Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing semiconductor package substrate or printed wiring board

Abstract

A photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, the photosensitive resin composition having an absorbance per 1 [mu] m thickness with respect to light having a wavelength of 365 nm of more than 0.0041 and 0.0130 or less.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a semiconductor package substrate or a printed wiring board. Background Art

[0002] In the field of manufacturing semiconductor package substrates and printed wiring boards, as a resist material for etching and plating, a photosensitive element (laminate) having a structure in which a photosensitive resin composition and a layer containing the photosensitive resin composition (hereinafter referred to as a "photosensitive layer") are formed on a support and a protective film is arranged on the photosensitive layer is widely used.

[0003] When a semiconductor package substrate or a printed wiring board is manufactured using a photosensitive element, first, the photosensitive layer of the photosensitive element is laminated on a circuit forming substrate. Next, active light is irradiated to a predetermined portion of the photosensitive layer to cure the exposed portion. After that, after the support is peeled off, the unexposed portion of the photosensitive layer is removed with a developer, thereby forming a resist pattern on the substrate. Next, using the resist pattern as a mask, the substrate formed with the resist pattern is subjected to an etching process or a plating process to form a circuit pattern on the substrate, and finally the cured portion (resist pattern) of the photosensitive layer is peeled off from the substrate.

[0004] As a method of exposure, a photosensitive layer is pattern-exposed through a mask film or the like. In recent years, a projection exposure method has been used in which active light rays of an image of a projected photomask are irradiated onto the photosensitive layer through a lens for exposure. As a light source for the projection exposure method, an ultra-high pressure mercury lamp is used. Usually, an exposure machine that uses i-ray monochromatic light (365nm) as an exposure wavelength is more commonly used, but h-ray monochromatic light (405nm) can sometimes also be used as an exposure wavelength of iHG mixed line.

[0005] Compared with the contact exposure method, the projection exposure method is an exposure method that can ensure high resolution and high alignment. Therefore, in recent years, when miniaturization of circuit formation of semiconductor package substrates and printed wiring boards is required, the projection exposure method has attracted much attention.

[0006] With the high density of semiconductor package substrates and printed circuit boards in recent years, the demand for photosensitive resin compositions with excellent resolution and adhesion has increased. In particular, in the production of package substrates, photosensitive resin compositions that can form resist patterns with a line width / space width of 10 / 10 (unit: μm) or less are required. For example, Patent Document 1 studies the use of a predetermined photopolymerizable compound to improve resolution and adhesion.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2013-195712 Summary of the invention

[0010] Technical issues to be solved by the invention

[0011] As semiconductor package substrates and printed wiring boards become more densely populated and semiconductor packages become more highly integrated, photosensitive resin compositions are required to have further improved resolution and adhesion and to be able to form a resist pattern having a good resist shape close to a rectangle.

[0012] Here, an object of the present invention is to provide a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a semiconductor package substrate or a printed wiring board that can form a resist pattern having a good resist shape and good resolution and adhesion.

[0013] Means for solving technical problems

[0014] In order to achieve the above-mentioned object, the present invention provides the following photosensitive resin composition, photosensitive element, resist pattern forming method and semiconductor package substrate or printed wiring board manufacturing method.

[0015] [1] A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, wherein the absorbance of the photosensitive resin composition per 1 μm thickness with respect to light of a wavelength of 365 nm is greater than 0.0041 and less than 0.0130.

[0016] [2] The photosensitive resin composition according to [1] above, wherein the absorbance of the photosensitive resin composition per 1 μm thickness with respect to light of a wavelength of 365 nm is 0.0080 or less.

[0017] [3] The photosensitive resin composition according to [1] or [2], wherein the content of the photopolymerization initiator (C) is 3.0 parts by mass or more relative to 100 parts by mass of the total amount of the binder polymer (A) and the photopolymerizable compound (B).

[0018] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the (C) photopolymerization initiator is 5.0 parts by mass or more relative to 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound.

[0019] [5] The photosensitive resin composition according to any one of [1] to [4], further comprising (D) a sensitizer.

[0020] [6] The photosensitive resin composition according to [5], wherein the (D) sensitizer comprises at least one selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds and coumarin compounds.

[0021] [7] The photosensitive resin composition according to [5] or [6], wherein the content of the sensitizer (D) is 0.03 parts by mass or less relative to 100 parts by mass of the total amount of the binder polymer (A) and the photopolymerizable compound (B).

[0022] [8] The photosensitive resin composition according to any one of [5] to [7], wherein the mass ratio of the content of the above-mentioned (C) photopolymerization initiator to the content of the above-mentioned (D) sensitizer, i.e., the content of (C) photopolymerization initiator / the content of (D) sensitizer, is 80 or more.

[0023] [9] The photosensitive resin composition according to any one of [1] to [8], further comprising (E) a hydrogen donor, wherein the content of the (E) hydrogen donor is 0.3 parts by mass or more relative to 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound.

[0024]

[10] The photosensitive resin composition according to [9] above, wherein the content of the hydrogen donor (E) is 0.55 parts by mass or more relative to 100 parts by mass of the total amount of the binder polymer (A) and the photopolymerizable compound (B).

[0025]

[11] The photosensitive resin composition according to [9] or

[10] , wherein the total content of the (C) photopolymerization initiator and the (E) hydrogen donor is 4.0 parts by mass or more relative to 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound.

[0026]

[12] The photosensitive resin composition according to any one of [1] to

[11] , which is used for forming a resist pattern using a projection exposure method.

[0027]

[13] A photosensitive element comprising a support and a photosensitive layer formed on the support and comprising the photosensitive resin composition according to any one of [1] to

[12] above.

[0028]

[14] The photosensitive element according to

[13] above, wherein the support has a haze of 0.01 to 1.0%.

[0029]

[15] The photosensitive element according to

[13] or

[14] , wherein the number of particles having a diameter of 5 μm or more contained in the support is 5 particles / mm 2 the following.

[0030]

[16] The photosensitive element according to any one of

[13] to

[15] , comprising an intermediate layer containing polyvinyl alcohol between the support and the photosensitive layer.

[0031]

[17] A method for forming a resist pattern, comprising: a photosensitive layer forming step of laminating a photosensitive layer comprising the photosensitive resin composition described in any one of [1] to

[12] on a substrate; an exposure step of irradiating a predetermined portion of the photosensitive layer with active light to form a photocured portion; and a development step of removing an area other than the predetermined portion of the photosensitive layer from the substrate.

[0032]

[18] The method for forming a resist pattern according to

[17] above, wherein in the exposure step, the photocured portion is formed by irradiating active light rays by projection exposure.

[0033]

[19] A method for forming a resist pattern, comprising: a photosensitive layer forming step of laminating a photosensitive layer of the photosensitive element described in any one of

[13] to

[16] on a substrate; an exposure step of irradiating a specified portion of the photosensitive layer with active light to form a photocured portion; and a development step of removing an area other than the specified portion of the photosensitive layer from the substrate.

[0034]

[20] The method for forming a resist pattern according to

[19] above, wherein, in the exposure step, the photocured portion is formed by irradiating active light rays by projection exposure.

[0035]

[21] A method for manufacturing a semiconductor package substrate or a printed wiring board, comprising: forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the resist pattern forming method described in

[17] or

[18] above.

[0036]

[22] A method for manufacturing a semiconductor package substrate or a printed wiring board, comprising: forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the resist pattern forming method described in

[19] or

[20] above.

[0037] Effects of the Invention

[0038] According to the present invention, a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a semiconductor package substrate or a printed wiring board can be provided, which can form a resist pattern having a good resist shape and good resolution and adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a schematic cross-sectional view showing a photosensitive element according to one embodiment. DETAILED DESCRIPTION

[0040] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0041] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. In this specification, the term "layer" includes structures of shapes formed on a portion of the surface when viewed from a top view, in addition to structures of shapes formed on the entire surface. In this specification, "(meth)acrylic acid" refers to at least one of "acrylic acid" and its corresponding "methacrylic acid". The same applies to other similar expressions such as (meth)acrylates.

[0042] In this specification, the numerical range represented by "~" indicates a range including the numerical values ​​recorded before and after "~" as the minimum value and the maximum value, respectively. In the numerical range recorded in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage can be replaced by the upper limit or lower limit of the numerical range of other stages. Furthermore, in the numerical range recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the examples.

[0043] In the present specification, when referring to the amount of each component in a composition, if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of the plurality of substances present in the composition.

[0044] [Photosensitive resin composition]

[0045] The photosensitive resin composition of this embodiment contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. The absorbance of the photosensitive resin composition per 1 μm thickness with respect to light of a wavelength of 365 nm is greater than 0.0041 and less than 0.0130.

[0046] The photosensitive resin composition of this embodiment contains the above-mentioned (A) to (C) components as essential components, and has an absorbance of greater than 0.0041 and less than 0.0130 per 1 μm thickness with respect to light of a wavelength of 365 nm, thereby being able to form a resist pattern having a good resist shape and to obtain good resolution and adhesion.

[0047] The photosensitive resin composition of the present embodiment may contain component (D): a sensitizer. In addition, the photosensitive resin composition of the present embodiment may contain component (E): a hydrogen donor. Furthermore, the photosensitive resin composition of the present embodiment may further contain other components other than the above-mentioned components (A) to (E). The following is a more detailed description of each component used in the photosensitive resin composition of the present embodiment.

[0048] (Component (A): Binder polymer)

[0049] The photosensitive resin composition comprises one or more of the components (A). Examples of the components (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins. The components (A) may include acrylic resins in order to further improve the alkali developability.

[0050] The acrylic resin has a structural unit derived from, for example, (meth)acrylic acid, and may further have a structural unit derived from other monomers other than (meth)acrylic acid. The other monomers may be one or more.

[0051] The other monomers may include, for example, (meth)acrylates. Examples of (meth)acrylates include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, and aryl (meth)acrylates.

[0052] Other monomers may include alkyl (meth)acrylates from the viewpoint of improving alkali developability and stripping properties. The alkyl group of the alkyl (meth)acrylate may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or structural isomers thereof, and may be an alkyl group having 1 to 4 carbon atoms from the viewpoint of further improving stripping properties.

[0053] When the other monomers include an alkyl (meth)acrylate, the content of the alkyl (meth)acrylate may be 1% by mass or more, 2% by mass or more, or 3% by mass or more from the viewpoint of excellent release properties, and may be 80% by mass or less, 60% by mass or less, or 50% by mass or less from the viewpoint of further improving resolution and adhesion, based on the total amount of monomers constituting the component (A).

[0054] The other monomers may include styrene or a styrene derivative from the viewpoint of further improving resolution and adhesion. Examples of the styrene derivative include vinyltoluene and α-methylstyrene.

[0055] When other monomers include styrene or styrene derivatives, the content of styrene and styrene derivatives may be 40% by mass or more, 45% by mass or more, 47% by mass or more, or 50% by mass or more from the viewpoint of further improving the resolution, and may be 90% by mass or less, 85% by mass or less, or 80% by mass or less from the viewpoint of developability, based on the total amount of monomers constituting component (A).

[0056] Other monomers may include hydroxyalkyl (meth)acrylates from the viewpoint of further improving resolution and adhesion. Hydroxyalkyl (meth)acrylates may be, for example, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, and the like. Furthermore, in the hydroxyalkyl (meth)acrylate unit, when the number of carbon atoms in the alkyl portion is 3 or more, a branched structure may be provided. As component (A), by using an acrylic resin having a structural unit derived from hydroxyalkyl (meth)acrylate, the minimum development time can be shortened and productivity can be improved, and the lamination of the photosensitive layer comprising the photosensitive resin composition can be improved.

[0057] When other monomers include hydroxyalkyl (meth)acrylate, the content of hydroxyalkyl (meth)acrylate may be 0.5 mass % or more, 0.75 mass % or more, or 1.0 mass % or more from the viewpoint of dispersibility, and may be 20 mass % or less, 15 mass % or less, or 8 mass % or less from the viewpoint of water absorption, based on the total amount of monomers constituting component (A).

[0058] In addition, examples of other monomers include acrylic acid amides such as diacetone acrylic acid amide, acrylonitrile, ethers of vinyl alcohol such as vinyl-n-butyl ether, alkyl (meth)acrylates, benzyl (meth)acrylates such as benzyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-bromoacrylic acid, α-chloroacrylic acid, β-furfuryl (meth)acrylate, β-styrene (meth)acrylate, maleic acid, maleic anhydride, maleic acid monoesters such as monomethyl maleic acid, monoethyl maleic acid, and monoisopropyl maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

[0059] The acid value of the component (A) may be 100 mgKOH / g or more, 120 mgKOH / g or more, 140 mgKOH / g or more, or 150 mgKOH / g or more from the viewpoint of enabling appropriate development, and may be 250 mgKOH / g or less, 240 mgKOH / g or less, or 230 mgKOH / g or less from the viewpoint of improving the adhesion (developer resistance) of the cured product of the photosensitive resin composition. The acid value of the component (A) can be adjusted by the content of the structural unit constituting the component (e.g., the structural unit derived from (meth)acrylic acid).

[0060] The acid value of component (A) can be measured as follows. First, accurately weigh 1 g of the binder polymer to be measured for the acid value. Add 30 g of acetone to the accurately weighed binder polymer to dissolve it evenly. Next, phenolphthalein as an indicator is appropriately added to the solution and titrated using a 0.1N potassium hydroxide (KOH) aqueous solution. The acid value is determined by calculating the number of mg of KOH required to neutralize the acetone solution of the binder polymer to be measured. When a solution formed by mixing a binder polymer with a synthetic solvent, a diluent solvent, etc. is used as the measurement object, the acid value is calculated by the following formula.

[0061] Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)

[0062] In the formula, Vf represents the titration amount of the KOH aqueous solution (mL), Wp represents the mass (g) of the solution containing the measured binder polymer, and I represents the ratio (mass %) of the nonvolatile component in the solution containing the measured binder polymer.

[0063] When the binder polymer is mixed with a volatile component such as a synthetic solvent or a diluent solvent and prepared, the acid value can be measured by heating at a temperature 10° C. or higher than the boiling point of the volatile component for 1 to 4 hours before accurate weighing to remove the volatile component.

[0064] The weight average molecular weight (Mw) of the component (A) may be 10,000 or more, 20,000 or more, or 25,000 or more from the viewpoint of excellent adhesion (developer resistance) of the cured product of the photosensitive resin composition, and may be 100,000 or less, 80,000 or less, or 60,000 or less from the viewpoint of enabling appropriate development. The degree of dispersion (Mw / Mn) of the component (A) may be, for example, 1.0 or more or 1.5 or more, and may be 3.0 or less or 2.5 or less from the viewpoint of further improving adhesion and resolution.

[0065] Weight average molecular weight and dispersion degree can be measured by gel permeation chromatography (GPC) using the calibration curve of standard polystyrene, for example. More specifically, it is possible to measure under the conditions described in the embodiments. In addition, about the compound with low molecular weight, when it is difficult to measure with the measuring method of the above-mentioned weight average molecular weight, it is also possible to measure the molecular weight with other methods, calculate its average.

[0066] The content of component (A) is based on the total solid content of the photosensitive resin composition. From the viewpoint of excellent film formability, it can be 20% by mass or more, 30% by mass or more, or 40% by mass or more. From the viewpoint of further excellent sensitivity and resolution, it can be 90% by mass or less, 80% by mass or less, or 65% by mass or less.

[0067] (Component (B): photopolymerizable compound)

[0068] The photosensitive resin composition comprises one or more of the components (B). The component (B) has at least one ethylenically unsaturated bond and is not particularly limited if it is a photopolymerizable compound. The component (B) may comprise a polyfunctional monomer having two or more reactive groups that react via free radicals. From the viewpoint of further improving alkali developability, resolution, and release properties after curing, the component (B) may comprise a bisphenol A type (meth) acrylate compound.

[0069] Examples of the bisphenol A type (meth)acrylate compound include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane. From the viewpoint of further improving resolution and release properties, the component (B) may include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, etc.

[0070] As commercially available bisphenol A type (meth)acrylate, for example, as 2,2-bis(4-((meth)acryloyloxydipropoxy)phenyl)propane, BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) can be mentioned, as ethoxylated bisphenol A dimethacrylate, BP-2EM (manufactured by Kyoeisha Chemical Co., Ltd., product name) can be mentioned, and as 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane, BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) and FA-321M (manufactured by Showa Denko Materials Co., Ltd., product name) can be mentioned. These bisphenol A type (meth)acrylates can be used alone or in combination of two or more.

[0071] The content of bisphenol A type (meth) acrylate can be 40 to 98 mass %, 50 to 97 mass %, 60 to 95 mass % or 70 to 90 mass % based on the total amount of component (B). When the content is 40 mass % or more, the resolution, adhesion and the inhibition of the generation of the resist foot portion become better, and when it is 98 mass % or less, the development time is appropriately shortened, and it is more difficult to generate development residues.

[0072] As the (B) component other than the bisphenol type (meth) acrylate, from the viewpoint of improving the flexibility of the cured product (cured film), at least one of the polyalkylene glycol di(meth) acrylates having at least one of the (poly)oxyethylene chain and the (poly)oxypropylene chain in the molecule may be further included, and the polyalkylene glycol di(meth) acrylate having both of the (poly)oxyethylene chain and the (poly)oxypropylene chain in the molecule may be further included. As the above-mentioned polyalkylene glycol di(meth) acrylate, for example, FA-023M (manufactured by Showa Denko Materials Co., Ltd., product name), FA-024M (manufactured by Showa Denko Materials Co., Ltd., product name) and NK ESTER HEMA-9P (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) can be cited. These can be used alone or in combination of two or more.

[0073] The content of the polyalkylene glycol di(meth)acrylate may be 2 to 40% by mass, 3 to 30% by mass, or 5 to 20% by mass based on the total amount of the component (B).

[0074] As the (B) component other than the above, nonylphenoxy polyethyleneoxy acrylate, phthalic acid compounds, (meth) acrylic acid polyol esters, (meth) acrylic acid alkyl esters, etc. can also be used. Among them, from the viewpoint of improving the resolution, adhesion, resist shape and the peeling characteristics after curing in a well-balanced manner, the (B) component can include at least one selected from nonylphenoxy polyethyleneoxy acrylate and phthalic acid compounds. However, the refractive index of these compounds is relatively low, so from the viewpoint of improving the resolution, its content is based on the total amount of the (B) component, and can be 5 to 50 mass %, 5 to 40 mass % or 10 to 30 mass %.

[0075] Examples of the nonylphenoxy polyethyleneoxy acrylate include nonylphenoxy trivinyloxy acrylate, nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, nonylphenoxy hexavinyloxy acrylate, nonylphenoxy heptavinyloxy acrylate, nonylphenoxy octavinyloxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxy decavinyloxy acrylate, and nonylphenoxy undecvinyloxy acrylate.

[0076] As phthalic acid compounds, for example, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate can be mentioned, among which γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate can be mentioned. γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate is commercially available as FA-MECH (manufactured by Showa Denko Materials Co., Ltd., product name).

[0077] From the viewpoint of improving sensitivity and reducing tailing, the component (B) may contain a (meth)acrylic polyol. Examples of the (meth)acrylate polyol ester include trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, trimethylolpropane polybutoxy tri(meth)acrylate, trimethylolpropane polyethoxy polypropoxy tri(meth)acrylate, trimethylolethane polyethoxy tri(meth)acrylate, trimethylolethane polypropoxy tri(meth)acrylate, trimethylolethane polybutoxy tri(meth)acrylate, trimethylolethane polyethoxy polypropoxy tri(meth)acrylate, pentaerythritol polyethoxy tri(meth)acrylate, pentaerythritol polypropoxy tri(meth)acrylate, pentaerythritol polybutoxy tri(meth)acrylate, pentaerythritol polyethoxy polypropoxy tri(meth)acrylate, glycerol polyethoxy tri(meth)acrylate, glycerol polypropoxy tri(meth)acrylate, glycerol polybutoxy tri(meth)acrylate, and glycerol polyethoxy polypropoxy tri(meth)acrylate.

[0078] The content of component (B) is preferably 20 to 60 parts by mass, more preferably 30 to 55 parts by mass, and further preferably 35 to 50 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (B). When the content of component (B) is within this range, the photosensitive resin composition has better resolution, adhesion, and resist formation, as well as better photosensitivity and coating properties.

[0079] (Component (C): photopolymerization initiator)

[0080] The photosensitive resin composition may contain one or more of the components (C). Components (C) include hexaarylbiimidazole compounds; benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinophenyl]-1-butanone. Aromatic ketones such as 1-phenoxy-propanone; quinones such as alkyl anthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, etc.

[0081] The component (C) may contain a hexaarylbisimidazole compound from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. The aryl group of the hexaarylbisimidazole compound may be a phenyl group, etc. The hydrogen atom bonded to the aryl group of the hexaarylbisimidazole compound may be substituted with a halogen atom (chlorine atom, etc.).

[0082] The hexaarylbisimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. From the perspective of easily obtaining excellent sensitivity, resolution, and adhesion, the hexaarylbisimidazole compound may include a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole.

[0083] The content of the hexaarylbisimidazole compound may be 90% by mass or more, 95% by mass or more, or 99% by mass or more based on the total amount of the component (C) in order to easily obtain excellent sensitivity, resolution, and adhesion. The component (C) may consist only of the hexaarylbisimidazole compound.

[0084] The content of the component (C) can be 3.0 parts by mass or more, 4.0 parts by mass or more, 5.0 parts by mass or more, or 5.5 parts by mass or more, and can be 10 parts by mass or less, 9.0 parts by mass or less, 8.5 parts by mass or less, or 8.0 parts by mass or less, relative to 100 parts by mass of the total amount of the components (A) and (B), from the viewpoint of being able to further improve sensitivity, resolution and adhesion, and to easily form a resist pattern having a better resist shape. That is, the content of the component (C) can be 3.0 to 10 parts by mass, 4.0 to 9.0 parts by mass, 5.0 to 8.5 parts by mass, or 5.5 to 8.0 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B). In particular, by setting the content of the component (C) to 3.0 parts by mass or more, the adhesion can be further improved. Furthermore, by setting the content of the component (C) within the above range, it is easy to adjust the absorbance of the photosensitive resin composition per 1 μm thickness with respect to light of a wavelength of 365 nm to a range of more than 0.0041 and less than 0.0130. Furthermore, by setting the content of the component (C) within the above range, it is easy to obtain a photosensitive resin composition suitable for forming a resist pattern using a projection exposure method.

[0085] ((D) ingredient: sensitizer)

[0086] The photosensitive resin composition may contain one or more of the components (D). The component (D) may be a photosensitizer. Examples of the component (D) include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, stilbene compounds, and triarylamine compounds.

[0087] Examples of pyrazoline compounds include 1-phenyl-3-(4-methoxystyrene)-5-(4-methoxyphenyl)pyrazoline, 1-phenyl-3-(4-tert-butylstyrene)-5-(4-tert-butylphenyl)pyrazoline, and 1-phenyl-3-biphenyl-5-(4-tert-butylphenyl)pyrazoline. Examples of anthracene compounds include 9,10-dibutoxyanthracene and 9,10-diphenylanthracene. Examples of coumarin compounds include 3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), and 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]lysin-11-one.

[0088] From the viewpoint of being able to further improve sensitivity, resolution and adhesion and to easily form a resist pattern having a better resist shape, the component (D) may include at least one selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds and coumarin compounds, and may also include at least one selected from the group consisting of 9,10-dibutoxyanthracene, 4,4'-bis(diethylamino)benzophenone, and 1-phenyl-3-(4-methoxystyrene)-5-(4-methoxyphenyl)pyrazoline. Furthermore, when exposure is performed at an exposure wavelength of about 405 nm, from the viewpoint of further improving sensitivity, resolution and adhesion, the component (D) may include at least one selected from the group consisting of pyrazoline compounds and anthracene compounds.

[0089] When the photosensitive resin composition includes component (D), its content can be 0.01 mass parts or more, or 0.02 mass parts or more, and can be 1.5 mass parts or less, 1.0 mass parts or less, 0.8 mass parts or less, 0.5 mass parts or less, 0.2 mass parts or less, 0.1 mass parts or less, 0.05 mass parts or less, or 0.03 mass parts or less, from the viewpoint of being able to further improve sensitivity, resolution and adhesion and easily form a resist pattern with a better resist shape, relative to the total amount of 100 mass parts of components (A) and (B). Particularly, by reducing the content of component (D) to below the above-mentioned upper limit, there is a tendency to make the resist shape better. In addition, when the content of component (D) is set to below 0.03 mass parts, there is a tendency to further improve the acid degreasing treatment resistance before plating of the resist and the plating solution resistance of the resist. Furthermore, by setting the content of the component (D) within the above range, it is easy to adjust the absorbance of the photosensitive resin composition per 1 μm thickness with respect to light of a wavelength of 365 nm to a range of more than 0.0041 and less than 0.0130. Furthermore, by setting the content of the component (D) within the above range, it is easy to obtain a photosensitive resin composition suitable for forming a resist pattern using a projection exposure method.

[0090] When the photosensitive resin composition contains the component (D), the mass ratio of the content of the component (C) to the content of the component (D) (the content of the component (C) / the content of the component (D)) may be 40 or more, 50 or more, 80 or more, 100 or more, 150 or more, or 200 or more, and may be 500 or less, 400 or less, or 300 or less. By setting the mass ratio within the above range, there is a tendency that the adhesion can be further improved. In addition, by setting the mass ratio within the above range, it is easy to adjust the absorbance of the photosensitive resin composition per 1 μm thickness with respect to light of a wavelength of 365 nm to a range of more than 0.0041 and less than 0.0130. Furthermore, by setting the mass ratio within the above range, there is a tendency that a photosensitive resin composition suitable for forming a resist pattern using a projection exposure method can be easily obtained.

[0091] ((E) component: hydrogen donor)

[0092] The photosensitive resin composition may contain one or more of the components (E). The component (E) is a hydrogen-donating compound. When the photosensitive resin composition contains the component (E), the sensitivity, resolution and adhesion of the photosensitive resin composition are improved, and a resist pattern having a better resist shape is easily formed.

[0093] Examples of the component (E) include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, N-phenylglycine, and colorless crystal violet. These may be used alone or in combination of two or more.

[0094] When the photosensitive resin composition includes (E) component, its content can further improve sensitivity, resolution and adhesion relative to the total amount of (A) component and (B) component 100 mass parts, and it is easy to form a resist pattern with a better resist shape. It can be 0.3 mass parts or more, 0.5 mass parts or more, 0.55 mass parts or more, 0.6 mass parts or more, 0.7 mass parts or more, or 0.75 mass parts or more, and can be 2 mass parts or less, 1.5 mass parts or less, 1.0 mass parts or less, or 0.9 mass parts or less. In particular, by setting the content of (E) component to 0.3 mass parts or more, it is possible to further improve adhesion. In addition, by increasing the content of (E) component, under conditions where the adhesion is unfavorable under low exposure conditions or development conditions that are longer than usual, it is possible to improve adhesion. In addition, when the content of (E) component is 2 mass parts or less, it is possible to further shorten the stripping time of the resist pattern.

[0095] When the photosensitive resin composition includes component (E), the total content of component (C) and component (E) can be 4.0 parts by mass or more, 5.0 parts by mass or more, or 6.0 parts by mass or more, or 12.0 parts by mass or less, 10.0 parts by mass or less, or 9.0 parts by mass or less, from the viewpoint of further improving sensitivity, resolution and adhesion and easily forming a resist pattern with a better resist shape, relative to 100 parts by mass of the total amount of component (A) and component (B). By setting the total content of component (C) and component (E) to 4.0 parts by mass or more, adhesion can be further improved. In addition, by setting the total content of component (C) and component (E) to the above range, it is easy to adjust the absorbance of the photosensitive resin composition per 1 μm thickness relative to light of a wavelength of 365 nm to a range of more than 0.0041 and less than 0.0130. Furthermore, by setting the total content of the component (C) and the component (E) within the above range, it is easy to obtain a photosensitive resin composition suitable for forming a resist pattern using a projection exposure method.

[0096] (Heterocyclic Compound)

[0097] The photosensitive resin composition of the present embodiment may further contain a heterocyclic compound. Thus, the resolution and adhesion of the photosensitive resin composition can be further improved. As heterocyclic compounds, for example, 5-carboxybenzotriazole and 5-amino-1H-tetrazole can be cited. In particular, by containing a benzotriazole derivative such as 5-carboxybenzotriazole in the photosensitive resin composition, the resist removal property from the substrate can be improved. These can be used alone or in combination of two or more.

[0098] When the photosensitive resin composition contains a heterocyclic compound, the content thereof may be 0.01 to 5.0 mass %, 0.03 to 3.0 mass %, or 0.1 to 1.5 mass % based on the total solid content of the photosensitive resin composition. When the content of the heterocyclic compound is 0.01 mass % or more, there is a tendency to further improve the resolution and adhesion, and when it is 5.0 mass % or less, there is a tendency to shorten the development time and peeling time of the photosensitive layer.

[0099] (Polymerization Inhibitor)

[0100] The photosensitive resin composition of the present embodiment may further contain a polymerization inhibitor. Thus, the resolution of the photosensitive resin composition is good. And the temperature stability of the film is improved. As a polymerization inhibitor, for example, tert-butylcatechol and 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl can be cited. In particular, when the photosensitive resin composition contains 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl (4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl), the lamination of the photosensitive layer containing the photosensitive resin composition can be improved. These can be used alone or in combination of two or more.

[0101] When the photosensitive resin composition contains a polymerization inhibitor, the content thereof may be 0.001 to 1.0 mass %, 0.005 to 0.5 mass %, or 0.01 to 0.1 mass % based on the total solid content of the photosensitive resin composition. When the content of the polymerization inhibitor is 0.001 mass % or more, the resolution can be further improved, and when it is 1.0 mass % or less, the sensitivity can be further improved.

[0102] (Other ingredients)

[0103] The photosensitive resin composition can also further contain other components as needed. As other components, for example, photopolymerizable compounds (oxetane compounds, etc.) having at least one cyclic ether group that can be cationically polymerized in the molecule, cationic polymerization initiators, tribromophenyl sulfone, photochromic agents, thermal coloring inhibitors, plasticizers (p-toluenesulfonamide, etc.), silane coupling agents, pigments, dyes (malachite green, diamond green, etc.), fillers, defoamers, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, developers, thermal crosslinking agents, etc. can be cited. These can be used alone or in combination of two or more. The content of other components can be about 0.01 to 20% by mass.

[0104] The photosensitive resin composition may contain at least one organic solvent in order to improve the handling properties of the photosensitive composition or to adjust the viscosity and storage stability. As the organic solvent, commonly used organic solvents may be used without particular limitation. Examples of organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and mixed solvents thereof. For example, it may be used as a solution (hereinafter referred to as a "coating solution") in which component (A), component (B), and component (C) are dissolved in an organic solvent and the solid content is about 30 to 60% by mass. In addition, the solid content refers to the residual component obtained by removing the volatile component from the solution of the photosensitive resin composition.

[0105] (Absorbance)

[0106] The absorbance of the light of wavelength 365nm of the photosensitive resin composition of this embodiment per 1μm relative to the thickness is greater than 0.0041 and less than 0.0130. By the absorbance being greater than 0.0041, the sensitivity, resolution and adhesion can be improved. And, when the absorbance is less than 0.0130, the sensitivity, resolution and adhesion can be improved, and a resist pattern with a good resist shape can be formed. From the viewpoint of further improving the sensitivity, resolution and adhesion, the absorbance can be more than 0.0045, more than 0.0050, more than 0.0055, or more than 0.0060, and from the viewpoint of further improving the sensitivity, resolution and adhesion and making the resist shape better, it can be less than 0.0120, less than 0.0110, less than 0.0100, less than 0.0090, or less than 0.0080.

[0107] The absorbance of the photosensitive resin composition can be appropriately adjusted by the types and contents of the above-mentioned (B) photopolymerizable compound, (C) photopolymerization initiator, (D) sensitizer, (E) hydrogen donor, and other components.

[0108] Absorbance of the photosensitive resin composition The photosensitive resin composition is formed into a film to form a photosensitive layer, and the absorbance of the photosensitive layer can be measured with an ultraviolet visible spectrophotometer such as U-3310 spectrophotometer (manufactured by Hitachi High-Tech Corporation) to measure the absorbance of light with a wavelength of 365 nm. The absorbance per 1 μm thickness of the photosensitive resin composition can be obtained by dividing the absorbance measured on the above-mentioned photosensitive layer by the thickness of the photosensitive layer (unit: μm).

[0109] [Photosensitive element]

[0110] The photosensitive element of this embodiment includes a support and a photosensitive layer formed on the support and containing the above-mentioned photosensitive resin composition. When the photosensitive element of this embodiment is used, after the photosensitive layer is laminated on the substrate, it can be exposed without peeling off the support. The photosensitive element can include a protective layer on the surface of the photosensitive layer opposite to the support. In addition, the photosensitive element can include an intermediate layer between the support and the photosensitive layer.

[0111] Figure 1 FIG. 1 is a schematic cross-sectional view of a photosensitive element according to one embodiment. Figure 1 As shown in , the photosensitive element 1 includes a support 2 , a photosensitive layer 3 provided on the support 2 , and a protective layer 4 provided on the side of the photosensitive layer 3 opposite to the support 2 .

[0112] (Support 2)

[0113] As a support, a heat-resistant and solvent-resistant polymer film (support film) such as polyester such as polyethylene terephthalate (PET), polypropylene, polyethylene and other polyolefins can be used. Among them, PET film can be used from the viewpoint of being easy to obtain and having excellent operability (especially heat resistance, heat shrinkage, breaking strength) of the manufacturing process.

[0114] The haze of the support can be 0.01 to 1.0% or 0.01 to 0.5%. When the haze of the support is 0.01% or more, there is a tendency to easily manufacture the support itself, and when it is 1.0% or less, there is a tendency to reduce the micro defects that can be produced in the resist pattern. Here, "haze" refers to turbidity. The haze of the present invention refers to a value measured using a commercially available haze meter (turbidimeter) according to the method specified in JIS K 7105. The haze can be measured, for example, by a commercially available turbidimeter such as NDH-5000 (manufactured by NIPPONDENSHOKU INDUSTRIES Co., LTD).

[0115] The number of particles with a diameter of 5 μm or more contained in the support is 5 / mm 2The average particle size of the particles may be less than 5 μm, less than 1 μm or less than 0.1 μm. In addition, the lower limit of the average particle size is not particularly limited and may be more than 0.001 μm.

[0116] As commercially available products of these supports, for example, there are three-layer biaxially oriented PET films containing particles in the outermost layer, such as "QS48" (TORAY INDUSTRIES, INC.), "FB40" (TORAY INDUSTRIES, INC.), "FS-31" (TORAY INDUSTRIES, INC.), and "HTF-01" (Teijin Film Solutions Limited); and two-layer biaxially oriented PET films having a layer containing particles on one side, such as "A-1517" (TOYOBO CO., LTD.) and "R705G" (Mitsubishi Chemical Corporation).

[0117] The thickness of the support may be 1 to 100 μm, 5 to 50 μm, or 5 to 30 μm. When the thickness is 1 μm or more, cracking of the support can be suppressed when the support is peeled off, and when the thickness is 100 μm or less, a decrease in resolution can be suppressed.

[0118] (Middle layer)

[0119] The photosensitive element may have an intermediate layer (not shown) between the above-mentioned support and the photosensitive layer. The intermediate layer may be a barrier layer with gas barrier properties. By having such an intermediate layer (barrier layer), the adverse effects of oxygen mixing on the photosensitive layer when the support is peeled off for exposure can be reduced. The intermediate layer may be a layer containing a water-soluble resin. In addition, the intermediate layer may be a layer containing a water-soluble resin and an alcohol having a carbon number of 3 or more. In this case, even if the intermediate layer does not contain a peeling accelerator, the support can be smoothly peeled off from the intermediate layer, thereby suppressing the deterioration of the resolution of the formed resist pattern when the photosensitive layer is exposed through the intermediate layer after the support is peeled off.

[0120] The intermediate layer is a layer formed using the intermediate layer forming resin composition of the present embodiment described later. The intermediate layer forming resin composition of the present embodiment may contain a water-soluble resin, an alcohol having a carbon number of 3 or more, and water. In addition, the intermediate layer may be water-soluble or soluble in a developer. In addition, based on the view that the intermediate layer can further improve the gas barrier properties, the adhesive force between the support and the intermediate layer may be smaller than the adhesive force between the intermediate layer and the photosensitive layer. That is, it can be said that when the support is peeled off from the photosensitive element, the unintended peeling of the intermediate layer and the photosensitive layer is suppressed.

[0121] Here, "water-soluble resin" refers to a resin having a solubility of 5 g or less in 100 mL of hexane at 25°C. The solubility can be calculated by mixing hexane at 25°C and the dried water-soluble resin and checking whether there is white turbidity. Specifically, a sample 1 obtained by adding a mixed solution of dried water-soluble resin A (g) and hexane (100 mL-A) and a sample 2 obtained by adding only 100 mL of hexane are prepared in a colorless and transparent glass container with a frosted glass stopper. Then, after the samples in the glass container are shaken and mixed thoroughly, it is confirmed that the bubbles have disappeared. After confirmation, the two containers are immediately placed side by side under diffuse sunlight or light equivalent thereto, and the state of the solution of sample 1 and the state of the solution of sample 2 are compared. When comparing sample 1 and sample 2, the amount of addition A (g) at which sample 1 begins to become more turbid or the suspension of solid components begins to be observed is set as the solubility of the water-soluble resin in 100 mL of hexane at 25°C.

[0122] As water-soluble resin, for example, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polyimides, etc. can be cited. From the viewpoint of further improving the gas barrier property of the intermediate layer, and further suppressing the deactivation of the free radicals generated by the active light for exposure, the water-soluble resin can include polyvinyl alcohol. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, for example. The saponification degree of the polyvinyl alcohol used in the present embodiment can be 50 mol% or more, 70 mol% or more, or 80 mol% or more. In addition, the upper limit of the saponification degree is 100 mol%. By including polyvinyl alcohol having a saponification degree of 50 mol% or more, there is a tendency to further improve the gas barrier property of the intermediate layer, and further improve the resolution of the formed resist pattern. In addition, the "saponification degree" of this specification refers to the value measured according to JIS K 6726 (1994) (test method for polyvinyl alcohol) specified in Japanese Industrial Standards.

[0123] The polyvinyl alcohol can be used in combination with two or more different saponification degrees, viscosities, polymerization degrees, modified species, etc. The average polymerization degree of the polyvinyl alcohol can be 300 to 5000, 300 to 3500, or 300 to 2000. In addition, the water-soluble resin can be used alone or in combination with two or more. The water-soluble resin can include, for example, polyvinyl alcohol and polyvinyl pyrrolidone. In this case, the mass ratio (PVA:PVP) between polyvinyl alcohol and polyvinyl pyrrolidone can be 40:60 to 90:10, 50:50 to 90:10, or 60:40 to 90:10.

[0124] The content of the water-soluble resin in the intermediate layer forming resin composition of the present embodiment can be 50 to 300 parts by mass, 60 to 250 parts by mass, 70 to 200 parts by mass, 80 to 150 parts by mass, or 80 to 125 parts by mass relative to 500 parts by mass of water from the viewpoint of improving gas barrier properties.

[0125] The alcohol having 3 or more carbon atoms may be a monohydric alcohol or a polyhydric alcohol (excluding the plasticizer of the polyhydric alcohol compound described later). The carbon number of the alcohol having 3 or more carbon atoms refers to the sum of the carbon atoms of the alcohol, which may be 10 or less, 8 or less, 7 or less, 6 or less, or 5 or less. The alcohol having 3 or more carbon atoms may contain at least one selected from the group consisting of compounds represented by the following chemical formulas (1) to (3) and compounds represented by the following general formula (4). By containing these alcohols having 3 or more carbon atoms, the peelability of the intermediate layer and the support can be further improved.

[0126]

[0127]

[0128] In the general formula (4), R 11 represents an alkyl group, R 12 represents an alkylene group. And, R 11 The base and R 12 The sum of the carbon atoms of the groups is 3 or more. 11 The basis and R 12 The sum of the carbon numbers of the groups may be 10 or less, 8 or less, 7 or less, 6 or less, or 5 or less from the viewpoint of further improving the affinity with water. 11 The alkyl group represented by can be an alkyl group having 1 to 4 carbon atoms, and R 12 The alkylene group represented by may be an alkylene group having 1 to 3 carbon atoms. 11 The alkyl group represented by R 12 The alkylene groups represented by the above may or may not have a substituent. 11The number of carbon atoms and R 12 The carbon number of the group is set to include the carbon number of the substituent. In addition, the alcohol having 3 or more carbon atoms represented by the general formula (4) may be 2-butoxy-ethanol or 1-methoxy-2-propanol.

[0129] The alcohols having 3 or more carbon atoms may be used alone or in combination of two or more. In addition, the solubility of the alcohols having 3 or more carbon atoms in water at 20° C. may be 300 mL / 100 mL of water or more, 500 mL / 100 mL of water or more, or 1000 mL / 100 mL of water or more from the viewpoint of further suppressing the layer separation of the intermediate layer.

[0130] The "solubility of alcohols with a carbon number of 3 or more in water at 20°C" in this specification means that it can be calculated by mixing the alcohol with water at 20°C and checking for the presence of white turbidity. Specifically, prepare sample 3 obtained by adding AmL of a mixed solution of the alcohol and (100-A)mL of water, and sample 4 obtained by adding only water (100mL) to a colorless and transparent glass container with a frosted glass stopper. Then, shake and mix sample 3 and sample 4 in the glass container thoroughly, and confirm that the bubbles have disappeared. After confirmation, immediately place the two containers side by side under diffuse sunlight or light equivalent thereto, and compare the state of the solution in sample 3 and the state of the solution in sample 4. Compare sample 3 and sample 4, and set the amount of the alcohol added AmL when sample 3 is observed to be more turbid as the solubility of the alcohol in water at 20°C.

[0131] The content of alcohols having 3 or more carbon atoms in the resin composition for forming the intermediate layer of the present embodiment can be 100 to 500 parts by mass, 110 to 480 parts by mass, 120 to 460 parts by mass, 125 to 440 parts by mass, 125 to 420 parts by mass, or 125 to 400 parts by mass relative to 500 parts by mass of water. When the content is 100 parts by mass or more, there is a tendency that the peelability of the formed intermediate layer and the support body is improved, and when it is 500 parts by mass or less, there is a tendency that the solubility of the water-soluble resin is improved, and the intermediate layer is easily formed.

[0132] The content of the alcohol having a carbon number of 3 or more in the intermediate layer of the present embodiment can be more than 0% by mass and less than 2.0% by mass, 0.001 to 2.0% by mass, or 0.005 to 1.0% by mass, based on the total amount of the intermediate layer (the total solid content of the intermediate layer forming resin composition forming the intermediate layer). When the content is less than 2.0% by mass, there is a tendency to suppress the diffusion of alcohols in subsequent steps, when it exceeds 0% by mass, there is a tendency to improve the peelability of the intermediate layer and the support, and when it is more than 0.001% by mass, there is a tendency to further improve the peelability of the intermediate layer and the support.

[0133] The resin composition for forming the intermediate layer of the present embodiment may contain alcohols having a carbon number of less than 3. In the case of containing alcohols having a carbon number of less than 3, the content thereof may be 125 to 375 parts by mass or 150 to 325 parts by mass relative to 500 parts by mass of water. When the content is 125 parts by mass or more, there is a tendency that the solubility of the water-soluble resin is improved and the intermediate layer is easily formed, and when it is 375 parts by mass or less, there is a tendency that the peelability of the formed intermediate layer and the support body is improved. In addition, the content of alcohols having a carbon number of less than 3 in the intermediate layer of the present embodiment may be 0.1 to 10% by mass, or may be 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of alcohols having a carbon number of more than 3 in the intermediate layer, from the perspective of improving the peelability of the intermediate layer and the support body.

[0134] Furthermore, the intermediate layer forming resin composition of the present embodiment may contain known additives such as a plasticizer and a surfactant within a range not impairing the effects of the present invention. Furthermore, it may contain a peeling accelerator within a range not impairing the effects of the present invention.

[0135] As a plasticizer, for example, from the viewpoint of improving elongation, a polyol compound can be contained. For example, glycerols such as glycerol, dipropylene glycol, and tripropylene glycol, (poly) alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol, trimethylolpropane, etc. can be mentioned. These plasticizers can be used alone or in combination of two or more.

[0136] The intermediate layer of the photosensitive element of the present embodiment can be formed by, for example, applying the intermediate layer-forming resin composition of the present embodiment on a support and drying the coating.

[0137] The thickness of the intermediate layer is not particularly limited. From the perspective of ease of removal of the intermediate layer, the thickness of the intermediate layer may be 12 μm or less, 10 μm or less, 8 μm or less, 7 μm or less, or 6 μm or less. Furthermore, from the perspective of ease of formation and resolution of the intermediate layer, the thickness of the intermediate layer may be 1.0 μm or more, 1.5 μm or more, 2 μm or more, 3 μm or more, or 4 μm or more.

[0138] In addition, the intermediate layer of this embodiment may have photosensitivity, but its photosensitivity is lower than that of the photosensitive layer. In addition, the intermediate layer may not have photosensitivity. In the case where the intermediate layer does not have photosensitivity, there is a tendency that the photosensitivity stability of the photosensitive layer is further improved. In addition, "photosensitivity" means, for example, that the photosensitive layer is exposed, and a post-exposure heat treatment is performed as needed, and then, when the photosensitive layer is developed using a developer for removing the uncured portion of the photosensitive layer, a resist pattern can be formed.

[0139] (Photosensitive layer 3)

[0140] The photosensitive layer 3 is a layer formed using the above-mentioned photosensitive resin composition. The thickness of the photosensitive layer 3 after drying (after the organic solvent is volatilized when the photosensitive resin composition contains an organic solvent) can be appropriately selected according to the purpose, and the thickness after drying can be 1 to 100 μm, 3 to 50 μm, 5 to 40 μm, or 10 to 30 μm. When the thickness of the photosensitive layer is 1 μm or more, industrial coating becomes easy and productivity is improved. When it is 100 μm or less, the adhesion and resolution are further improved.

[0141] (Protective layer 4)

[0142] The photosensitive element may be a polymer film having heat resistance and solvent resistance. As the protective layer, a film in which the adhesive force between the photosensitive layer and the protective layer is smaller than the adhesive force between the photosensitive layer and the support may be used, and a low fisheye film may also be used. Specifically, for example, a film that can be used as the above-mentioned support may be cited. From the viewpoint of the peelability of the photosensitive layer, a polyethylene film may be used. The thickness of the protective layer varies depending on the application, but may be about 1 to 100 μm.

[0143] [Method for producing photosensitive element]

[0144] The photosensitive element can be manufactured, for example, as follows. The photosensitive element can be manufactured by a manufacturing method including a step of preparing a coating liquid of the above-mentioned photosensitive resin composition, a step of applying the coating liquid on a support to form a coating layer, and a step of drying the coating layer to form a photosensitive layer. The coating liquid can be applied to the support by a known method such as roller coating, comma coating, gravure coating, air knife coating, die coating, rod coating, etc.

[0145] There is no particular limitation on the drying of the coating layer as long as at least a portion of the organic solvent can be removed from the coating layer. Drying can be performed at 70 to 150° C. for about 5 to 30 minutes, for example. From the viewpoint of preventing the diffusion of the organic solvent in subsequent steps, the amount of residual organic solvent in the photosensitive layer after drying can be 2% by mass or less.

[0146] Since the photosensitive layer of the photosensitive element is a layer formed using the above-mentioned photosensitive resin composition, the absorbance relative to the light of wavelength 365nm per 1μm of this thickness can be greater than 0.0041 and less than 0.0130. By the above-mentioned absorbance being greater than 0.0041, the sensitivity, resolution and adhesion can be improved. And when the above-mentioned absorbance is less than 0.0130, the sensitivity, resolution and adhesion can be improved, and a resist pattern with a good resist shape can be formed. From the viewpoint of further improving sensitivity, resolution and adhesion, the above-mentioned absorbance can be more than 0.0045, more than 0.0050, more than 0.0055, or more than 0.0060, and from the viewpoint of further improving sensitivity, resolution and adhesion and making the resist shape better, it can be less than 0.0120, less than 0.0110, less than 0.0100, less than 0.0090, or less than 0.0080.

[0147] The photosensitive element can be used appropriately in the method for forming a resist pattern described later, for example. In particular, from the perspective of resolution, it is suitable for use in a manufacturing method for forming a conductor pattern by plating. Furthermore, the photosensitive element can be used appropriately when forming a resist pattern using a projection exposure method.

[0148] [Method for forming resist pattern]

[0149] The method for forming a resist pattern of the present embodiment comprises: a photosensitive layer forming step of laminating a photosensitive layer comprising the above-mentioned photosensitive resin composition or a photosensitive layer of the above-mentioned photosensitive element on a substrate; an exposure step of irradiating a prescribed portion of the photosensitive layer with active light to form a photocured portion; and a developing step of removing an area other than the prescribed portion of the photosensitive layer from the substrate. The method for forming a resist pattern may also have other steps as needed. In addition, a resist pattern is also referred to as a photocured pattern or a relief pattern of a photosensitive resin composition. Furthermore, the method for forming a resist pattern is also referred to as a method for manufacturing a substrate with a resist pattern.

[0150] (Photosensitive layer forming step)

[0151] As a method for forming a photosensitive layer on a substrate, for example, a photosensitive resin composition can be applied and dried, or the photosensitive layer of the photosensitive element can be heated after removing the protective layer from the photosensitive element and pressed against the above-mentioned substrate. In the case of using a photosensitive element, a laminated body consisting of a substrate, a photosensitive layer and a support body, which are stacked in sequence, can be obtained. In addition, in the case where the photosensitive element has an intermediate layer, a state in which an intermediate layer is arranged between the photosensitive layer and the support body. There is no particular limitation as a substrate, but generally a circuit forming substrate having an insulating layer and a conductor layer formed on the insulating layer, a metal substrate for metal mask manufacturing, a metal substrate or an alloy substrate, and the like chip pad (die pad) (substrate for lead frame) and the like can be used.

[0152] From the viewpoint of further improving the resolution, the surface roughness (Sa) of the substrate may be 1 to 200 nm, or 3 to 100 nm. When Sa is 3 to 100 nm, haloing due to the unevenness of the substrate surface can be suppressed, and the resolution is further improved.

[0153] When a photosensitive element is used, the heating of the photosensitive layer and / or the substrate during pressure bonding can be performed at a temperature of 70 to 130°C. Pressure bonding can be performed at about 0.1 to 1.0 MPa (1 to 10 kgf / cm 2 The substrate is preferably heated to 70 to 130°C, but the substrate may be preheated to further improve adhesion and tracking properties.

[0154] (Exposure process)

[0155] In the exposure process, at least a portion of the photosensitive layer formed on the substrate is irradiated with active light, and the portion irradiated with active light is photocured to form a latent image. At this time, if the support present on the photosensitive layer is transparent to the active light, the active light can be irradiated through the support, but if the support is light-shielding, the active light is irradiated to the photosensitive layer after the support is removed. In addition, if an intermediate layer is provided between the photosensitive layer and the support, only the support is removed, and the intermediate layer remains in the photosensitive layer. In this case, the photosensitive layer is exposed to active light through the intermediate layer.

[0156] As an exposure method, a method of irradiating active light in an image form through a negative or positive mask pattern called an original image (mask exposure method) can be cited. In addition, a method of irradiating active light in an image form by a projection exposure method can be adopted. In the method for forming the resist pattern involved in this embodiment, it is preferred to irradiate active light by projection exposure to form a photocured portion. In addition, as an exposure method, a contact exposure method, a direct drawing exposure method, etc. can be used.

[0157] As the light source of the active light, a known light source can be used, for example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, a semiconductor laser, ultraviolet light such as an LED, or a light source that effectively radiates visible light. The wavelength of the active light can be in the range of 340 nm to 430 nm, or in the range of 355 nm to 375 nm.

[0158] In addition, from the viewpoint of improving pattern formation, after exposure, post-exposure baking (PEB) may be performed using a hot plate, a dryer, etc. The heating conditions are not particularly limited, but the heating may be performed at a temperature of 60 to 120° C. or 70 to 110° C. for 15 seconds to 5 minutes or 30 seconds to 3 minutes.

[0159] (Development Process)

[0160] In the development process, at least a portion of the photosensitive layer other than the photocured portion is removed from the substrate, thereby forming a resist pattern on the substrate. In the case where there is a support on the photosensitive layer, the area other than the photocured portion (also referred to as the unexposed portion) is removed (developed) after the support is removed. In the case where there is an intermediate layer and the intermediate layer is water-soluble, the uncured portion other than the photocured portion can be removed by a developer after the intermediate layer is removed by washing with water. In the case where the intermediate layer is soluble in the developer, the uncured portion other than the photocured portion and the intermediate layer can be removed by a developer. The development method includes wet development and dry development, and wet development can be widely used.

[0161] In the case of wet development, a developer corresponding to the photosensitive resin composition is used to develop by a known development method. As the development method, there can be cited methods using immersion, rotary immersion, spraying, brushing, slapping, brushing, swing immersion, etc. From the viewpoint of improving resolution, a high-pressure spray method can be used. It is also possible to combine two or more of these methods for development.

[0162] The structure of the developer can be appropriately selected according to the structure of the photosensitive resin composition, and examples thereof include alkaline aqueous solutions and organic solvent developers.

[0163] From the perspective of safety, stability and good operability, an alkaline aqueous solution can be used as a developer. As the salt base of the alkaline aqueous solution, an alkali hydroxide such as lithium, sodium or potassium hydroxide; an alkali carbonate such as lithium, sodium, potassium or ammonium carbonate or hydrogen carbonate; an alkali metal phosphate such as potassium phosphate and sodium phosphate; an alkali metal pyrroline salt such as sodium pyrroline acid and potassium pyrroline acid; borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine, etc. can be used.

[0164] As the alkaline aqueous solution used for development, a diluted solution of 0.1 to 5% by mass of sodium carbonate, a diluted solution of 0.1 to 5% by mass of potassium carbonate, a diluted solution of 0.1 to 5% by mass of sodium hydroxide, a diluted solution of 0.1 to 5% by mass of sodium tetraborate, etc. can be used. The pH of the alkaline aqueous solution used for development can be set in the range of 9 to 11, and its temperature can be adjusted according to the alkali developability of the photosensitive layer.

[0165] The alkaline aqueous solution may contain, for example, a surfactant, a defoaming agent, a small amount of an organic solvent for accelerating development, etc. In addition, examples of the organic solvent used in the alkaline aqueous solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0166] Examples of organic solvents used in organic solvent developers include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. To prevent ignition, water may be added to these organic solvents to a concentration of 1 to 20% by mass to prepare an organic solvent developer.

[0167] The resist pattern forming method of the present embodiment may include: after removing the uncured portion in the development step, heating at about 60 to 250° C. or 0.2 to 10 J / cm 2 A step of further curing the resist pattern by exposing the resist pattern to light for about 10 minutes.

[0168] [Method for manufacturing semiconductor package substrate or printed wiring board]

[0169] The manufacturing method of the semiconductor package substrate or printed wiring board of the present embodiment includes: a process of etching or plating a substrate formed with a resist pattern by the above-mentioned resist pattern forming method to form a conductor pattern. The manufacturing method of the semiconductor package substrate or printed wiring board may also include other processes such as a resist pattern removal process as needed.

[0170] In the plating process, the conductor layer provided on the substrate is plated using the resist pattern formed on the substrate as a mask. After the plating process, the resist can be removed by removing the resist pattern described later, and the conductor layer covered by the resist can be etched to form a conductor pattern.

[0171] The plating method may be electrolytic plating or electroless plating. In the etching process, the resist pattern formed on the substrate is used as a mask to etch away the conductor layer provided on the substrate to form a conductor pattern. The etching method may be appropriately selected according to the conductor layer to be removed. Examples of etching solutions include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, and the like.

[0172] After the above-mentioned etching process or plating process, the resist pattern on the substrate can be removed. The removal of the resist pattern can be stripped by, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the above-mentioned development process. As the strongly alkaline aqueous solution, for example, an amine stripping solution (15 volume % R-100S + 8 volume % R-101 aqueous solution (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.)) can be used. In addition, as the strongly alkaline aqueous solution, a 1-10 mass % sodium hydroxide aqueous solution, a 1-10 mass % potassium hydroxide aqueous solution, etc. can be used.

[0173] When the resist pattern is removed after the plating treatment, the conductor layer covered by the resist is further etched by etching to form a conductor pattern, thereby manufacturing a desired semiconductor package substrate and a printed wiring board. The etching method at this time can be appropriately selected according to the conductor layer to be removed. For example, the above-mentioned etching solution can be applied.

[0174] The method for manufacturing a semiconductor package substrate or printed wiring board involved in this embodiment can be applied not only to the manufacture of a single-layer semiconductor package substrate or printed wiring board, but also to the manufacture of a multi-layer semiconductor package substrate or printed wiring board, and can also be applied to the manufacture of a semiconductor package substrate or printed wiring board having a small-diameter through hole.

[0175] Example

[0176] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples.

[0177] <Synthesis of Binder Polymer A-1>

[0178] 270 g of methacrylic acid, 500 g of styrene, 200 g of benzyl methacrylate, 30 g of 2-hydroxyethyl methacrylate, and 9 g of azobisisobutyronitrile as polymerizable monomers (monomers) were mixed to prepare a solution (a). Furthermore, 1.4 g of azobisisobutyronitrile was mixed with a mixed solution of 160 g of 1-methoxy-2-propanol and 120 g of toluene to prepare a solution (b). A mixed solution of 450 g of 1-methoxy-2-propanol and 380 g of toluene was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet tube, and nitrogen was blown into the flask while stirring to raise the temperature to 80°C. The solution (a) was added dropwise to the mixed solution in the flask at a constant dropping rate for 4 hours, and then stirred at 80°C for 2 hours. Next, the solution (b) was added dropwise at a constant dropping rate for 10 minutes to the solution in the flask, and the solution in the flask was stirred at 80°C for 3 hours. Furthermore, the solution in the flask was heated to 90°C for 30 minutes, kept at 90°C for 6 hours, and then the stirring was stopped and cooled to room temperature (25°C) to obtain a solution of the binder polymer A-1. The non-volatile component (solid content) of the solution of the binder polymer A-1 was 49% by mass. The weight average molecular weight (Mw) of the binder polymer A-1 is shown in Table 1.

[0179] <Synthesis of Binder Polymer A-2>

[0180] 270 g of methacrylic acid, 450 g of styrene, 230 g of benzyl methacrylate, 50 g of methyl methacrylate, and 6 g of azobisisobutyronitrile as polymerizable monomers (monomers) were mixed to prepare a solution (a). Furthermore, 1.4 g of azobisisobutyronitrile was mixed with a mixed solution of 180 g of 1-methoxy-2-propanol and 150 g of toluene to prepare a solution (b). A mixed solution of 400 g of 1-methoxy-2-propanol and 340 g of toluene was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet tube, and nitrogen was blown into the flask while stirring to raise the temperature to 80°C. The solution (a) was added dropwise to the mixed solution in the flask at a constant dropping rate for 4 hours, and then stirred at 80°C for 2 hours. Next, the solution (b) was added dropwise at a constant dropping rate for 10 minutes to the solution in the flask, and the solution in the flask was stirred at 80°C for 3 hours. Furthermore, the solution in the flask was heated to 90°C for 30 minutes, kept at 90°C for 6 hours, and then the stirring was stopped and cooled to room temperature (25°C) to obtain a solution of the binder polymer A-2. The non-volatile component (solid content) of the solution of the binder polymer A-2 was 49% by mass. The weight average molecular weight (Mw) of the binder polymer A-2 is shown in Table 1.

[0181] The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a calibration curve of standard polystyrene. The conditions of GPC were as follows.

[0182] (GPC conditions)

[0183] Column: Connect Gelpack GL-R440, Gelpack GL-R450 and Gelpack GL-R400M (all from ShowaDenko Materials Co., Ltd.)

[0184] Eluent: Tetrahydrofuran

[0185] Measurement temperature: 40℃

[0186] Flow rate: 2.05mL / min

[0187] Detector: Hitachi L-2490 RI (Hitachi, Ltd.)

[0188] [Table 1]

[0189]

[0190] [Examples 1 to 14 and Comparative Examples 1 to 5]

[0191] <Preparation of photosensitive resin composition>

[0192] The photosensitive resin compositions of the Examples and Comparative Examples were prepared by mixing (A) a binder polymer with (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a sensitizer, (E) a hydrogen donor, other components and a solvent in the amounts (parts by mass) shown in Tables 2 to 4 below. In addition, the amounts of the components other than the solvent shown in Tables 2 to 4 are the mass (solid content) of the non-volatile components. In addition, the evaluation results of the evaluation described later are also shown in Tables 2 to 4.

[0193] (Component (A): Binder polymer)

[0194] Binder polymers A-1 to A-2 synthesized by the above method were used.

[0195] (Component (B): photopolymerizable compound)

[0196] B-1: 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (manufactured by Showa Denko Materials Co., Ltd., product name: FA-321M, EO number: 10 (average value))

[0197] B-2: (PO)(EO)(PO)-modified polyethylene glycol dimethacrylate (manufactured by Showa Denko Materials Co., Ltd., product name: FA-024M, EO number: 6 (average value), PO number: 12 (average value))

[0198] B-3: Ethoxylated bisphenol A dimethacrylate (EO number: 2.6 (average value)) (manufactured by Kyoeisha Chemical Co., Ltd., product name: BP-2EM)

[0199] B-4: 2,2-bis(4-(methacryloyloxypolyethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: BPE-200, EO number: 4 (average value))

[0200] B-5: EO-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name: DPEA-12)

[0201] (Component (C): photopolymerization initiator)

[0202] C-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., product name: B-CIM)

[0203] ((D) ingredient: sensitizer)

[0204] D-1: 1-phenyl-3-(4-methoxyphenyl)-5-(4-methoxyphenyl)-pyrazoline

[0205] D-2: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Chemicals Ltd., product name: DBA)

[0206] D-3: 4,4'-bis(diethylamino)benzophenone (manufactured by HODOGAYA CHEMICAL CO., LTD., product name: EAB)

[0207] ((E) component: hydrogen donor)

[0208] E-1: Colorless crystal violet (manufactured by YAMADA CHEMICAL CO., LTD.)

[0209] (Other ingredients)

[0210] F-1: Malachite green (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) (dye)

[0211] F-2: tert-butylcatechol (manufactured by FUJIFILM Wako Pure Chemical Corporation) (polymerization inhibitor)

[0212] F-3: 4-Hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl (manufactured by ADEKA CORPORATION, product name: LA-7RD)

[0213] F-4: Benzotriazole derivative (manufactured by SANWA KASEI CORP., product name: SF-808H) (heterocyclic compound)

[0214] <Production of Photosensitive Element Not Having Intermediate Layer (Examples 1 to 4, 6, 8 to 14 and Comparative Examples 1 to 5)>

[0215] The solution of the photosensitive resin composition was uniformly applied on the support shown in Tables 2 to 4 below. After that, it was dried in a hot air convection dryer at 90°C for 10 minutes, and after drying, a photosensitive layer having a thickness shown in Tables 2 to 4 below was formed. Next, a polyethylene film (manufactured by Tamapoly CO., LTD., product name "NF-15A") was laminated on the photosensitive layer as a protective layer to obtain a photosensitive element.

[0216] <Preparation of Photosensitive Elements Having Intermediate Layers (Examples 5 and 7)>

[0217] At room temperature, 60 parts by mass of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., product name: PVA-205, saponification degree = 87 mol%) and 40 parts by mass of polyvinyl pyrrolidone (manufactured by NIPPON SHOKUBAI CO., LTD., product name: K-30) were slowly added to 500 parts by mass of water and 250 parts by mass of 1-propanol and mixed. The mixed solution was heated to 90°C and stirred for 1 hour, and cooled to room temperature to obtain a resin composition for forming an intermediate layer. Next, the resin composition for forming an intermediate layer was uniformly coated on the support shown in Table 2 below, and dried for 10 minutes with a hot air convection dryer at 95°C to form an intermediate layer with a thickness of 5μm after drying. Next, a solution of the photosensitive resin composition was uniformly coated on the above intermediate layer. Thereafter, it was dried for 10 minutes with a hot air convection dryer at 90°C, and after drying, a photosensitive layer having a thickness shown in Tables 2 to 4 below was formed. Next, a polyethylene film (manufactured by Tamapoly CO., LTD., product name "NF-15A") was laminated on the photosensitive layer as a protective layer to obtain a photosensitive element.

[0218] (Support)

[0219] FS-31: A three-layer biaxially oriented polyethylene terephthalate film having an antistatic layer on the side opposite to the side on which the photosensitive resin composition is applied and a layer containing fine particles on the front and back surfaces (manufactured by TORAY INDUSTRIES, INC., product name "FS-31", thickness: 16 μm, number of particles with a diameter of 5 μm or more: 0 particles / mm 2 , haze: 0.4%) FB40: a three-layer biaxially oriented polyethylene terephthalate film having a layer containing microparticles on the surface and the back (manufactured by TORAY INDUSTRIES, INC., product name "FB40", thickness: 16 μm, number of particles with a diameter of 5 μm or more: 1 particle / mm 2 , haze: 0.7%)

[0220] R705G: A biaxially oriented polyethylene terephthalate film having a double-layer structure having an antistatic layer on the side opposite to the side on which the photosensitive resin composition is applied and containing fine particles on the side opposite to the side on which the photosensitive resin composition is applied (manufactured by Mitsubishi Chemical Corporation, product name "R705G", thickness: 16 μm, number of particles with a diameter of 5 μm or more: 0 particles / mm 2 , haze: 0.4%)

[0221] <Measurement of absorbance and transmittance>

[0222] A photosensitive element was laminated (stacked) on the surface of a glass slide (manufactured by Matsunami Glass Ind., Ltd., white glass slide cut No. 1S1126). The protective layer was peeled off and the photosensitive layer of the photosensitive element was brought into contact with the surface of the glass slide, and the lamination was performed using a hot roller at 110°C, a pressing pressure of 0.4 MPa, and a roller speed of 1.0 m / min. After the photosensitive layer was laminated on the glass slide, the support was peeled off. In the case where an intermediate layer was provided on the support, both the support and the intermediate layer were peeled off. In the case where the intermediate layer could not be peeled off from the photosensitive layer, a photosensitive element without an intermediate layer consisting of the photosensitive layer and the support was prepared separately, and the photosensitive layer was laminated on the glass slide using the method described above, and the absorbance and transmittance were measured. The absorbance and transmittance of the photosensitive layer were measured using a U-3310 spectrophotometer (manufactured by Hitachi High-Tech Corporation) under the following measurement conditions: wavelength range: 330 to 700 nm, scanning speed: 300 nm / min, scanning interval: 0.50 nm, and slit width: 2 nm. The baseline measurement was performed using an untreated glass slide as a reference and sample. The measurement was performed by setting a glass slide with a laminated photosensitive layer on the sample side support and setting an untreated glass slide on the reference side support. Based on the obtained absorption spectrum, the absorbance and transmittance of the exposure wavelength (365 nm) were recorded as the absorbance and transmittance of the photosensitive layer. In addition, the absorbance per 1 μm thickness was calculated by dividing the absorbance of the photosensitive layer by the thickness of the photosensitive layer.

[0223] <Production of laminate>

[0224] A substrate on which copper was sputtered on a polyethylene terephthalate film (surface roughness Sa: 3 nm, manufactured by GEOMATEC Co., Ltd., a titanium film with a thickness of 10 nm was formed by sputtering on the flat side surface of a polyethylene terephthalate film with a thickness of 125 μm (manufactured by TOYOBO CO., LTD., product name: A4160), and a copper film with a thickness of 100 nm was further formed by sputtering on the titanium surface) was heated to 80°C, and a photosensitive element was laminated (stacked) on the copper surface of the substrate. The protective layer was peeled off and the photosensitive layer of the photosensitive element was brought into contact with the copper surface of the copper substrate, and laminated using a hot roller at 110°C, a pressing pressure of 0.4 MPa, and a roller speed of 1.0 m / min. Thus, a laminated body in which a substrate, a photosensitive layer, and a support were laminated in sequence, or a laminated body in which a substrate, a photosensitive layer, an intermediate layer, and a support were laminated in sequence was obtained. The obtained laminated body was used as a test piece in the test shown below.

[0225] <Determination of minimum development time>

[0226] The support was peeled off from the test piece to expose the photosensitive layer, and a 1 mass % sodium carbonate aqueous solution at 30° C. was sprayed. The time until the photosensitive layer was completely removed was measured and taken as the minimum development time.

[0227] <Resolution and Adhesion Evaluation>

[0228] A chrome glass (Glasschromium) type exposure tool (Phototool) as a negative film for evaluating resolution and adhesion (resolution negative film: a film having a wiring pattern with line width / space width of 3x / x and (x: 1.0 to 18.0 (0.5 increments), unit: μm), adhesion negative film: a film having a wiring pattern with line width / space width of x / 3x and x / x (x: 1.0 to 18.0 (0.5 increments), unit: μm)) was arranged on the support of the test piece, and the photosensitive layer was exposed at a predetermined energy using a projection exposure device (manufactured by USHIO INC., product name "UX-2240-SM-XJ01") using an ultra-high pressure mercury lamp (365nm) as a light source. After exposure, the support was peeled off to expose the photosensitive layer, and a 1 mass % sodium carbonate aqueous solution at 30°C was sprayed for twice the minimum development time to remove the unexposed portion (development treatment). However, in Examples 5 and 7, by providing an intermediate layer with gas barrier properties, the inhibition of the photocuring reaction caused by the hindrance of free radical polymerization by oxygen in the air can be reduced. Therefore, in order to form an excellent resist pattern without exposing through the support, after peeling off the support, an exposure tool is arranged on the intermediate layer for exposure.

[0229] After the development process, the resolution and adhesion were evaluated by the value of the minimum line width / space width in the resist pattern in which the space portion (unexposed portion) was cleanly removed and the line portion was not distorted, snaking, or formed incompletely (exposed portion). At this time, the line width / space width of the resist line width of the adhesion negative pattern (x / x) = 10μm / 10μm was recorded as the value of the line width / space width evaluated by the above-mentioned prescribed energy as the resolution (3x / x) and adhesion (x / 3x). The smaller the value, the better the resolution and adhesion.

[0230] <Evaluation of resist shape>

[0231] For the pattern with line width / space width = 8μm / 8μm in the resist pattern after development, a scanning electron microscope (SEM, product name: SU-1500, manufactured by Hitachi High-Tech Corporation, acceleration voltage: 15.0kV) was used to measure the line width of the top (x) and bottom (y) of the resist. The taper rate (y / x) is obtained from the measured value as the evaluation criterion for the resist shape. The closer the taper rate is to 1, the closer the resist shape is to a rectangle, which can be called good. In the resist shape, a taper rate of 0.85 or more and less than 1.1 is evaluated as "A", and a taper rate of less than 0.85 is evaluated as "B".

[0232] (Test for measuring the occurrence of micro-defects in resists)

[0233] In order to examine the micro-defect occurrence of the resist in some examples, an exposure tool of chrome glass (adhesion negative film: a sheet having a wiring pattern with a line width / space width of 15 / 15 μm) was arranged on the support of the test piece as a negative film for measuring the micro-defect occurrence of the resist, and the photosensitive layer was exposed at a predetermined energy using a projection exposure device (manufactured by USHIO INC., product name "UX-2240-SM-XJ01") using an ultra-high pressure mercury lamp (365 nm) as a light source. However, in Example 5, by providing an intermediate layer having a gas barrier property, the inhibition of the photocuring reaction caused by the inhibition of radical polymerization by oxygen in the air can be reduced, and thus, in order to form an excellent resist pattern without exposure through the support, the exposure tool was arranged on the intermediate layer after the support was peeled off and exposure was performed. At this time, the exposure amount of the resist line width of 10.0 μm in the adhesion negative pattern (x / x) of <Evaluation of resolution and adhesion> is set to the above-mentioned specified energy. After exposure, the support is peeled off to expose the photosensitive layer, and a 1% by mass sodium carbonate aqueous solution at 30°C is sprayed for twice the minimum development time to remove the unexposed part (development treatment). Next, using a microscope or an automatic optical inspection device (AOI), count the number of resist defective parts with resist defects of more than 5 μm. The line length of 1 mm and the number of lines of 5000 are set as the observation unit, and the average value when the number n is set to 5 is set as the number of micro-defective parts of the resist. Among the number of micro-defective parts of the resist, the number of defects less than 10 is evaluated as "A", and the number of defects greater than 10 is evaluated as "B".

[0234] [Table 2]

[0235]

[0236] [Table 3]

[0237]

[0238] [Table 4]

[0239]

[0240] Explanation of symbols

[0241] 1- photosensitive element, 2- support, 3- photosensitive layer, 4- protective layer.

Claims

1. A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, wherein: The photosensitive resin composition has an absorbance per 1 μm thickness with respect to light of a wavelength of 365 nm of greater than 0.0041 and less than or equal to 0.0130.

2. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition has an absorbance of 0.0080 or less per thickness of 1 μm with respect to light of a wavelength of 365 nm.

3. The photosensitive resin composition according to claim 1, wherein The content of the (C) photopolymerization initiator is 3.0 parts by mass or more based on 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound.

4. The photosensitive resin composition according to claim 1, wherein The content of the (C) photopolymerization initiator is 5.0 parts by mass or more based on 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound. The photosensitive resin composition according to claim 1 , further comprising (D) a sensitizer.

6. The photosensitive resin composition according to claim 5, wherein The (D) sensitizer includes at least one selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, and coumarin compounds.

7. The photosensitive resin composition according to claim 5, wherein The content of the (D) sensitizer is 0.03 parts by mass or less based on 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound.

8. The photosensitive resin composition according to claim 5, wherein The mass ratio of the content of the (C) photopolymerization initiator to the content of the (D) sensitizer, that is, the content of the (C) photopolymerization initiator / the content of the (D) sensitizer, is 80 or more.

9. The photosensitive resin composition according to claim 1, further comprising (E) a hydrogen donor, The content of the (E) hydrogen donor is 0.3 parts by mass or more based on 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound.

10. The photosensitive resin composition according to claim 9, wherein The content of the (E) hydrogen donor is 0.55 parts by mass or more based on 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound.

11. The photosensitive resin composition according to claim 9, wherein The total content of the (C) photopolymerization initiator and the (E) hydrogen donor is 4.0 parts by mass or more based on 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound. 12 . The photosensitive resin composition according to claim 1 , which is used for forming a resist pattern using a projection exposure method. 13 . A photosensitive element comprising a support and a photosensitive layer formed on the support and comprising the photosensitive resin composition according to claim 1 .

14. The photosensitive element according to claim 13, wherein The support has a haze of 0.01 to 1.0%.

15. The photosensitive element according to claim 13, wherein The number of particles with a diameter of 5 μm or more contained in the support is 5 particles / mm 2 the following. 16 . The photosensitive element according to claim 13 , comprising an intermediate layer containing polyvinyl alcohol between the support and the photosensitive layer.

17. A method for forming a resist pattern, comprising: A photosensitive layer forming step of laminating a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 12 on a substrate; An exposure step of irradiating a predetermined portion of the photosensitive layer with active light to form a photocured portion; and A developing step of removing a region of the photosensitive layer other than the predetermined portion from the substrate.

18. A method for forming a resist pattern, comprising: A photosensitive layer forming step of laminating the photosensitive layer of the photosensitive element according to claim 13 on a substrate; An exposure step of irradiating a predetermined portion of the photosensitive layer with active light to form a photocured portion; and A developing step of removing a region of the photosensitive layer other than the predetermined portion from the substrate.

19. A method for manufacturing a semiconductor package substrate or a printed circuit board, comprising: A step of forming a conductor pattern by etching or plating the substrate on which the resist pattern is formed by the resist pattern forming method according to claim 17.

20. A method for manufacturing a semiconductor package substrate or a printed circuit board, comprising: A step of forming a conductor pattern by etching or plating the substrate on which the resist pattern is formed by the resist pattern forming method according to claim 18.

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