Photosensitive resin composition and method for manufacturing circuit board using the same

Abstract

To provide a photosensitive resin composition capable of forming a cured film having superior adhesion reliability even to an inorganic substrate.SOLUTION: A photosensitive resin composition comprises the following components: (A) a resin having a phenolic hydroxyl group; (B) a compound having a methylol group or an alkoxyalkyl group; (C) an aliphatic compound having two or more functional groups selected from one or more kinds of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group; (D) a photosensitive acid-producing agent; and (E) a silane coupling agent having an acid anhydride group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a photosensitive resin composition and a method for manufacturing a circuit board using the same.

Background Art

[0002] In the manufacture of semiconductor elements or printed wiring boards, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer (coating film) is formed on a substrate (a chip in the case of a semiconductor element, a substrate in the case of a printed wiring board) by applying a photosensitive resin composition, etc., and the exposed portion is cured by irradiating actinic light through a predetermined pattern. Further, a resin pattern, which is a cured film of the photosensitive resin composition, is formed on the substrate by selectively removing the unexposed portion using a developer. Therefore, the photosensitive resin composition is required to be excellent in sensitivity to actinic light, ability to form a fine pattern (resolution), etc. For example, Patent Document 1 discloses a photosensitive resin composition excellent in resolution.

[0003] Further, Patent Document 2 discloses a method for manufacturing a circuit board having a further miniaturized conductor pattern using a photosensitive resin composition excellent in resolution.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] When a cured film is formed on an inorganic substrate such as a SiO2 wafer using a photosensitive resin composition, the cured film is required to have adhesion to the inorganic substrate. However, although the cured film formed using a conventional photosensitive resin composition has good initial adhesion to the inorganic substrate, its adhesion decreases when it is placed in a high-temperature and high-humidity environment for a long time, and there is a problem of poor adhesion reliability.

[0006] Therefore, an object of the present disclosure is to provide a photosensitive resin composition capable of forming a cured film excellent in adhesion reliability to an inorganic substrate, and a method for manufacturing a circuit board using the same.

Means for Solving the Problems

[0007] In order to achieve the above object, the present disclosure provides the following photosensitive resin composition and a method for manufacturing a circuit board using the same. [1] A photosensitive resin composition containing (A) component: a resin having a phenolic hydroxyl group, (B) component: a compound having a methylol group or an alkoxyalkyl group, (C) component: an aliphatic compound having two or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group, (D) component: a photosensitive acid generator, and (E) component: a silane coupling agent having an acid anhydride group. [2] The photosensitive resin composition according to [1] above, wherein the content of the (E) component is 0.5 to 10% by mass based on the total solid content of the photosensitive resin composition. [3] The photosensitive resin composition according to [1] or [2] above, wherein the content of the (E) component is 1 to 10 parts by mass with respect to 100 parts by mass of the (A) component. [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein the (E) component is a compound represented by the following general formula (II).

Chemical formula

Effect of the Invention

[0008] According to the present disclosure, it is possible to provide a photosensitive resin composition capable of forming a cured film excellent in adhesion reliability even on an inorganic substrate, and a method for manufacturing a circuit board using the same.

Brief Description of the Drawings

[0009]

Figure 1

Embodiments for Carrying Out the Invention

[0010] Hereinafter, an embodiment of the present disclosure will be specifically described, but the present disclosure is not limited thereto. In the following embodiments, it goes without saying that the constituent elements (including element steps, etc.) are not necessarily essential except in cases where they are specifically indicated and in cases where they are considered clearly essential in principle. This also applies to numerical values and ranges, and should be interpreted as not unduly limiting the present disclosure.

[0011] In addition, in this specification, the terms "layer" and "film" include, in addition to the structure formed over the entire surface when observed as a plan view, the structure formed only in part. The term "step" includes not only an independent step but also the step even when it cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved. "EO modification" means a compound having a (poly)oxyethylene group, and "PO modification" means a compound having a (poly)oxypropylene group. Here, the "(poly)oxyethylene group" means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The "(poly)oxypropylene group" means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. The numerical range indicated using "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value of a numerical range at a certain step may be replaced with the upper limit value or the lower limit value of a numerical range at another step. Also, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "A or B" means that either one of A and B may be included, or both may be included. The materials exemplified below can be used alone or in combination of two or more without particular notice. The content of each component in the composition means the total amount of the plurality of substances present in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In this specification, the "solid content" refers to the non-volatile content excluding the volatile substances (such as water and solvent) contained in the photosensitive resin composition, and includes components that are liquid, syrup-like, or wax-like at room temperature (around 25°C).

[0012] [Photosensitive Resin Composition] The photosensitive resin composition of the present embodiment contains component (A): a resin having a phenolic hydroxyl group, component (B): a compound having a methylol group or an alkoxyalkyl group, component (C): an aliphatic compound having two or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group, component (D): a photosensitive acid generator, and component (E): a silane coupling agent having an acid anhydride group. According to the photosensitive resin composition of the present embodiment, by combining and using the above components (A) to (D) and the above component (E), a cured film excellent in adhesion reliability to an inorganic substrate can be formed.

[0013] The photosensitive resin composition of the present embodiment may further contain component (F): a silicone compound. The photosensitive resin composition of the present embodiment may further contain component (G): at least one solvent selected from the group consisting of ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, lactate ester, and γ-butyrolactone. Hereinafter, each component will be described.

[0014] <Component (A)> The resin having a phenolic hydroxyl group as component (A) is not particularly limited, but is preferably a resin soluble in an aqueous alkali solution, and a novolak resin is particularly preferable from the viewpoint of improving resolution. Such a novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.

[0015] Examples of the above phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, and the like.

[0016] Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

[0017] Specific examples of such novolak resins include phenol / formaldehyde condensation novolak resins, cresol / formaldehyde condensation novolak resins, phenol-naphthol / formaldehyde condensation novolak resins and the like.

[0018] Examples of the component (A) other than novolak resins include polyhydroxystyrene and its copolymers, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, phenol-dicyclopentadiene condensation resins and the like. The component (A) can be used alone or in combination of two or more.

[0019] From the viewpoint of further improving the resolution, developability, heat shock resistance, heat resistance, etc. of the resulting cured film, the weight average molecular weight of the component (A) is preferably 100,000 or less, more preferably 1,000 to 80,000, still more preferably 2,000 to 50,000, and particularly preferably 2,000 to 20,000. Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) method and converted from a standard polystyrene calibration curve.

[0020] In the photosensitive resin composition of the present embodiment, the content of the component (A) is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, based on 100 parts by mass of the total solid content (total amount of components excluding the solvent) of the photosensitive resin composition. When the content of the component (A) is within this range, the film formed using the resulting photosensitive resin composition tends to have further excellent developability with an aqueous alkali solution.

[0021] <Component (B)> The photosensitive resin composition of this embodiment contains, as component (B), a compound having a methylol group or an alkoxyalkyl group. Component (B) is preferably a compound further having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring. Here, the aromatic ring means a hydrocarbon group having aromaticity (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples include a benzene ring and a naphthalene ring. The heterocyclic ring means a cyclic group having at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), and examples include a pyridine ring, an imidazole ring, a pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring, and a pyrimidinone ring. The alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), and examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. The alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group via an oxygen atom. Also, the two alkyl groups may be different from each other, and are, for example, alkyl groups having 1 to 10 carbon atoms.

[0022] By containing component (B), when the photosensitive layer after resin pattern formation is heated and cured, component (B) reacts with component (A) to form a crosslinked structure, preventing the resin pattern from becoming fragile and deforming, and improving the heat resistance. Specifically, a compound further having a phenolic hydroxyl group or a compound further having a hydroxymethylamino group can preferably be used, but does not include the compounds defined as component (A) and component (C) described below. Component (B) can be used alone or in combination of two or more.

[0023] As described below, by including component (D) in the photosensitive resin composition, an acid is generated upon irradiation with actinic rays or the like. Due to the catalytic action of the generated acid, a negative pattern can be formed by the reaction of alkoxyalkyl groups in component (B) with each other or the reaction of an alkoxyalkyl group in component (B) and component (A) with alcohol elimination. Further, due to the catalytic action of the generated acid, a negative pattern can be formed by the reaction of methylol groups in component (B) with each other or the reaction of a methylol group in component (B) and component (A) with alcohol elimination.

[0024] The compound further having the phenolic hydroxyl group can increase the dissolution rate of the unexposed portion during development with an alkaline aqueous solution and improve the sensitivity by further having a phenolic hydroxyl group in addition to the methylol group or alkoxyalkyl group, thereby enabling not only the reaction with component (C) or component (A), but also the improvement of the solubility, photosensitivity, mechanical properties, etc. of the compound in a well-balanced manner. Considering the balance of solubility in an alkaline aqueous solution, photosensitivity, mechanical properties, etc., the weight average molecular weight of the compound having the phenolic hydroxyl group is preferably 94 to 2,000, more preferably 108 to 2,000, and still more preferably 108 to 1,500.

[0025] As the compound further having the phenolic hydroxyl group, conventionally known ones can be used, but the compound represented by the following general formula (1) is preferable because it is excellent in the balance between the effect of promoting the dissolution of the unexposed portion and the effect of preventing melting during the curing of the photosensitive resin film.

[0026] [Chemical formula] In general formula (1), Z represents a single bond or a divalent organic group, and R 24 and R 25 each independently represent a hydrogen atom or a monovalent organic group, and R 26 and R 27each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. Here, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group; and a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom. R 24 ~R 27 When there are a plurality of them, they may be the same or different from each other.

[0027] The compound represented by the general formula (1) is preferably a compound represented by the general formula (2).

[0028] [Chemical formula] In the general formula (2), X 1 represents a single bond or a divalent organic group, and a plurality of Rs each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

[0029] Further, as the compound having the phenolic hydroxyl group, a compound represented by the general formula (3) may be used.

[0030] [Chemical formula] In the general formula (3), a plurality of Rs each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

[0031] In general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by Z include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group, and propylene group; alkylidene groups having 2 to 10 carbon atoms such as ethylidene group; arylene groups having 6 to 30 carbon atoms such as phenylene group; groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atom; sulfonyl group; carbonyl group; ether bond; sulfide bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (4).

[0032]

Chemical formula

[0033] Examples of the compound further having the above hydroxymethylamino group include (poly)(N-hydroxymethyl)melamine, (poly)(N-hydroxymethyl) glycoluril, (poly)(N-hydroxymethyl) benzoguanamine, (poly)(N-hydroxymethyl)urea, and the like. Further, a nitrogen-containing compound obtained by alkyl etherifying all or part of the hydroxymethylamino groups of these compounds may also be used. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and it may contain an oligomer component formed by partial self-condensation. Specifically, hexakis(methoxymethyl)melamine, hexakis(butoxymethyl)melamine, tetrakis(methoxymethyl)glycoluril, tetrakis(butoxymethyl)glycoluril, tetrakis(methoxymethyl)urea, and the like can be mentioned.

[0034] Specifically, the compound having the above hydroxymethylamino group is preferably a compound represented by the general formula (5) or a compound represented by the general formula (6).

[0035]

Chemical formula

Chemical formula

[0036] The content of component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, and particularly preferably 10 to 35 parts by mass with respect to 100 parts by mass of component (A). When the content of component (B) is 5 parts by mass or more, the reaction in the exposed portion is sufficient, so the resolution is less likely to decrease, and the chemical resistance and heat resistance tend to be good. When it is 60 parts by mass or less, it becomes easier to form a film of the photosensitive resin composition on a desired support, and the resolution tends to be good.

[0037] <Component (C)> The photosensitive resin composition of this embodiment contains, as component (C), an aliphatic compound having two or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group. Component (C) improves the adhesiveness, that is, the tackiness, between the photosensitive resin composition and the support. Furthermore, it can increase the dissolution rate of the unexposed portion during development with an aqueous alkali solution and improve the resolution. From the viewpoints of tackiness and solubility in an aqueous alkali solution, the molecular weight of component (C) is preferably 92 to 2,000, more preferably 106 to 1,500, and particularly preferably 134 to 1,300 in terms of weight average molecular weight considering the balance. Here, the "aliphatic compound" means a compound whose main skeleton is an aliphatic skeleton and does not contain an aromatic ring or a heterocyclic ring.

[0038] As the functional group of component (C), a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group is preferable, a glycidyloxy group or an acryloyloxy group is more preferable, and a glycidyloxy group is even more preferable. Also, from the viewpoints of sensitivity and resolution, component (C) preferably has three or more of the above functional groups, and more preferably has four or more of the above functional groups. The upper limit of the number of the above functional groups is not particularly limited, but is, for example, 12. Specific examples of component (C) include compounds represented by general formulas (7) to (10).

[0039]

Chemical formula

[0040] Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 - hexanediol diglycidyl ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerol triglycidyl ether, glycerol propoxylate triglycidyl ether, 1,4 - cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2 - cyclohexanedicarboxylate, and the like. These compounds having a glycidyloxy group can be used alone or in combination of two or more.

[0041] Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether are preferred in terms of excellent sensitivity and resolution.

[0042] Compounds having a glycidyloxy group are commercially available, for example, as Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (all manufactured by Kyoeisha Chemical Co., Ltd., trade names), alkyl type epoxy resin ZX-1542 (manufactured by Nippon Steel Chemical & Material Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, and Denacol EX-850L (all manufactured by Nagase ChemteX Corporation, trade names), and Shofree PETG (manufactured by Resona Holdings, Inc., trade name).

[0043] Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, EO-modified pentaerythritol tetraacrylate, PO-modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO-modified pentaerythritol triacrylate, PO-modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO-modified trimethylolpropane acrylate, PO-modified trimethylolpropane acrylate, trimethylolpropane acrylate, EO-modified glycerin triacrylate, PO-modified glycerin triacrylate, glycerin triacrylate, and the like. These compounds having an acryloyloxy group can be used alone or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

[0044] Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetramethacrylate, EO-modified pentaerythritol tetramethacrylate, PO-modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO-modified pentaerythritol trimethacrylate, PO-modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO-modified trimethylolpropane methacrylate, PO-modified trimethylolpropane methacrylate, trimethylolpropane methacrylate, EO-modified glycerin trimethacrylate, PO-modified glycerin trimethacrylate, glycerin trimethacrylate, and the like. These compounds having a methacryloyloxy group can be used alone or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

[0045] Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. These compounds having a hydroxyl group can be used alone or in combination of two or more.

[0046] When the component (C) is an aliphatic compound having two or more glycidyloxy groups, its chlorine content is preferably 4000 mass ppm or less, more preferably 2000 mass ppm or less, still more preferably 1000 mass ppm or less, particularly preferably 500 mass ppm or less, and extremely preferably 100 mass ppm or less. By using a compound satisfying the above chlorine content, good insulation reliability can be obtained.

[0047] The content of component (C) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, and particularly preferably 30 to 55 parts by mass with respect to 100 parts by mass of component (A). When the content of component (C) is 20 parts by mass or more, crosslinking in the exposed area becomes sufficient and the tackiness tends to be sufficient. When it is 70 parts by mass or less, it becomes easier to form a film of the photosensitive resin composition on a desired support, and the resolution is less likely to decrease.

[0048] <Component (D)> The photosensitive acid generator as component (D) is a compound that generates an acid upon irradiation with actinic rays or the like. Here, the molar extinction coefficient of component (D) in h-line or i-line (the coefficient obtained by converting the absorbance of a specific sample when using a cell with a concentration of the analysis species of 1 mol / L and an optical path length of 1 cm) is preferably 100 or more from the viewpoint of improving the sensitivity, resolution, pattern formation, etc. in the process using a direct drawing exposure apparatus for h-line or i-line actinic rays.

[0049] Component (D) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays in the h-line or i-line region or the like. Examples of component (D) include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and the like. Among them, from the viewpoint of ease of availability, component (D) is preferably at least one selected from the group consisting of onium salt compounds and sulfonimide compounds. In particular, when using a solvent, component (D) is preferably an onium salt compound from the viewpoint of excellent solubility in the solvent. Specific examples thereof are shown below.

[0050] Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium heptadecafluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tris(pentafluoroethyl)trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium tris[(trifluoromethyl)sulfonyl]methanide, and other diaryliodonium salts; triarylsulfonium salts, and the like. Among them, from the viewpoint of further improving sensitivity and thermal stability, sulfonium salts are preferred, and from the viewpoint of excellent sensitivity in the h-line region and further improving thermal stability, triarylsulfonium salts are more preferred. Further, as the onium salt compound, onium borate salts and onium galate salts are preferred. The onium salt compound can be used alone or in combination of two or more.

[0051] Examples of the triarylsulfonium salt as the component (D) include at least one cation selected from the group consisting of a compound represented by the following formula (d1), a compound represented by the following formula (d2), a compound represented by the following formula (d3), and a compound represented by the following formula (d4), and an anion having at least one skeleton selected from the group consisting of a tetraphenylborate skeleton, a tetraphenylgallate skeleton, an alkylsulfonate skeleton having 1 to 20 carbon atoms, a phenylsulfonate skeleton, a 10-camphorsulfonate skeleton, a trisalkylsulfonylmethanide skeleton having 1 to 20 carbon atoms, a tetrafluoroborate skeleton, a tetrafluorogallate skeleton, a hexafluoroantimonate skeleton, and a hexafluorophosphate skeleton.

[0052] [Chemistry]

[0053] [Chemistry]

[0054] [Chemistry]

[0055] [Chemistry]

[0056] The hydrogen atoms of the phenyl groups in formulas (d1), (d2), (d3), and (d4) may be substituted with at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms. When there are a plurality of substituents, they may be the same or different from each other.

[0057] In addition, the hydrogen atoms of the phenyl groups in the above-mentioned tetraphenylborate skeleton and tetraphenylgallate skeleton may be substituted with at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms. When there are a plurality of substituents, they may be the same or different from each other.

[0058] The hydrogen atoms of the above-mentioned alkyl sulfonate skeleton may be substituted with at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. When there are a plurality of substituents, they may be the same or different from each other.

[0059] The hydrogen atom of the phenyl group in the phenyl sulfonate skeleton may be substituted with at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms. When there are a plurality of substituents, they may be the same or different from each other.

[0060] The hydrogen atom of the trisalkylsulfonylmethanide skeleton may be substituted with at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. When there are a plurality of substituents, they may be the same or different from each other.

[0061] The fluorine atom of the hexafluorophosphate skeleton may be substituted with at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 12 carbon atoms. When there are a plurality of substituents, they may be the same or different from each other.

[0062] From the viewpoint of further excellent sensitivity, resolution, and insulation properties, the sulfonium salt used as the component (D) preferably has, as a cation, at least one selected from the group consisting of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium, and tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium.

[0063] As the anion of the sulfonium salt used as the (D) component, it is preferably a compound having at least one selected from the group consisting of trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, tris[(trifluoromethyl)sulfonyl]methanide, 10-camphorsulfonate, tris(pentafluoroethyl)trifluorophosphate, tetrakis(pentafluorophenyl)borate, and tetrakis(pentafluorophenyl)gallate.

[0064] Specific examples of the sulfonium salt include (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium nonafluorobutanesulfonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)gallate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tetrakis(pentafluorophenyl)gallate, and the like. The sulfonium salt can be used alone or in combination of two or more.

[0065] Similar to the above-mentioned triarylsulfonium salt compound, examples of the sulfonimide compound used as a photosensitive acid generator excellent in sensitivity in the h-line region include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthylimide, N-(p-toluenesulfonyloxy)-1,8-naphthalimide, N-(10-camphorsulfonyloxy)-1,8-naphthalimide, and the like. The sulfonimide compound can be used alone or in combination of two or more.

[0066] (D) Each of the compounds exemplified above as the component can be used alone or in combination of two or more.

[0067] (D) From the viewpoint of further improving the sensitivity, resolution, pattern shape, etc. of the photosensitive resin composition of the present embodiment, the content of the component (D) is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, 1 to 10 parts by mass, 3 to 10 parts by mass, 5 to 10 parts by mass, or 6 to 10 parts by mass with respect to 100 parts by mass of the component (A).

[0068] <(E) component> The photosensitive resin composition of the present embodiment contains, as the component (E), a silane coupling agent having an acid anhydride group. By using a silane coupling agent having an acid anhydride group, the adhesion reliability of the obtained cured film to the inorganic substrate can be improved. The component (E) can be used alone or in combination of two or more.

[0069] Examples of the acid anhydride group include groups such as carboxylic acid anhydride groups. Examples of the carboxylic acid anhydride group include groups derived from succinic anhydride, groups derived from maleic anhydride, groups derived from glutaric anhydride, and the like. The acid anhydride group may be a group derived from succinic anhydride from the viewpoint of further enhancing the adhesion reliability of the cured film to the inorganic substrate.

[0070] Component (E) may be a compound represented by the following general formula (I). Si(OR 31 ) f (R 32 ) 3-f X …(I) In formula (I), R 31 represents an alkyl group, R 32 represents a monovalent organic group, X represents a monovalent organic group having an acid anhydride group, and f represents an integer of 1 to 3. When f is 2 or 3, a plurality of R 31 may be the same as or different from each other. When f is 1, a plurality of R 32 may be the same as or different from each other. Here, R 31 may be an alkyl group having 1 to 6 carbon atoms, and R 32 may be an alkyl group having 1 to 6 carbon atoms or a hydroxyl group. Also, f may be 2 or 3, and may be 3.

[0071] Further, from the viewpoint of further enhancing the adhesion reliability of the cured film to the inorganic substrate, component (E) is preferably a compound represented by the following general formula (II).

Chemical formula

[0072] Examples of commercially available (E) components include 3-trimethoxysilylpropyl succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-12-967C), [(3-triethoxysilyl)propyl] succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., trade name), and the like.

[0073] The content of the (E) component is preferably 0.5 to 10% by mass, more preferably 1 to 8% by mass, and still more preferably 1.5 to 5% by mass based on the total solid content of the photosensitive resin composition. When the content of the (E) component is 0.5% by mass or more, the adhesion reliability of the cured film to the inorganic substrate can be further improved. When the content of the (E) component is 10% by mass or less, an increase in viscosity during long-term storage of the photosensitive resin composition can be suppressed.

[0074] The content of the (E) component is preferably 1 to 10 parts by mass, more preferably 1.5 to 9 parts by mass, and still more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the (A) component. When the content of the (E) component with respect to 100 parts by mass of the (A) component is 1% by mass or more, the reaction between the (A) component and the (E) component proceeds easily during the formation of the cured film, and the adhesion reliability of the cured film to the inorganic substrate can be further improved. When the content of the (E) component is 10% by mass or less, an increase in viscosity during long-term storage of the photosensitive resin composition can be suppressed.

[0075] <(F) component> The silicone compound as the (F) component is a leveling agent capable of imparting smoothness to the surface of the coating film. By orienting on the surface of the coating film after coating, the surface smoothness can be ensured or the wettability to the substrate surface can be improved. These function by orienting in the photosensitive resin composition and reducing the surface tension.

[0076] (F) component is not particularly limited as long as it is a silicone compound. Among them, from the perspective of the leveling effect, it is particularly preferable to use a compound having a polysiloxane structure. Further, as the silicone compound, from the viewpoint of compatibility with other organic components constituting the coating film, a modified silicone compound having an organic group that is likely to be compatible with the other organic components is more preferable. Specific examples thereof are shown below.

[0077] (F) component includes polyether-modified polymethylsiloxane, polyether-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, polyether-modified polymethyldialkylsiloxane, aralkyl-modified polymethylsiloxane, aralkyl-modified polymethyldisiloxane, aralkyl-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkyldisiloxane, phenyl-modified polymethylsiloxane, phenyl-modified polymethyldisiloxane, phenyl-modified polymethylalkylsiloxane, phenyl-modified polymethylalkyldisiloxane, acrylate or methacrylate-modified polymethylsiloxane, acrylate or methacrylate-modified polydimethylsiloxane, acrylate or methacrylate-modified polymethylalkylsiloxane, acrylate or methacrylate-modified polymethylalkyldisiloxane, etc.

[0078] (F) component content, from the viewpoint of making the coating film surface smoothness, sensitivity, resolution, pattern shape, etc. of the photosensitive resin composition of this embodiment better, is preferably 0.01 to 1.0 parts by mass, more preferably 0.03 to 0.5 parts by mass, based on 100 parts by mass of the total solid content excluding the (F) component in the photosensitive resin composition.

[0079] <(G) component> The photosensitive resin composition of this embodiment may contain, as component (G), at least one solvent selected from the group consisting of ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, lactate ester, and γ-butyrolactone. By using these solvents, even when the resolution is good and the film thickness of the coating film is reduced, a highly reliable device can be manufactured in a high-humidity environment. The reason is not necessarily clear, but the influence on components (A) to (F) by these solvents is extremely small, and they have a certain boiling point, which can prevent the decrease in coating film strength due to the volatilization of the solvent during the formation of the coating film. These are considered to be part of the reasons.

[0080] Examples of the alkyl group in ethylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether acetate include a methyl group, an ethyl group, an n-propyl group, isopropyl, etc. Among them, a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.

[0081] Examples of the lactate ester include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, etc. Among them, methyl lactate or ethyl lactate is preferable, and ethyl lactate is more preferable.

[0082] From the viewpoint of improving the insulation reliability of the formed resin pattern, component (G) is preferably ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, or lactate ester, more preferably propylene glycol monoalkyl ether acetate or lactate ester, and still more preferably propylene glycol monomethyl ether acetate or ethyl lactate.

[0083] The content of component (G) is preferably 30 to 200 parts by mass, more preferably 60 to 120 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding component (G).

[0084] In addition, the photosensitive resin composition of this embodiment may further contain solvents other than the component (G), such as propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; cellosolves such as ethyl cellosolve and butyl cellosolve, carbitols such as butyl carbitol, aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; and ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone. In that case, the content of the solvent other than the component (G) is preferably 50% by mass or less, more preferably 25% by mass or less, and still more preferably substantially not contained (for example, 2% by mass or less) of the total solvent.

[0085] <Other Components> The photosensitive resin composition of this embodiment may contain other components other than the above-described components. Examples of the other components include colorants, adhesion aids, leveling agents, inorganic fillers, silane coupling agents other than the component (E) described above, inhibitors for reactions accompanying irradiation with actinic rays, and adhesion aids.

[0086] [Photosensitive Element] The photosensitive resin composition of this embodiment may be used in the state of a photosensitive element. The photosensitive element includes a support and a photosensitive layer provided on the support, and the photosensitive layer contains the above-mentioned photosensitive resin composition. The photosensitive layer can be formed from the above-mentioned photosensitive resin composition. The photosensitive element of this embodiment may further include a protective film covering the photosensitive layer on the photosensitive layer.

[0087] As the above-mentioned support, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. The thickness of the above-mentioned support (polymer film) may be 5 to 50 μm. The above-mentioned polymer film may be laminated on both sides of the photosensitive layer with one as the support and the other as the protective film for use.

[0088] As the above-mentioned protective film, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.

[0089] The above-mentioned photosensitive layer can be formed by applying the above-mentioned photosensitive resin composition on a support or a protective film and drying it. Examples of the coating method include a dipping method, a spraying method, a bar coating method, a roll coating method, and a spin coating method. The thickness of the above-mentioned photosensitive layer varies depending on the application, but after drying the photosensitive layer, it is preferably 1 to 50 μm, more preferably 2 to 40 μm, and even more preferably 3 to 30 μm.

[0090] [Method for manufacturing a circuit board] FIG. 1 is a diagram showing a method for manufacturing a circuit board according to an embodiment of the present disclosure. The method for manufacturing a circuit board according to this embodiment includes: (a) applying the above-described photosensitive resin composition onto substrate 1 and drying the photosensitive resin composition to form a photosensitive layer 2; (b) exposing the photosensitive layer 2 in a predetermined pattern, developing it, and further performing a heat treatment to form a resin pattern 4; (c) plating the exposed portions of substrate 1 and the exposed portions of resin pattern 4 to form a conductor layer 7; and (d) removing a part of conductor layer 7 to form a conductor pattern 8 (circuit). That is, the method for manufacturing a circuit board according to this embodiment is a method for manufacturing a circuit board provided with a resin pattern 4 formed using a predetermined pattern and a miniaturized conductor pattern 8 on substrate 1. Here, the resin pattern is a pattern of resin obtained by curing a photosensitive layer on which a predetermined pattern is formed, and part or all of the resin in the resin pattern is cured. That is, the resin pattern means a cured film. Hereinafter, each step will be described in detail.

[0091] <Step (a)> (Step (a)) is a step of applying the above-described photosensitive resin composition onto substrate 1 and drying the photosensitive resin composition to form a photosensitive layer 2 (see FIG. 1(a)). That is, (Step (a)) can also be said to be a step of obtaining a substrate provided with a photosensitive layer 2 containing the photosensitive resin composition.

[0092] Examples of the method for applying the photosensitive resin composition onto the substrate include a dipping method, a spraying method, a bar coating method, a roll coating method, and a spin coating method. The thickness of the coating film can be appropriately controlled by adjusting the coating means, the solid content concentration, and the viscosity of the photosensitive resin composition. The thickness of photosensitive layer 2 varies depending on the application, but it is preferably 1 to 20 μm, more preferably 2 to 10 μm, after drying.

[0093] As the substrate 1, for example, inorganic substrates such as SiO2 wafers, glass substrates, SiN wafers, silicon wafers, and alumina substrates can be used. According to the photosensitive resin composition of the present embodiment, even when such an inorganic substrate is used, a cured film having excellent adhesion reliability can be formed. Note that, as the substrate 1, other than inorganic substrates may be used. As the substrate 1, a copper foil with resin, a copper-clad laminate, or the like may be used. Further, as the substrate 1, a silicon wafer with a metal sputter film, an inorganic substrate with a cured resin layer formed using a photosensitive resin composition, or the like may be used.

[0094] <(b) Process> (The (b) process is a process of obtaining the resin pattern 4 by exposing the photosensitive layer 2 in a predetermined pattern, developing it, and further performing a heat treatment (see FIGS. 1(b) and (c)).

[0095] First, the photosensitive layer 2 is exposed in a predetermined pattern through a predetermined mask pattern. Examples of the actinic rays used for exposure include light rays using a g-line stepper as a light source; ultraviolet rays using a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-line stepper, etc. as a light source; electron beams; laser light rays, and the like. The exposure amount is appropriately selected depending on the light source used, the thickness of the coating film, etc. For example, when irradiating ultraviolet rays to a coating film with a thickness of 1 to 20 μm using a high-pressure mercury lamp, the exposure amount may be about 10 to 3000 mJ / cm 2 or so.

[0096] Next, the exposed photosensitive layer 2 is developed with an alkaline developer to dissolve and remove the regions other than the regions cured by exposure (unexposed portions), thereby obtaining the photosensitive layer 2 with a predetermined pattern formed (see FIG. 1(b)). The region removed here becomes the region (circuit groove 3) where the conductor pattern 8 is to be formed. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, a paddle developing method, and the like. The developing conditions are usually 20 to 40°C for 20 seconds to 5 minutes.

[0097] As the alkaline developer, for example, an alkaline aqueous solution prepared by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, etc. in water so that the concentration becomes about 1 to 10% by mass, or an alkaline aqueous solution such as aqueous ammonia can be used. Among them, an aqueous solution of tetramethylammonium hydroxide is preferably used in terms of excellent resolution of the resin pattern 4. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution. After development with the alkaline developer, it is washed with water and dried.

[0098] Next, the resin pattern 4 is obtained by heat-treating the photosensitive layer 2 on which a predetermined pattern is formed (see Fig. 1(c)). By performing the heat treatment, insulating film characteristics are exhibited. The conditions of the heat treatment are not particularly limited and can be adjusted according to the use of the cured product. For example, the heating temperature may be 50 to 250 °C and the heating time may be 30 minutes to 10 hours.

[0099] Also, the heat treatment may be performed in two steps for the purpose of allowing curing to proceed sufficiently, preventing deformation of the shape of the obtained resin pattern 4, etc. When performing the heat treatment in two steps, for example, the heating temperature and heating time in the first step can be 50 to 120 °C and 5 minutes to 2 hours respectively, and the heating temperature and heating time in the second step can be 80 to 200 °C and 10 minutes to 10 hours respectively.

[0100] When performing the heat treatment under the above conditions, the heating equipment is not particularly limited, and for example, a general oven or an infrared furnace can be used.

[0101] In the method for manufacturing a circuit board according to the present embodiment, heat treatment (post-exposure bake) may be performed before development after exposure. The conditions of the post-exposure bake vary depending on the content of the photosensitive resin composition, the thickness of the coating film, etc., but usually, it is preferably heated at 70 to 150 °C for 1 to 60 minutes, and more preferably heated at 80 to 120 °C for 1 to 60 minutes.

[0102] <(c) Process> (c) The process is a process of forming the conductor layer 7 by plating the exposed portions of the substrate 1 and the resin pattern 4 (see FIGS. 1(d) and (e)). Note that the exposed portion of the substrate 1 refers to the region where no resin pattern is formed on the surface of the substrate 1 where the resin pattern is formed.

[0103] The method of the plating process is not particularly limited, and for example, it may be a method using electrolytic plating, electroless plating, or sputtering.

[0104] The thickness of the conductor layer 7 can be appropriately adjusted according to the height of the wiring groove to be formed, but it is preferably 1 to 35 μm, and more preferably 2 to 25 μm.

[0105] The conductor layer 7 may be composed of a seed metal layer 5 and a plating layer 6 grown thereon. That is, the (c) process may include a process of forming the seed metal layer 5 on the exposed portions of the substrate 1 and the resin pattern 4 (see FIG. 1(d)). When forming the seed metal layer 5, the plating layer 6 can be formed by performing a plating process on the formed seed metal layer 5 (see FIG. 1(e)).

[0106] The method of forming the seed metal layer 5 is not particularly limited, and examples thereof include electroless plating and sputtering.

[0107] When forming the seed metal layer 5 by electroless plating, the metal constituting the seed metal layer 5 may be, for example, a single metal such as gold, platinum, silver, copper, aluminum, cobalt, chromium, nickel, titanium, tungsten, iron, tin, indium, etc., or may be a solid solution (alloy) of two or more metals such as nickel-chromium alloy. Among these, the metal constituting the seed metal layer 5 is preferably chromium, nickel, titanium, nickel-chromium alloy, aluminum, zinc, copper-nickel alloy, copper-titanium alloy, gold, silver or copper from the viewpoints of versatility of metal film formation, cost, ease of removal by etching, etc., more preferably chromium, nickel, titanium, nickel-chromium alloy, aluminum, zinc, gold, silver or copper, and particularly preferably titanium or copper. Also, the seed metal layer 5 may be a single layer or may have a multilayer structure in which two or more different metals are laminated.

[0108] When forming the seed metal layer 5 by electroless plating, an electroless plating solution is used. As the electroless plating solution, a known autocatalytic type electroless plating solution can be used, and the metal species, reducing agent species, complexing agent species, hydrogen ion concentration, dissolved oxygen concentration, etc. contained in the electroless plating solution are not particularly limited. As the electroless plating, for example, an electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; an electroless nickel-phosphorus plating solution using sodium hypophosphite as a reducing agent; an electroless nickel-boron plating solution using dimethylaminoborane as a reducing agent; an electroless palladium plating solution; an electroless palladium-phosphorus plating solution using sodium hypophosphite as a reducing agent; an electroless gold plating solution; an electroless silver plating solution; an electroless nickel-cobalt-phosphorus plating solution using sodium hypophosphite as a reducing agent, etc. can be used.

[0109] Also, the method of forming the seed metal layer 5 by electroless plating may be, for example, a method in which a catalytic nucleus such as silver, palladium, zinc, cobalt, etc. is attached to the portion where the seed metal layer 5 is to be formed, and then a metal thin film is formed on the catalytic nucleus using the above-mentioned electroless plating solution.

[0110] The method of attaching a catalytic nucleus to the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4 is not particularly limited. For example, a solution in which a metal compound, salt, or complex of a metal serving as a catalytic nucleus is dissolved in water or an organic solvent (for example, alcohol and chloroform) so that the concentration is 0.001 to 10% by mass is prepared, and the substrate 1 on which the resin pattern 4 is formed is immersed in this solution, and then the metal in the solution is reduced to precipitate the metal. In addition, the solution in the above method may contain an acid, an alkali, a complexing agent, a reducing agent, etc., as necessary.

[0111] When forming the seed metal layer 5 by sputtering, as the metal constituting the seed metal layer 5, for example, the same metal as that used when forming the seed metal layer 5 by electroless plating can be used.

[0112] The metal constituting the plating layer 6 is not particularly limited, but copper is preferable. As a method of forming the plating layer 6 on the seed metal layer 5, for example, a method of growing plating by wet plating such as electrolytic plating can be mentioned.

[0113] The seed metal layer 5 can be subjected to rust prevention treatment using a rust preventive before forming the plating layer 6.

[0114] When forming the seed metal layer 5, the thickness of the seed metal layer 5 is not particularly limited, but it is preferably 10 nm to 5000 nm, more preferably 20 nm to 2000 nm, still more preferably 30 nm to 1000 nm, particularly preferably 50 nm to 500 nm, and extremely preferably 50 nm to 300 nm. When the thickness is 10 nm or more, the plating layer 6 tends to be uniformly formed by electrolytic plating, and when the thickness is 5000 nm or less, the removal time of the seed metal layer by etching or polishing can be appropriately shortened, so that the cost of removing the seed metal layer 5 can be suppressed.

[0115] After the formation of the conductor layer 7, the conductor layer 7 may be heated for the purpose of improving adhesion or the like. The heating temperature is usually 50 to 350°C, preferably 80 to 250°C. Note that the heating may be performed under pressure conditions. Examples of the pressurization method include a method using physical pressurization means such as a hot press machine or a pressure heating roll machine. The pressure to be applied is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. Within this range, the adhesion between the seed metal layer 5 and the resin pattern 4 or the substrate 1 tends to be excellent.

[0116] <(d) process> (d) The process is a process of removing a part of the conductor layer 7 to form a conductor pattern 8 (see Fig. 1(f)). As shown in Fig. 1(e), the conductor layer 7 is formed on the entire exposed surface of the substrate 1 and the exposed surface of the resin pattern 4. That is, plating (metal film) is also formed in regions other than the region (circuit groove 3) where the conductor pattern 8 is to be formed. Therefore, the (d) process can be said to be a process of removing the metal film formed in the region other than the circuit groove 3 in the conductor layer 7.

[0117] The method of removing a part of the conductor layer 7 may be a known method for removing metal. For example, it may be a method by mechanical polishing and / or a method by etching.

[0118] When removing a part of the conductor layer 7 by mechanical polishing, the mechanical polishing method is preferably a Chemical Mechanical Polishing (hereinafter also referred to as "CMP") method. The method of removing a part of the conductor layer 7 by the CMP method is, for example, attaching a polishing cloth (polishing pad) on a polishing platen, immersing the surface of the polishing cloth with a metal polishing agent, pressing the surface of the conductor layer 7 against the surface of the polishing cloth, and rotating the polishing platen while applying a predetermined pressure (hereinafter referred to as "polishing pressure") to the surface of the conductor layer 7 from the back surface, and removing a part of the conductor layer 7 by the mechanical friction between the polishing agent and the surface of the conductor layer 7.

[0119] The abrasive for CMP may contain, for example, an oxidizing agent and solid abrasive grains (hereinafter simply referred to as "abrasive grains"), and may further contain, if necessary, a metal oxide dissolving agent, a protective film forming agent, etc. The basic mechanism of CMP using an abrasive containing an oxidizing agent and abrasive grains is considered as follows. First, the surface of the metal film to be polished is oxidized by the oxidizing agent to form an oxide layer, and it is considered that the metal film is polished by scraping off the oxide layer with the abrasive grains. When polished by such a mechanism, the oxide layer on the surface of the metal film formed in the circuit groove 3 hardly touches the polishing cloth, so the effect of scraping by the abrasive grains is less likely to reach the metal film formed in the circuit groove 3. Therefore, as the CMP polishing progresses, the metal film in the region other than the circuit groove 3 is removed and the polished surface tends to be flattened.

[0120] The abrasive is preferably an abrasive that can be used in the range of a polishing rate of 5000 to 3000 Å / min.

[0121] When removing a part of the conductor layer 7 by etching, examples of the etching method include the sandblasting method and the wet etching process. In the case of the sandblasting method, for example, etching is performed by spraying cutting particles such as silica and alumina onto the portion of the conductor layer 7 to be removed. In the case of the wet etching process, etching is performed using an etching solution. As the etching solution, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, an ammonium persulfate aqueous solution, and a hydrogen peroxide etching solution can be used.

[0122] The thickness of the portion of the conductor layer 7 removed in the step (d), that is, the metal film in the region other than the circuit groove 3, may be about 0.1 to 35 μm.

[0123] The circuit board manufactured by the above method can have a semiconductor element mounted at the corresponding location to ensure electrical connection. Also, by the above method, a circuit board having a miniaturized conductor pattern 8 can be obtained.

Example

[0124] Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited to these examples in any way.

[0125] (Examples 1 to 4 and Comparative Examples 1 to 3) ><Preparation of Photosensitive Resin Composition> Each component shown in Table 1 was blended in the blending amounts (unit: parts by mass) shown in the same table to obtain the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3.

[0126] In addition, the abbreviations in Table 1 are as follows. A-1: Cresol novolak resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000) B-1: 1,3,4,6-Tetrakis(methoxymethyl) glycoluril (manufactured by Sankyo Chemical Co., Ltd., trade name: Nikalac MX-270) C-1: Trimethylolpropane triglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX-321L, total chlorine content: 3000 ppm by mass) C-2: Pentaerythritol tetraglycidyl ether (manufactured by Resonac Co., Ltd., trade name: Shoffree PETG, total chlorine content: less than 10 ppm by mass) D-1: Triarylsulfonium salt (manufactured by San-Apro Ltd., trade name: CPI-310B, anion: tetrakis(pentafluorophenyl) borate) D-2: Triarylsulfonium salt (manufactured by San-Apro Ltd., trade name: CPI-310FG) E-1: 3-Trimethoxysilylpropyl succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-12-967C) E’-1: 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403) F-1: Acrylate-modified polysiloxane (manufactured by Evonik Japan Co., Ltd., trade name: RC-711) G-1: Propylene glycol monomethyl ether acetate (manufactured by FUJIFILM Wako Pure Chemical Corporation, product name: 2-methoxy-1-methylethyl acetate)

[0127] <Adhesion of cured film (initial)>[ The photosensitive resin composition was spin-coated on a SiO2 wafer as an inorganic substrate and heated on a hot plate at 120 °C for 3 minutes to prepare a coating film with a thickness of 10 μm. The prepared coating film was exposed to i-line (365 nm) using an aligner exposure apparatus (manufactured by Mikasa Co., Ltd., product name: Mask Aligner ML-210FM) at an exposure dose of 1000 mJ / cm 2 and exposed over the entire surface.

[0128] Next, the exposed coating film was heated at 85 °C for 4 minutes (post-exposure bake). Then, heat treatment was performed at 180 °C for 60 minutes using a solvent drying safety specification thermostat (manufactured by Kusumoto Chemical Co., Ltd., product name: HG220) to form a cured film with a thickness of 10 μm.

[0129] Next, using a cross-cut guide (manufactured by Co-Tech Co., Ltd., product name "CCJ-1") and a cutter (NT cutter eA-300), 11 cuts were made vertically and horizontally at 1 mm intervals in the cured film to create 100 grids. After firmly pressing cellophane tape (manufactured by Nichiban Co., Ltd., product name "CT1535") onto the grid portion, the tape was peeled off and the number of peeled grids was measured. The same evaluation was performed 3 times and the average value was obtained. Based on the following criteria, the adhesion was evaluated from this average value. The results are shown in Table 1. A: The number of peeled grids is less than 10 B: The number of peeled grids is 10 or more and less than 90 C: The number of peeled grids is 90 or more

[0130] <Adhesion of cured film after high temperature and high humidity test>[ In the same manner as the above <adhesion of the cured film (initial)>, a cured film of the photosensitive resin composition was formed on the SiO2 wafer. The SiO2 wafer on which the cured film was formed was left standing for 100 hours in an environment of a temperature of 130 °C and a humidity of 85% RH, and a high-temperature and high-humidity test was conducted. After the test, the adhesion was evaluated in the same manner as the above <adhesion of the cured film (initial)>. The results are shown in Table 1.

[0131] <Insulation reliability> A comb-shaped electrode substrate was prepared in which a copper wiring with a thickness of 4 μm and a line width / space width of 10 μm / 10 μm was formed on a Si substrate having a SiO2 film on its surface via a seed layer (Ti / Cu = 25 μm / 150 μm). After spin-coating the photosensitive resin composition of Example 4 on the copper wiring of the comb-shaped electrode substrate, it was heated at 120 °C for 3 minutes to form a coating film. The formed coating film was exposed to i-line (365 nm) with an exposure amount of 1000 mJ / cm 2 over the entire surface using an aligner exposure apparatus (manufactured by Mikasa Co., Ltd., trade name: Mask Aligner ML-210FM), and then heated at 85 °C for 4 minutes (post-exposure bake) to form a cured film with a thickness of 7 μm.

[0132] Using the above comb-shaped electrode substrate on which the cured film was formed, the insulation reliability was evaluated by b-HAST (biased-Highly Accelerated Stress Test). The b-HAST conditions were an applied voltage of 3.3 V, a temperature of 130 °C, and a humidity of 85% RH. As a result, the cured film formed using the photosensitive resin composition of Example 4 could maintain an electrical resistance value of 10 8 Ω or more for 100 hours, and it was confirmed that it had good insulation reliability.

[0133]

Table 1

Explanation of symbols

[0134] 1... Substrate, 2... Photosensitive layer, 3... Circuit groove, 4... Resin pattern, 5... Seed metal layer, 6... Plated layer, 7... Conductor layer, 8... Conductor pattern.

Claims

1. Component (A): A resin having a phenolic hydroxyl group, Component (B): A compound having a methylol group or an alkoxyalkyl group, Component (C): An aliphatic compound having two or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group, Component (D): A photosensitive acid generator, and Component (E): A silane coupling agent having an acid anhydride group, A photosensitive resin composition containing the same.

2. The photosensitive resin composition according to Claim 1, wherein the content of the component (E) is 0.5 to 10% by mass based on the total solid content of the photosensitive resin composition.

3. The photosensitive resin composition according to Claim 1, wherein the content of the component (E) is 1 to 10 parts by mass with respect to 100 parts by mass of the component (A).

4. The photosensitive resin composition according to Claim 1, wherein the component (E) is a compound represented by the following general formula (II). 【Chemical 1】 [In formula (II), R ３３ , R ３４ and R ３５ each independently represents an alkyl group having 1 to 6 carbon atoms, and g represents an integer of 1 to 10.]

5. The photosensitive resin composition according to Claim 1, wherein the component (C) includes an aliphatic compound having two or more glycidyloxy groups.

6. (a) A step of applying the photosensitive resin composition according to any one of Claims 1 to 5 onto a substrate and drying the photosensitive resin composition to form a photosensitive layer; (b) A step of exposing the photosensitive layer in a predetermined pattern, developing it, and further performing a heat treatment to obtain a resin pattern; (c) A step of plating the exposed portions of the substrate and the exposed portions of the resin pattern to form a conductor layer; (d) A step of removing a part of the conductor layer to form a conductor pattern; A method for manufacturing a circuit board comprising the above steps.

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