width of the unexposed area 1 (S: space) and the width of the exposed area 10 (L: line) will be formed.

[0202] When the obtained resist pattern was observed with an optical microscope at a magnification of 100x, the minimum line width at which the line portions (exposed areas) did not meander or break, and the space portions (unexposed areas) were removed without residue, was determined as the "resolution line width (unit: μm)". A smaller value indicates better resolution.

[0203] The results regarding the above are shown in the table below.

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213] According to this disclosure, it is possible to provide a photosensitive resin laminate that can achieve a resist pattern with good adhesion and sensitivity while maintaining high resolution. Such a photosensitive resin laminate can be suitably used in precision metal foil processing such as the manufacture of printed circuit boards, flexible printed circuit boards, lead frames or metal masks, in the manufacture of semiconductor packages such as ball grid arrays (BGAs) or chip-size packages (CSPs), in the manufacture of tape substrates such as TABs or COFs, in the manufacture of semiconductor bumps, indium tin oxide (ITO) electrodes or address electrodes, electromagnetic shields, and the like.

[0214] 1: Light-blocking area 10: Transmitting area 100, 100A, 100B: Areas L: Line S: Space

Claims

1. A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor, wherein the (D) polymerization inhibitor contains 0.002 to 0.3% by mass of a compound having an aromatic ring in which two or more hydrogen atoms are substituted with a group represented by XH (wherein X is at least one selected from O, NH, and NR', and R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms), and having a MolLogP of 2.35 or less, with respect to the total solid content of the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein at least one of the groups represented by XH is a hydroxyl group.

3. A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor, wherein the polymerization inhibitor (D) is represented by the following formula (1) and has a MolLogP of 2.35 or less (D １ A photosensitive resin composition containing 0.002 to 0.3% by mass of the compound relative to the total solid content of the photosensitive resin composition. {In formula (1), X is at least one selected from O, NH, and NR', R represents at least one selected from the group consisting of a halogen atom; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a carboxyl group; or an alkyl group having 1 to 10 carbon atoms, R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms, a represents an integer of 1 or more, b represents an integer of 0 or more, and the sum of a and b is an integer between 2 and 5.} 4. The above (D １ The photosensitive resin composition according to claim 3, wherein a is 2 or more in the compound.

5. The above (D １ The photosensitive resin composition according to claim 3 or 4, wherein a is 2 in the compound.

6. The above (D １ The photosensitive resin composition according to claim 3 or 4, wherein b is 1 or more in the compound.

7. The above (D １ The photosensitive resin composition according to claim 3 or 4, wherein X is an oxygen atom (O) in the compound.

8. The above (D １ The photosensitive resin composition according to claim 3 or 4, wherein in the compound, R is a carboxyl group.

9. A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; and (D) a polymerization inhibitor, wherein the (D) polymerization inhibitor contains 0.002 to 0.3% by mass of a compound having an aromatic ring in which three or more hydrogen atoms are substituted with a group represented by XH (wherein X is at least one selected from O, NH, and NR', and R' represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms; a carbonyl group having 1 to 20 carbon atoms; a carboxyl group having 1 to 20 carbon atoms; and a sulfonyl group having 1 to 20 carbon atoms) with respect to the total solid content of the photosensitive resin composition.

10. The photosensitive resin composition according to claim 9, wherein at least one of the groups represented by XH is a hydroxyl group.

11. A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; (C) a polymerization initiator; (D) a polymerization inhibitor, wherein the polymerization inhibitor (D) is represented by the following formula (1), and in the formula (1), a is 2 or more (D ２ A photosensitive resin composition containing 0.002 to 0.3% by mass of the compound relative to the total solid content of the photosensitive resin composition. {In formula (1), X is at least one selected from O, NH, and NR', R represents at least one selected from the group consisting of halogen atoms; C1-C20 alkyl groups; C3-C10 cycloalkyl groups; carboxyl groups; or carboxyalkyl groups having C1-C10; R' represents at least one selected from the group consisting of C1-C20 alkyl groups; C1-C20 carbonyl groups; C1-C20 carboxyl groups; and C1-C20 sulfonyl groups; a represents an integer of 2 or more, b represents an integer of 0 or more, and the sum of a and b is an integer between 2 and 5.} 12. The above (D ２ The photosensitive resin composition according to claim 11, wherein b is 1 or more in the compound.

13. The aforementioned (D ２ ) compound, wherein X is an oxygen atom (O), the photosensitive resin composition according to claim 11 or 12.

14. The above (D ２ The photosensitive resin composition according to claim 11 or 12, wherein in the compound, R is a carboxyl group.

15. The photosensitive resin composition according to any one of claims 1 to 4, 9 to 12, wherein the polymerization initiator (C) comprises at least one of a hexaarylbiimidazole compound or an acridine compound.

16. The photosensitive resin composition according to any one of claims 1 to 4, 9 to 12, wherein the (C) polymerization initiator is contained in an amount of 4.0% by mass or more based on the total solid content of the photosensitive resin composition.

17. The polymerization inhibitor (D) is a thermal polymerization inhibitor that further contains a nitrogen atom (D ３ A photosensitive resin composition according to any one of claims 1 to 4, 9 to 12, comprising the compound.

18. The photosensitive resin composition according to any one of claims 1 to 4, 9 to 12, wherein the polymerization initiator (C) contains at least one of a hexaarylbiimidazole compound or an acridine compound, and the ratio of the content of the polymerization inhibitor (D) to the polymerization initiator (C) is in the range of 1:50 to 1:1500.

19. The photosensitive resin composition according to any one of claims 1 to 4, 9 to 12, wherein the compound having an ethylenically unsaturated bond (B) contains a compound having a bisphenol A skeleton.

20. The photosensitive resin composition according to any one of claims 1 to 4, 9 to 12, wherein the (A) alkali-soluble polymer contains constituent units derived from the following components: (a-1) (meth)acrylic acid; and (a-2) compounds having aromatic hydrocarbon groups.

21. The photosensitive resin composition according to any one of claims 1 to 4, 9 to 12, wherein the (A) alkali-soluble polymer contains constituent units derived from the following components: (a-1) (meth)acrylic acid; (a-2) compounds having aromatic hydrocarbon groups; and (a-3) hydroxyalkyl (meth)acrylate.

22. The polymerization inhibitor (D) is at least one compound selected from the group consisting of compounds represented by formula (1) and having a MolLogP greater than 2.35; phenothiazine; phenothiazine derivatives; phenoxazine; and phenoxazine derivatives; (D ４ A photosensitive resin composition according to any one of claims 3, 4, 11, or 12, further comprising the compound.

23. In the polymerization inhibitor (D) mentioned above, １ ) compound, or the (D ２ ) The total content d1 (mass%) of the compound and the (D ４ The photosensitive resin composition according to claim 22, wherein the ratio d1:d2 of the total compound content d2 (mass%) is in the range of 5:1 to 1:

5.

24. A photosensitive resin laminate comprising a temporary support layer and a photosensitive resin layer made of the photosensitive resin composition described in any one of claims 1 to 4 or 9 to 12.

25. The photosensitive resin laminate according to claim 24, further comprising a protective layer.

26. A method for forming a resist pattern using the photosensitive resin laminate described in claim 24.

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