Method for producing photosensitive resin film, photosensitive element, and laminate

Abstract

To provide a photosensitive resin film capable of obtaining a hardened material pattern of a space part having a high aspect ratio, and a photosensitive element with the photosensitive resin film.SOLUTION: A photosensitive resin film 1a with a thickness of 35-300 μm contains a binder polymer, a photopolymerizable compound, a photoinitiator, and a polymerization inhibitor. The binder polymer includes a polymer in which (meth)acrylic acid alkyl having a 3 or more C alkyl group is provided as a monomer unit. A photosensitive element 1 comprises the photosensitive resin film 1a, and a support film 1b for supporting the photosensitive resin film 1a.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a photosensitive resin film, a photosensitive element, a method for producing a laminate, and the like. [Background technology]

[0002] In the field of manufacturing semiconductor integrated circuits (LSIs), wiring boards, etc., photosensitive materials are used as resist materials for producing conductor patterns. For example, in the manufacture of wiring boards, a resist pattern is formed using a photosensitive resin composition, and then a conductor pattern, metal posts, etc. are formed by plating. Specifically, (1) a photosensitive layer is formed on a substrate using a photosensitive resin composition, (2) the photosensitive layer is exposed through a predetermined mask pattern, (3) a resist pattern is formed by selectively removing (peeling) the parts where the conductor pattern, metal posts, etc. are to be formed by development, and (4) a conductor layer such as copper is formed on the removed parts by plating, and then the resist pattern is removed, thereby manufacturing a wiring board having a conductor pattern, metal posts, etc. (see, for example, Patent Document 1 below). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2000-356852 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, in electronic components such as inductors, it has been considered to form a conductor pattern having a conductor layer with a high aspect ratio in a thick layer state. Such a conductor pattern can be obtained, for example, by irradiating a photosensitive layer with light, removing the unexposed parts to form spaces, and forming a conductor layer in the spaces. Therefore, for a photosensitive resin film for obtaining a photosensitive layer as a thick film, it is required to obtain a cured pattern of the space parts having a high aspect ratio.

[0005] An object of one aspect of the present disclosure is to provide a photosensitive resin film capable of obtaining a cured pattern of a space portion having a high aspect ratio as a thick film.Another object of the present invention is to provide a photosensitive element including the photosensitive resin film.Another object of the present invention is to provide a method for producing a laminate using the above-mentioned photosensitive resin film. [Means for solving the problem]

[0006] One aspect of the present disclosure relates to a photosensitive resin film that contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a polymerization inhibitor, wherein the binder polymer includes a polymer having, as a monomer unit, an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms, and has a thickness of 35 to 300 μm.

[0007] Such a photosensitive resin film makes it possible to obtain a cured pattern with spaces having a high aspect ratio.

[0008] Another aspect of the present invention relates to a photosensitive element comprising the above-mentioned photosensitive resin film and a support that supports the photosensitive resin film.

[0009] Another aspect of the present invention relates to a method for producing a laminate, comprising the steps of forming a photosensitive layer on a substrate using the above-mentioned photosensitive resin film, photocuring a portion of the photosensitive layer, and removing at least a portion of an uncured portion of the photosensitive layer to form a cured product pattern. Effect of the Invention

[0010] According to one aspect of the present disclosure, a photosensitive resin film capable of obtaining a cured pattern of a space portion having a high aspect ratio as a thick film can be provided. According to another aspect of the present invention, a photosensitive element including the photosensitive resin film can be provided. According to another aspect of the present invention, a method for producing a laminate using the above-mentioned photosensitive resin film can be provided. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view illustrating an example of a photosensitive element. [Diagram 2] 1A to 1C are schematic cross-sectional views showing an example of a method for producing a laminate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, embodiments of the present disclosure will be described in detail.

[0013] The numerical range "A or more" means A and a range exceeding A. The numerical range "A or less" means A and a range less than A. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a certain stage of the numerical range can be arbitrarily combined with the upper limit or lower limit of the numerical range of another stage. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification may be used alone or in combination of two or more. When a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. The term "layer" includes a structure having a shape formed on the entire surface when observed as a plan view, as well as a structure having a shape formed on a part of the surface. The term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. "(Meth)acrylate" means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as "(meth)acrylic acid". "Alkyl group" may be linear, branched, or cyclic, unless otherwise specified. The content of monomer units of (meth)acrylic acid compounds (e.g., alkyl (meth)acrylate) means the total content of monomer units of acrylic acid compounds and monomer units of methacrylic acid compounds.

[0014] <Photosensitive resin film, cured product, and photosensitive resin composition> The photosensitive resin film according to this embodiment contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polymerization inhibitor, in which the binder polymer contains a polymer having, as a monomer unit, an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms, and has a thickness of 35 to 300 μm.

[0015] The photosensitive resin film according to this embodiment is a thick film having a thickness of 35 μm or more. Conventionally, when the film thickness is thick, it is difficult to form a space portion having a high aspect ratio due to reasons such as the difficulty of light passing to the bottom of the photosensitive layer. On the other hand, according to the photosensitive resin film according to this embodiment, when components (A) to (D) are used in combination, component (A) contains a polymer having an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms as a monomer unit, thereby improving the developability of the unexposed part of the photosensitive layer, thereby obtaining an excellent development contrast (the difference between the unexposed part and the exposed part), and improving the flexibility of the exposed part. Due to these actions, a cured product pattern of the space portion having a high aspect ratio can be obtained. However, the factor for obtaining a high aspect ratio is not limited to the above factor.

[0016] The photosensitive resin film according to this embodiment can provide excellent resolution and excellent pattern formability. The photosensitive resin film according to this embodiment can provide a cured pattern in the space portion having a high aspect ratio while providing excellent pattern formability. The photosensitive resin film according to this embodiment can be used in the manufacture of electronic components such as inductors (e.g., electronic circuit boards).

[0017] The cured product according to this embodiment is a cured product of the photosensitive resin film according to this embodiment. The cured product according to this embodiment may be a cured product pattern. Such a cured product pattern can be used as a resist pattern, and can be used to obtain a conductor pattern, a metal post, or the like. The cured product pattern may be a line shape (straight line shape).

[0018] The thickness of the photosensitive resin film according to the present embodiment is 35 to 300 μm. The thickness of the photosensitive resin film may be 40 μm or more, 45 μm or more, 50 μm or more, 55 μm or more, or 60 μm or more from the viewpoint of easily obtaining a cured product pattern of a space portion having a high aspect ratio. The thickness of the photosensitive resin film may be 250 μm or less, 200 μm or less, 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, 70 μm or less, or 60 μm or less from the viewpoint of excellent peelability of the photosensitive resin film. The thickness of the photosensitive resin film may be the average thickness of the thicknesses of 10 points.

[0019] The photosensitive resin composition according to the present embodiment contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polymerization inhibitor, and the binder polymer contains a polymer having, as a monomer unit, an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms. The photosensitive resin film according to the present embodiment can be obtained by forming the photosensitive resin composition according to the present embodiment into a film.

[0020] (Component (A): Binder polymer) The photosensitive resin film according to this embodiment contains a binder polymer as component (A). Component (A) can have a polymerizable monomer as a monomer unit, and can be obtained, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include alkyl (meth)acrylate, benzyl (meth)acrylate, 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, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, and β-furyl(meth)acrylic acid. , β-styryl(meth)acrylic acid, acrylamide (diacetone(meth)acrylamide, etc.), (meth)acrylonitrile, styrene compounds (styrene or styrene derivatives), vinyl alcohol ethers (vinyl-n-butyl ether, etc.), maleic acid, maleic anhydride, maleic acid monoesters (monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc. The photosensitive resin film according to this embodiment does not need to contain a binder polymer having an aromatic ring as component (A).

[0021] The (A) component includes a polymer having, as the (a1) component, an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms as a monomer unit (monomer unit a11). The (a1) component can have a monomer unit derived from an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms. The alkyl group of the alkyl (meth)acrylate may have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, a carboxylate salt group, an alkoxy group, an amino group, a halogeno group, and a glycidyl group. The (a1) component does not need to have an aromatic ring.

[0022] The number of carbon atoms of the alkyl group in the component (a1) is 3 or more from the viewpoint of obtaining a cured product pattern of the space portion having a high aspect ratio, and may be 4 or more from the viewpoint of easily obtaining a cured product pattern of the space portion having a high aspect ratio. The number of carbon atoms of the alkyl group in the component (a1) may be 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less from the viewpoint of easily obtaining a cured product pattern of the space portion having a high aspect ratio. From these viewpoints, the number of carbon atoms of the alkyl group in the component (a1) may be 3 to 10. When the alkyl group has a substituent, the number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent. From the viewpoint of obtaining a cured product pattern of the space portion having a high aspect ratio, the component (A) may contain a polymer having butyl (meth)acrylate as a monomer unit.

[0023] The content of the monomer unit a11 in the (a1) component may be in the following range based on the total amount of the (a1) component, from the viewpoint of easily obtaining a cured product pattern in the space portion having a high aspect ratio. The content of the monomer unit a11 may be 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, or 35 mass% or more. The content of the monomer unit a11 is 100 mass% or less, and may be less than 100 mass%, 90 mass% or less, 80 mass% or less, 60 mass% or less, 50 mass% or less, 45 mass% or less, 40 mass% or less, or 35 mass% or less. From these viewpoints, the content of the monomer unit a11 may be 5 to 100 mass%.

[0024] From the viewpoint of easily obtaining a cured product pattern of the space portion having a high aspect ratio, the (a1) component may have (meth)acrylic acid as a monomer unit (monomer unit a12). From the viewpoint of easily obtaining a cured product pattern of the space portion having a high aspect ratio, the content of the monomer unit a12 in the (a1) component may be in the following range based on the total amount of the (a1) component. The content of the monomer unit a12 may be 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, or 30 mass% or more. The content of the monomer unit a12 may be 60 mass% or less, 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less. From these viewpoints, the content of the monomer unit a12 may be 5 to 60 mass%.

[0025] From the viewpoint of easily obtaining a cured product pattern of the space portion having a high aspect ratio, the (a1) component may have methyl (meth)acrylate as a monomer unit (monomer unit a13). From the viewpoint of easily obtaining a cured product pattern of the space portion having a high aspect ratio, the content of the monomer unit a13 in the (a1) component may be in the following range based on the total amount of the (a1) component. The content of the monomer unit a13 may be 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, or 35 mass% or more. The content of the monomer unit a13 may be 60 mass% or less, 50 mass% or less, 45 mass% or less, 40 mass% or less, or 35 mass% or less. From these viewpoints, the content of the monomer unit a13 may be 5 to 60 mass%.

[0026] The content of the (a1) component in the (A) component may be in the following range based on the total mass of the (A) component, from the viewpoint of easily obtaining a cured product pattern of a space portion having a high aspect ratio. The content of the (a1) component may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, more than 50 mass%, 70 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, 99 mass% or more, or substantially 100 mass% (an embodiment in which the (A) component is substantially composed of the (a1) component). The content of the (a1) component may be 100 mass% or less, less than 100 mass%, 99 mass% or less, 98 mass% or less, 95 mass% or less, 90 mass% or less, 70 mass% or less, 50 mass% or less, less than 50 mass%, or 40 mass% or less. From these viewpoints, the content of the (a1) component may be 10 to 100 mass%.

[0027] The component (A) may contain, as the component (a2), a polymer that does not have, as a monomer unit, an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms. The component (a2) may have, as a monomer unit, at least one selected from the group consisting of (meth)acrylic acid, methyl (meth)acrylate, hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, and a styrene compound (e.g., styrene).

[0028] When the (a2) component has (meth)acrylic acid as a monomer unit (monomer unit a21), the content of the monomer unit a21 in the (a2) component may be in the following range based on the total amount of the (a2) component, from the viewpoint of easily obtaining a cured product pattern in a space portion having a high aspect ratio. The content of the monomer unit a21 may be 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, or 25 mass% or more. The content of the monomer unit a21 may be 60 mass% or less, 50 mass% or less, 40 mass% or less, or 30 mass% or less. From these viewpoints, the content of the monomer unit a21 may be 5 to 60 mass%.

[0029] When the (a2) component has methyl (meth)acrylate as a monomer unit (monomer unit a22), the content of the monomer unit a22 in the (a2) component may be in the following range based on the total amount of the (a2) component, from the viewpoint of easily obtaining a cured product pattern in a space portion having a high aspect ratio. The content of the monomer unit a22 may be 1 mass% or more, 3 mass% or more, or 5 mass% or more. The content of the monomer unit a22 may be 20 mass% or less, 15 mass% or less, 10 mass% or less, or 5 mass% or less. From these viewpoints, the content of the monomer unit a22 may be 1 to 20 mass%.

[0030] When the (a2) component has hydroxyethyl (meth)acrylate as a monomer unit (monomer unit a23), the content of the monomer unit a23 in the (a2) component may be in the following range based on the total amount of the (a2) component, from the viewpoint of easily obtaining a cured product pattern in a space portion having a high aspect ratio. The content of the monomer unit a23 may be 1 mass% or more, 2 mass% or more, or 3 mass% or more. The content of the monomer unit a23 may be 20 mass% or less, 15 mass% or less, 10 mass% or less, 5 mass% or less, or 3 mass% or less. From these viewpoints, the content of the monomer unit a23 may be 1 to 20 mass%.

[0031] When the (a2) component has benzyl (meth)acrylate as a monomer unit (monomer unit a24), the content of the monomer unit a24 in the (a2) component may be in the following range based on the total amount of the (a2) component, from the viewpoint of easily obtaining a cured product pattern in a space portion having a high aspect ratio. The content of the monomer unit a24 may be 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, or 23 mass% or more. The content of the monomer unit a24 may be 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 25 mass% or less, 23 mass% or less, or 20 mass% or less. From these viewpoints, the content of the monomer unit a24 may be 5 to 60 mass%.

[0032] When the (a2) component has a styrene compound as a monomer unit (monomer unit a25), the content of the monomer unit a25 in the (a2) component may be in the following range based on the total amount of the (a2) component, from the viewpoint of easily obtaining a cured product pattern in the space portion having a high aspect ratio. When the (a2) component has styrene as a monomer unit (monomer unit a26), the content of the monomer unit a26 in the (a2) component may be in the following range based on the total amount of the (a2) component, from the viewpoint of easily obtaining a cured product pattern in the space portion having a high aspect ratio. The content of the monomer unit a25 or the monomer unit a26 may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more. The content of the monomer unit a25 or the monomer unit a26 may be 80 mass% or less, 70 mass% or less, 60 mass% or less, 55 mass% or less, 50 mass% or less, or 45 mass% or less. From these viewpoints, the content of the monomer unit a25 or the monomer unit a26 may be 10 to 80 mass%. The content of the monomer unit a25 means the total amount of the content of the monomer unit of styrene and the content of the monomer unit of a styrene derivative.

[0033] When the (A) component contains the (a2) component, the content of the (a2) component in the (A) component may be in the following range based on the total mass of the (A) component, from the viewpoint of easily obtaining a cured product pattern in the space portion having a high aspect ratio. The content of the (a2) component may be 1 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, more than 50 mass%, or 60 mass% or more. The content of the (a2) component may be 90 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, or 65 mass% or less. From these viewpoints, the content of the (a2) component may be 1 to 90 mass%.

[0034] The weight average molecular weight (Mw) of the (a1) component or the (a2) component may be in the following range from the viewpoint of easily obtaining a cured product pattern in the space portion having a high aspect ratio. The weight average molecular weight may be 10000 or more, 15000 or more, 20000 or more, 25000 or more, 30000 or more, 35000 or more, 40000 or more, 45000 or more, or 50000 or more from the viewpoint of easily obtaining excellent developer resistance. The weight average molecular weight may be 300000 or less, 150000 or less, 100000 or less, 80000 or less, 60000 or less, 55000 or less, or 50000 or less from the viewpoint of easily suppressing the development time from being extended. From these viewpoints, the weight average molecular weight may be 10000 to 300000.

[0035] The number average molecular weight (Mn) of the (a1) component or the (a2) component may be in the following range from the viewpoint of easily obtaining a cured product pattern in the space portion having a high aspect ratio. The number average molecular weight may be 5000 or more, 8000 or more, 10000 or more, 12000 or more, 15000 or more, 16000 or more, 18000 or more, 20000 or more, or 21000 or more from the viewpoint of easily obtaining excellent developer resistance. The number average molecular weight may be 150000 or less, 80000 or less, 50000 or less, 40000 or less, 30000 or less, 25000 or less, or 21000 or less from the viewpoint of easily suppressing the development time from being extended. From these viewpoints, the number average molecular weight may be 5000 to 150000.

[0036] The degree of dispersion (weight average molecular weight / number average molecular weight) of the (a1) component or the (a2) component may be in the following range from the viewpoint of easily obtaining a cured pattern of a space portion having a high aspect ratio. The degree of dispersion may be 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, 2.1 or more, 2.2 or more, or 2.3 or more. The degree of dispersion may be 3.0 or less, 2.8 or less, 2.5 or less, or 2.4 or less. From these viewpoints, the degree of dispersion may be 1.0 to 3.0.

[0037] The weight average molecular weight and number average molecular weight in this specification are values ​​measured by gel permeation chromatography (GPC) and converted using standard polystyrene as a standard sample. The following conditions can be used as GPC conditions. {GPC conditions} Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.) Columns: Gelpack GL-R440, Gelpack GL-R450 and Gelpack GL-R400M (Showa Denko Materials Technoservice Co., Ltd., column specifications: 10.7 mmφ × 300 mm) Eluent: Tetrahydrofuran Measurement temperature: 40℃ Injection volume: 200μL Flow rate: 2.05mL / min Detector: L-2490 type RI (Hitachi High-Tech Corporation)

[0038] The acid value of the (a1) component or the (a2) component may be in the following range from the viewpoint of easily obtaining a cured pattern of a space portion having a high aspect ratio. The acid value may be 50 mgKOH / g or more, 80 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, 150 mgKOH / g or more, 180 mgKOH / g or more, or 190 mgKOH / g or more. The acid value may be 250 mgKOH / g or less, 230 mgKOH / g or less, 220 mgKOH / g or less, 210 mgKOH / g or less, or 200 mgKOH / g or less. From these viewpoints, the acid value may be 50 to 250 mgKOH / g, 50 to 200 mgKOH / g, or 100 to 200 mgKOH / g.

[0039] The acid value can be measured by the following procedure. First, the binder polymer is weighed in an Erlenmeyer flask. Next, a mixed solvent (mass ratio: toluene / methanol = 70 / 30) is added to dissolve the binder polymer, and then a phenolphthalein solution is added as an indicator. Then, the acid value is obtained by titration using a 0.1 mol / L (N / 10) potassium hydroxide solution (alcohol solution).

[0040] The content of the (A) component (total amount of the (a1) component and the (a2) component) may be in the following range relative to 100 parts by mass of the total amount of the (A) component and the (B) component, from the viewpoint of easily obtaining a cured product pattern of a space portion having a high aspect ratio. The content of the (A) component may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more. The content of the (A) component may be 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less. From these viewpoints, the content of the (A) component may be 10 to 90 parts by mass.

[0041] The content of the (a1) component may be in the following ranges relative to 100 parts by mass of the total of the (A) and (B) components, from the viewpoint of easily obtaining a cured pattern of the space portion having a high aspect ratio. The content of the (a1) component may be 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more. The content of the (a1) component may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less. From these viewpoints, the content of the (a1) component may be 10 to 90 parts by mass.

[0042] ((B) component: photopolymerizable compound) The photosensitive resin film according to this embodiment contains a photopolymerizable compound as component (B). As component (B), a compound having at least one ethylenically unsaturated bond in the molecule can be used.

[0043] Examples of the ethylenically unsaturated bond include an α,β-unsaturated carbonyl group (such as a (meth)acryloyl group). Examples of the photopolymerizable compound having an α,β-unsaturated carbonyl group include an α,β-unsaturated carboxylic acid ester of a polyhydric alcohol, a bisphenol type (meth)acrylate, an α,β-unsaturated carboxylic acid adduct of a glycidyl group-containing compound, a (meth)acrylate having a urethane bond, a nonylphenoxy polyethyleneoxy (meth)acrylate (also known as nonylphenoxy polyethylene glycol (meth)acrylate), a (meth)acrylate having a phthalic acid skeleton, and an alkyl (meth)acrylate.

[0044] Examples of the α,β-unsaturated carboxylic acid ester of a polyhydric alcohol include polyethylene glycol di(meth)acrylate having 2 to 14 ethylene groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene groups, polyethylene·polypropylene glycol di(meth)acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO·PO-modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and (meth)acrylate compounds having a skeleton derived from dipentaerythritol or pentaerythritol. "EO modified" means having a block structure of ethylene oxide (EO) groups, and "PO modified" means having a block structure of propylene oxide (PO) groups.

[0045] The (B) component may contain a polyalkylene glycol di(meth)acrylate from the viewpoint of easily improving the flexibility of the cured product pattern and easily obtaining a cured product pattern with a space portion having a high aspect ratio. The polyalkylene glycol di(meth)acrylate may have at least one of an EO group and a PO group, or may have both an EO group and a PO group. In a polyalkylene glycol di(meth)acrylate having both an EO group and a PO group, the EO group and the PO group may each be present in a continuous block form or may be present randomly. The PO group may be either an oxy-n-propylene group or an oxyisopropylene group. In the (poly)oxyisopropylene group, the secondary carbon of the propylene group may be bonded to an oxygen atom, and the primary carbon may be bonded to an oxygen atom.

[0046] Commercially available polyalkylene glycol di(meth)acrylate products include FA-023M (manufactured by Showa Denko Materials Co., Ltd.), FA-024M (manufactured by Showa Denko Materials Co., Ltd.), and NK Ester HEMA-9P (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0047] The component (B) may contain a (meth)acrylate having a urethane bond, from the viewpoint of easily improving the flexibility of the cured product pattern and easily obtaining a cured product pattern with a space portion having a high aspect ratio. Examples of the (meth)acrylate having a urethane bond include an addition reaction product of a (meth)acrylic monomer having a hydroxy group at the β-position with a diisocyanate (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.), tris((meth)acryloxytetraethylene glycol isocyanate)hexamethylene isocyanurate, EO-modified urethane di(meth)acrylate, PO-modified urethane di(meth)acrylate, and EO·PO-modified urethane di(meth)acrylate.

[0048] Commercially available EO-modified urethane di(meth)acrylate products include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-21EB (manufactured by Shin-Nakamura Chemical Co., Ltd.). Commercially available EO·PO-modified urethane di(meth)acrylate products include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0049] From the viewpoint of easily forming a thick cured pattern and easily improving the resolution and adhesion in a well-balanced manner, the (B) component may contain a (meth)acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol. The (meth)acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol may have four or more (meth)acryloyl groups and may be dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate.

[0050] The (B) component may contain a polyfunctional (meth)acrylate compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid. The polyfunctional (meth)acrylate compound may have at least one of an EO group and a PO group, or may have both an EO group and a PO group. Examples of such compounds include dipentaerythritol (meth)acrylate having an EO group. Examples of commercially available dipentaerythritol (meth)acrylate having an EO group include DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.).

[0051] The (B) component may contain a bisphenol type (meth)acrylate or a bisphenol A type (meth)acrylate from the viewpoint of easily obtaining a cured pattern of a space portion having a high aspect ratio and from the viewpoint of easily improving the resolution and peeling property after curing. Examples of the bisphenol A type (meth)acrylate include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (e.g., 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane. The component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane from the viewpoint of making it easier to obtain a cured product pattern in space portions having a high aspect ratio, and from the viewpoint of making it easier to further improve the resolution and pattern formability.

[0052] Commercially available products of 2,2-bis(4-((meth)acryloxydipropoxy)phenyl)propane include BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Commercially available products of 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane include BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and FA-321M (manufactured by Showa Denko Materials Co., Ltd.).

[0053] The (B) component may contain nonylphenoxy polyethyleneoxy (meth)acrylate from the viewpoint of easily obtaining a cured product pattern of a space part having a high aspect ratio. Examples of nonylphenoxy polyethyleneoxy (meth)acrylate include nonylphenoxy tetraethyleneoxy (meth)acrylate, nonylphenoxy pentaethyleneoxy (meth)acrylate, nonylphenoxy hexaethyleneoxy (meth)acrylate, nonylphenoxy heptaethyleneoxy (meth)acrylate, nonylphenoxy octaethyleneoxy (meth)acrylate, nonylphenoxy nonaethyleneoxy (meth)acrylate, nonylphenoxy decaethyleneoxy (meth)acrylate, and nonylphenoxy undecaethyleneoxy (meth)acrylate. Examples of commercially available nonylphenoxy polyethyleneoxy (meth)acrylate include FA-318A (manufactured by Showa Denko Materials Co., Ltd.).

[0054] Examples of (meth)acrylates having a phthalic acid skeleton include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, etc. Examples of commercially available products of γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate include FA-MECH (manufactured by Showa Denko Materials Co., Ltd.).

[0055] The content of the (B) component may be in the following range relative to 100 parts by mass of the total of the (A) and (B) components, from the viewpoint of easily obtaining a cured product pattern in the space portion having a high aspect ratio. The content of the (B) component may be 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. The content of the (B) component may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these viewpoints, the content of the (B) component may be 10 to 90 parts by mass.

[0056] (Component (C): Photopolymerization initiator) The photosensitive resin film according to the present embodiment contains a photopolymerization initiator as component (C). As component (C), a compound capable of polymerizing component (B) can be used. From the viewpoint of easily improving sensitivity and resolution in a well-balanced manner, component (C) may contain at least one selected from the group consisting of hexaarylbiimidazole derivatives and acridine compounds (compounds having an acridinyl group).

[0057] Examples of hexaarylbiimidazole derivatives include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-di methoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and the like.

[0058] Examples of the acridine compounds include 9-phenylacridine, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine, 9-(p-chlorophenyl)acridine, 9-(m-chlorophenyl)acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine, 9-pentylaminoacridine, bis(9-acridinyl)alkanes (1,2-bis(9-acridinyl)ethane, 1,4-bis(9-acridinyl)butane, 1,6-bis(9-acridinyl)hexane, 1,8-bis (9-acridinyl)octane, 1,10-bis(9-acridinyl)decane, 1,12-bis(9-acridinyl)dodecane, 1,14-bis(9-acridinyl)tetradecane, 1,16-bis(9-acridinyl)hexadecane, 1,18-bis(9-acridinyl)octadecane, 1,20-bis(9-acridinyl)eicosane, etc.), 1,3-bis(9-acridinyl)-2-oxapropane, 1,3-bis(9-acridinyl)-2-thiapropane, 1,5-bis(9-acridinyl)-3-thiapentane, etc.

[0059] The content of the component (C) may be within the following ranges relative to 100 parts by mass of the total amount of the components (A) and (B). From the viewpoint of easily improving photosensitivity, resolution, and adhesion, the content of the component (C) may be 0.1 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more. From the viewpoint of easily obtaining excellent pattern formability, the content of the component (C) may be 10 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, or 3 parts by mass or less. From these viewpoints, the content of the component (C) may be 0.1 to 10 parts by mass.

[0060] (Component (D): Polymerization inhibitor) The photosensitive resin film according to this embodiment contains a polymerization inhibitor as component (D). By using component (D), pattern formability can be improved.

[0061] From the viewpoint of easily improving pattern formability, the component (D) may contain a compound represented by the following general formula (I). [ka]

[0062] In formula (I), R 5 represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, an aryl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, a carboxylalkyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, or a heterocyclic group; m is an integer of 2 or more, n is an integer of 0 or more, m+n=6, and when n is an integer of 2 or more, R 5 may be the same or different. The aryl group may be substituted with an alkyl group having 1 to 20 carbon atoms.

[0063] R 5 From the viewpoint of easily improving compatibility with the component (A), R may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 5 The alkyl group having 1 to 20 carbon atoms represented by the following formula may be an alkyl group having 1 to 4 carbon atoms. m may be 2 or 3, or may be 2, from the viewpoint of facilitating improvement of resolution.

[0064] Examples of the compound represented by the above general formula (I) include catechol compounds (compounds having two hydroxy groups at the ortho positions on the benzene ring) such as catechol, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; resorcinol (resorcin), 2-methylreductase, resorcinol compounds such as resorcinol, 4-methylresorcinol, 5-methylresorcinol (orcinol), 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; hydroquinone compounds such as 1,4-hydroquinone, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; and trihydric phenol compounds such as pyrogallol and phloroglucinol.

[0065] From the viewpoint of easily improving the resolution and easily obtaining a cured product pattern in the space portion having a high aspect ratio, the component (D) may contain a catechol compound, may contain an alkyl catechol, may contain at least one selected from the group consisting of 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol, and may contain at least one selected from the group consisting of 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol.

[0066] The content of the (D) component may be in the following ranges relative to 100 parts by mass of the total amount of the (A) component and the (B) component. The content of the (D) component is greater than 0 parts by mass, and from the viewpoint of easily allowing the photoreaction of the photocured portion to proceed sufficiently and thus easily enhancing pattern formability, the content of the (D) component may be 0.001 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, or 0.015 parts by mass or more. From the viewpoint of easily shortening the exposure time, the content of the (D) component may be 1 part by mass or less, less than 1 part by mass, 0.8 parts by mass or less, 0.5 parts by mass or less, 0.3 parts by mass or less, 0.2 parts by mass or less, 0.15 parts by mass or less, 0.1 parts by mass or less, 0.08 parts by mass or less, 0.05 parts by mass or less, 0.03 parts by mass or less, or 0.02 parts by mass or less. From these viewpoints, the content of the (D) component may be more than 0 part by mass and not more than 1 part by mass, more than 0 part by mass and less than 1 part by mass, or 0.01 to 0.3 part by mass. When the (D) component contains a catechol compound, the content of the (D) component may be more than 0 part by mass and less than 1 part by mass.

[0067] (Component (E): Photosensitizer) The photosensitive resin film according to the present embodiment may contain a photosensitizer (excluding compounds corresponding to the component (C)) as the component (E). By using the component (E), it is easy to effectively utilize the absorption wavelength of the actinic ray used for exposure.

[0068] Examples of the (E) component include a benzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone compound, a thioxanthone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound, a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, an aminoacridine compound, etc. From the viewpoint of easily improving the resolution, the (E) component may contain a benzophenone compound or a dialkylaminobenzophenone compound.

[0069] Examples of the dialkylaminobenzophenone compound include 4,4'-dialkylbenzophenones such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone; 4-benzoyl-4'-methyldiphenyl sulfide; and the like.

[0070] From the viewpoint of easily improving photosensitivity and resolution, the content of the component (E) may be in the following range relative to 100 parts by mass of the total amount of the components (A) and (B). The content of the component (E) may be 0.001 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, or 0.02 parts by mass or more. The content of the component (E) may be 5 parts by mass or less, 1 part by mass or less, 0.5 parts by mass or less, 0.2 parts by mass or less, 0.1 parts by mass or less, or 0.05 parts by mass or less. From these viewpoints, the content of the component (E) may be 0.01 to 5 parts by mass.

[0071] (Other Ingredients) The photosensitive resin film according to the present embodiment may contain leuco crystal violet. This makes it easy to improve the photosensitivity and resolution of the photosensitive resin film in a well-balanced manner. Leuco crystal violet has properties as a color former (photocolor former) that absorbs light and develops a specific color, and it is believed that the above-mentioned effects are due to its properties. The content of leuco crystal violet may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass relative to 100 parts by mass of the total amount of the (A) component and the (B) component.

[0072] The photosensitive resin film according to the present embodiment may contain other components, such as dyes (e.g., malachite green), tribromophenyl sulfone, color formers (except leuco crystal violet), thermal color-developing inhibitors, plasticizers (e.g., p-toluenesulfonamide), pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling promoters, antioxidants, fragrances, imaging agents, and thermal crosslinking agents.

[0073] <Photosensitive element> The photosensitive element according to this embodiment includes the photosensitive resin film according to this embodiment and a support that supports the photosensitive resin film. Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. The photosensitive element 1 shown in Fig. 1 includes a photosensitive resin film 1a and a support film (support) 1b that supports the photosensitive resin film 1a. The photosensitive resin film 1a is disposed on the support film 1b.

[0074] Examples of the support film include polyester films such as polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, and polyethylene-2,6-naphthalate (PEN) film; and polyolefin films such as polypropylene film and polyethylene film.

[0075] The haze of the support film may be 0.01 to 5.0%, 0.01 to 1.5%, 0.01 to 1.0%, or 0.01 to 0.5%. The haze can be measured using a commercially available haze meter (turbidity meter) in accordance with the method specified in JIS K7105. The haze can be measured, for example, using a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd., product name).

[0076] The thickness of the support film may be 1 to 200 μm, 1 to 100 μm, 1 to 60 μm, 5 to 60 μm, 10 to 60 μm, 10 to 50 μm, 10 to 40 μm, 10 to 30 μm, or 10 to 25 μm. When the thickness of the support film is 1 μm or more, it is easy to prevent the support film from being torn when peeling off the support film. When the thickness of the support film is 200 μm or less, it is easy to obtain economic benefits.

[0077] The photosensitive element according to this embodiment may have a protective film on the surface of the photosensitive resin film opposite to the support film. The protective film may be a polymer film such as a polyethylene film or a polypropylene film. The protective film may be a polymer film similar to the support film, or a polymer film different from the support film. The adhesive strength between the protective film and the photosensitive resin film may be smaller than the adhesive strength between the support film and the photosensitive resin film.

[0078] The photosensitive resin film can be formed, for example, by applying a photosensitive resin composition onto a support film and then drying. The application can be performed using a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, etc. Drying can be performed, for example, at 70 to 150°C for about 5 to 30 minutes.

[0079] When applying the photosensitive resin composition onto the support film, a solvent may be added as necessary to use a photosensitive resin composition with a solid content of about 30 to 60 mass %. Examples of the solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether.

[0080] The form of the photosensitive element is not particularly limited, and may be in the form of a sheet or a roll wound around a core. When wound into a roll, the support film may be wound on the outside.

[0081] <Method of manufacturing laminate> The method for producing the laminate according to this embodiment includes a photosensitive layer formation step of forming a photosensitive layer on a base material (substrate, etc.) using the photosensitive resin film or photosensitive resin composition according to this embodiment, an exposure step of photocuring a portion of the photosensitive layer, and a development step of removing at least a portion of the uncured portion of the photosensitive layer to form a cured product pattern.

[0082] The method for producing a laminate according to this embodiment may be a method for producing (forming) a resist pattern, which obtains a cured product pattern as a resist pattern, and the method for producing a resist pattern includes the above-mentioned photosensitive layer forming step, exposure step, and development step. The "resist pattern" is a photocured product pattern of a photosensitive resin film, and can also be said to be a relief pattern. The method for producing a resist pattern can also be said to be a method for producing a substrate having a resist pattern.

[0083] In the photosensitive layer forming step, a photosensitive layer is formed on a substrate using the photosensitive resin film or photosensitive resin composition according to this embodiment. In the photosensitive layer forming step, a photosensitive layer may be formed on a substrate using the photosensitive resin film of the photosensitive element according to this embodiment, or the photosensitive layer may be formed on the substrate by laminating the photosensitive resin film of the photosensitive element according to this embodiment on the substrate. When the photosensitive element has a protective film, the photosensitive resin film can be laminated on the substrate after removing the protective film. In the photosensitive layer forming step, for example, the photosensitive resin film of the photosensitive element is heated to about 70 to 130° C. while being heated at a reduced pressure or normal pressure of about 0.1 to 1 MPa (1 to 10 kgf / cm 2 ). 2 The photosensitive resin film is laminated on the substrate by pressing it with a pressure of about 1000 MPa (about 1000 MPa) to form a photosensitive layer on the substrate. The thickness of the photosensitive layer may be the same as the thickness of the photosensitive resin film according to the present embodiment. As the substrate, a laminate including an insulating layer and a metal layer disposed on the insulating layer may be used, and for example, a copper-clad laminate having copper foil on one or both sides of a layer made of an insulating material such as glass fiber reinforced epoxy resin may be used.

[0084] In the exposure step, at least a part of the photosensitive layer can be irradiated with active light rays to form a photocured portion. In the exposure step, at least a part of the photosensitive layer can be irradiated with active light rays after removing the support film, or at least a part of the photosensitive layer can be irradiated with active light rays through the support film. Examples of the exposure method include a method of irradiating active light rays imagewise through a negative or positive mask pattern called artwork (mask exposure method), a method of irradiating active light rays imagewise by a projection exposure method, and a method of irradiating active light rays imagewise by a direct writing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method.

[0085] As the light source of the actinic rays, a light source that effectively radiates ultraviolet light or visible light may be used, and examples of such light include carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers (such as argon lasers), solid-state lasers (such as YAG lasers), and semiconductor lasers.

[0086] In the method for producing a laminate according to the present embodiment, from the viewpoint of improving adhesion, post-exposure bake (PEB) may be performed after the exposure step and before the development step. The temperature when performing PEB may be 50 to 100° C. As the heater, a hot plate, a box dryer, a heating roll, or the like may be used.

[0087] In the developing step, at least a portion of the photosensitive layer other than the photocured portion is removed from the substrate as the unexposed portion of the photosensitive layer, thereby forming a cured product pattern on the substrate. In the developing step, a portion or all of the unexposed portion of the photosensitive layer is removed. When a laminate having a metal layer disposed on an insulating layer is used as the substrate, the metal layer can be exposed by removing the unexposed portion of the photosensitive layer.

[0088] When a support film is present on the photosensitive layer, the support film can be removed, and then the portions of the photosensitive layer other than the photocured portions (unexposed portions) can be removed (developed). As the development method, wet development or dry development can be used.

[0089] In the case of wet development, development can be performed by a known development method using a developer that corresponds to the composition of the photosensitive layer. Examples of the development method include a dip method, a paddle method, a spray method, a brushing method, a slapping method, a scrubbing method, a method using a swinging immersion method, etc., and from the viewpoint of easily improving the resolution, a high-pressure spray method may be used. Development may be performed by combining two or more development methods.

[0090] The composition of the developer is appropriately selected depending on the composition of the photosensitive layer. Examples of the developer include an alkaline aqueous solution and an organic solvent developer.

[0091] As the developer, an alkaline aqueous solution may be used from the viewpoint of safety, stability, and good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxide (lithium, sodium, or potassium hydroxide, etc.), alkali carbonate (lithium, sodium, potassium, or ammonium carbonate or bicarbonate, etc.), alkali metal phosphate (potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphate (sodium pyrophosphate, potassium pyrophosphate, etc.), borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine, etc.

[0092] Examples of the alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution, a 0.1 to 5% by mass aqueous potassium carbonate solution, a 0.1 to 5% by mass aqueous sodium hydroxide solution, etc. The pH of the alkaline aqueous solution may be 9 to 11. The temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive layer.

[0093] The alkaline aqueous solution may contain, for example, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, etc. Examples of organic solvents used in the alkaline aqueous solution include acetone, ethyl acetate, an alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Examples of organic solvents used in the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, etc. The content of the organic solvent in the organic solvent developer may be adjusted to a range of 1 to 20% by mass by mixing the organic solvent with water.

[0094] In the method for producing the laminate according to the present embodiment, after the development step, heating at about 60 to 250° C. or applying a pressure of 0.2 to 10 J / cm may be performed as necessary.2 The method may further include a step of further curing the cured product pattern by exposure to light of about 100 nm.

[0095] The method for producing the laminate according to the present embodiment may include a conductor layer forming step of forming a conductor layer (e.g., a metal layer) on at least a part of the portion of the substrate where the cured product pattern is not formed after the development step. In the conductor layer forming step, a conductor pattern (e.g., a wiring pattern) may be obtained as the conductor layer, and the method for producing the laminate according to the present embodiment may be a method for producing (forming) a conductor pattern (e.g., a wiring pattern). Examples of materials constituting the conductor layer include copper, solder, nickel, and gold. The method for producing the laminate according to the present embodiment may be a method for producing a wiring board (e.g., a printed wiring board) having a conductor pattern.

[0096] In the conductor layer forming step, at least a part of the portion of the substrate where the cured product pattern is not formed may be plated to form a conductor layer. In the conductor layer forming step, at least a part of the portion of the substrate where the cured product pattern is not formed may be plated using the cured product pattern as a mask. When a laminate having a metal layer disposed on an insulating layer is used as the substrate, the metal layer exposed in the portion of the substrate where the cured product pattern is not formed may be plated.

[0097] The plating process may be an electrolytic plating process or an electroless plating process, which may include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as Watts bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating.

[0098] The method for producing a laminate according to the present embodiment may include a cured product removal step of removing at least a portion of the cured product pattern after the conductor layer formation step. In the cured product removal step, a part or the whole of the cured product pattern may be removed.

[0099] The cured product pattern can be peeled off and removed, for example, with an aqueous solution that is more strongly alkaline than the aqueous solution used in the development step. As the aqueous solution of the strong alkali, for example, a 1 to 10% by mass aqueous solution of sodium hydroxide, a 1 to 10% by mass aqueous solution of potassium hydroxide, etc. can be used. Methods for removing the cured product pattern include a dipping method and a spray method. The methods for removing the cured product pattern may be used alone or in combination.

[0100] When a laminate having a metal layer disposed on an insulating layer is used as a substrate, the portion of the metal layer that was covered with the cured product pattern is exposed in the cured product removal step. The method for producing a laminate according to this embodiment may include a step of removing the exposed portion of the metal layer after the cured product removal step. The metal layer can be removed, for example, by an etching process.

[0101] FIG. 2 is a schematic cross-sectional view showing an example of a method for producing a laminate. First, as shown in (a) of Fig. 2, in a photosensitive layer forming step, a photosensitive layer 10 is formed on a substrate 20 using the photosensitive element 1 of Fig. 1 or the like. In the photosensitive layer forming step, for example, a photosensitive resin film 1a of the photosensitive element 1 is laminated on the substrate 20 as the photosensitive layer 10, and then the support film 1b is peeled off. As the substrate 20, a laminate having a metal layer disposed on an insulating layer can be used. Next, as shown in FIG. 2(b), in an exposure step, the photosensitive layer 10 is irradiated with active light rays L to form a photocured portion. Next, as shown in FIG. 2(c), in a development step, the uncured portions of the photosensitive layer 10 are removed to form a cured pattern (resist pattern) 10a. Next, as shown in FIG. 2(d), in the conductor layer formation step, a plating process is performed using the cured material pattern 10a as a mask to form a conductor layer (plating layer) 30 in the portion of the substrate 20 where the cured material pattern 10a is not formed. 2(e), in a cured product removing step, the cured product pattern 10a is removed, thereby obtaining a laminate having a conductor layer 30 as a conductor pattern. EXAMPLES

[0102] The present disclosure will be described more specifically below with reference to examples, but the present disclosure is not limited to these examples.

[0103] <Preparation of Photosensitive Resin Element> A total of 56 parts by mass of the binder polymer shown in Table 1, 24 parts by mass of photopolymerizable compound B-1, 5 parts by mass of photopolymerizable compound B-2, 5 parts by mass of photopolymerizable compound B-3, 5 parts by mass of photopolymerizable compound B-4, 5 parts by mass of photopolymerizable compound B-5, 3 parts by mass of a photopolymerization initiator (B-CIM, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and 0.016 parts by mass of a polymerization inhibitor (TBC, 4-tert-butylcatechol, manufactured by DIC Corporation). A solution of a photosensitive resin composition was prepared by mixing 0.02 parts by mass of a photosensitizer (4,4'-bis(diethylamino)benzophenone, manufactured by Hodogaya Chemical Co., Ltd., trade name "EAB"), 0.35 parts by mass of a color former (LCV, leuco crystal violet, manufactured by Yamada Chemical Co., Ltd.), 0.008 parts by mass of a dye (MKG, malachite green, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 0.008 parts by mass of a leveling agent (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name "SH-193"). The unit of the amount of the binder polymer used in Table 1 is "parts by mass". When the blending component is a solution, the amount used is the amount converted to solid content.

[0104] Details of the binder polymer and the photopolymerizable compound are as follows.

[0105] (Binder polymer) A-1: Ethylene glycol monomethyl ether / acetone solution (solid content: 48% by mass) of a copolymer of methacrylic acid / methyl methacrylate / butyl methacrylate (mass ratio: 30 / 35 / 35, Mw: 50,000, Mn: 21,000, acid value: 196 mg KOH / g) A-2: Ethylene glycol monomethyl ether / toluene solution (solid content: 47% by mass) of a copolymer of methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate (mass ratio: 27 / 5 / 45 / 23, Mw: 51000, Mn: 22000, acid value: 176 mgKOH / g) A-3: Ethylene glycol monomethyl ether / toluene solution (solid content: 49% by mass) of a copolymer of methacrylic acid / 2-hydroxyethyl methacrylate / styrene / benzyl methacrylate (mass ratio: 27 / 3 / 50 / 20, Mw: 35000, Mn: 16000, acid value: 176 mgKOH / g)

[0106] (Photopolymerizable compound) Photopolymerizable compound B-1: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (manufactured by Showa Denko Materials Co., Ltd., product name "FA-321M", number of EO groups: 10 (average value)) Photopolymerizable compound B-2: polyalkylene glycol dimethacrylate (manufactured by Showa Denko Materials Co., Ltd., product name "FA-023M", number of EO groups: 6 (average value), number of PO groups: 12 (average value)) Photopolymerizable compound B-3: Polyoxyethylene urethane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "UA-11") Photopolymerizable compound B-4: Polyoxyethylene polyoxypropylene urethane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "UA-13") Photopolymerizable compound B-5: Nonylphenoxy polyethylene glycol acrylate (manufactured by Showa Denko Materials Co., Ltd., product name "FA-318A")

[0107] A solution of the photosensitive resin composition was uniformly applied onto a PET film (support film, thickness: 16 μm, manufactured by Toray Industries, Inc., product name: FB-40), and then dried at 70° C. for 10 minutes and at 100° C. for 10 minutes using a hot air convection dryer to produce a photosensitive element having a photosensitive layer (photosensitive resin film) made of the photosensitive resin composition on one side of the PET film. The thickness of 10 points of the photosensitive layer was measured using a measuring device manufactured by Nikon Corporation (main body: product name "MH-15", measuring stage: product name "MS-5C"), and the average thickness value was obtained. The average thickness value of the photosensitive layer is shown in Table 1.

[0108] <Evaluation> (resolution) A copper-clad laminate (manufactured by Showa Denko Materials Co., Ltd., product name "MCL-E-67") in which copper foil (thickness: 12 μm) was laminated on both sides of a glass fiber reinforced epoxy resin layer was washed with water. Then, pickling and washing with water were performed, and then drying was performed with an air flow. Next, the copper-clad laminate was heated to 80°C, and then a photosensitive element was laminated on the copper foil of the copper-clad laminate. The lamination was performed using a heat roll at 110°C at a pressure of 0.4 MPa and a roll speed of 1.0 m / min. As a result, a laminate in which the copper-clad laminate, the photosensitive layer, and the PET film were laminated in this order was obtained.

[0109] A phototool having a 41-step tablet with a density range of 0.00 to 2.00, density step of 0.05, tablet size of 20 mm x 187 mm, and each step size of 3 mm x 12 mm was placed on the PET film of the laminate as a negative mask. Next, the photosensitive layer was exposed to a parallel light exposure device (manufactured by Oak Manufacturing Co., Ltd., product name "EXM-1201") using a high-pressure mercury lamp as a light source with an energy amount such that the number of remaining steps after development of the 41-step tablet was 17.0 steps.

[0110] A test pattern (line width / space width: x / x (x: 8-100, unit: μm)) was placed on the PET film of the laminate as a negative for evaluating resolution. The photosensitive layer was then exposed with an energy amount that would result in 17.0 remaining steps after development of a 41-step tablet. The PET film was then peeled off, and the unexposed areas were removed (developed) by spraying a 1% by mass aqueous solution of sodium carbonate at 30°C for twice the shortest development time (the shortest time required for the unexposed areas to be removed), to obtain a resist pattern (cured product pattern).

[0111] After development, the space portions (unexposed portions) were completely removed, and the line portions (exposed portions) were formed without meandering or chipping. The resolution was evaluated based on the smallest line width / space width value among the resist patterns. The resolution was evaluated based on the minimum space width. The smaller this value, the better the resolution. The ratio of the thickness of the resist pattern to this minimum resolution value (aspect ratio: thickness of resist pattern / minimum resolution value) was also calculated. The results are shown in Table 1.

[0112] [Table 1] [Explanation of symbols]

[0113] Reference Signs List 1: photosensitive element, 1a: photosensitive resin film, 1b: support film (support), 10: photosensitive layer, 10a: cured product pattern, 20: substrate, 30: conductive layer, L: actinic light.

Claims

1. The composition contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a polymerization inhibitor, the binder polymer includes a polymer having, as a monomer unit, an alkyl (meth)acrylate having an alkyl group having 3 or more carbon atoms, A photosensitive resin film having a thickness of 35 to 300 μm (however, excluding a photosensitive resin composition for laser direct imaging exposure containing (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, (C1) an acridine compound, (C2) a 2,4,5-triaryl imidazole dimer, (D) a halogen compound, and (E) a polymerization inhibitor, the content of the polymerization inhibitor (E) being 20 to 100 ppm by mass; and a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond in the molecule, (C) a photopolymerization initiator, and (D) a polymerization inhibitor, the content of the polymerization inhibitor (D) being 20 to 100 ppm by mass based on the total amount of solids in the composition).

2. The photosensitive resin film according to claim 1 , wherein the binder polymer comprises a polymer having butyl (meth)acrylate as a monomer unit.

3. The photosensitive resin film according to claim 1 , wherein the photopolymerizable compound comprises a bisphenol (meth)acrylate.

4. The photosensitive resin film according to any one of claims 1 to 3, wherein the photopolymerizable compound comprises polyalkylene glycol di(meth)acrylate.

5. The photosensitive resin film according to any one of claims 1 to 4, wherein the photopolymerizable compound comprises a (meth)acrylate having a urethane bond.

6. The photosensitive resin film according to any one of claims 1 to 5, wherein the polymerization inhibitor comprises a catechol compound.

7. The photosensitive resin film according to claim 6 , wherein the content of the polymerization inhibitor is more than 0 part by mass and less than 1 part by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

8. The photosensitive resin film according to any one of claims 1 to 7, wherein the content of the polymerization inhibitor is 0.01 to 0.3 parts by mass per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

9. A photosensitive element comprising the photosensitive resin film according to any one of claims 1 to 8 and a support for supporting the photosensitive resin film.

10. A step of forming a photosensitive layer on a substrate using the photosensitive resin film according to any one of claims 1 to 8; photocuring a portion of the photosensitive layer; and removing at least a portion of the uncured portion of the photosensitive layer to form a cured pattern.

11. The method for producing a laminate according to claim 10 , further comprising the step of forming a conductive layer on at least a part of an area of ​​the substrate where the cured product pattern is not formed.

12. The method for producing a laminate according to claim 11 , further comprising a step of removing at least a portion of the cured product pattern.

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