Photosensitive element and method for forming resist pattern

Abstract

Provided are a photosensitive element that achieves both improved resolution and prevention of wrinkles during winding, and a method for forming a resist pattern. A photosensitive element comprising, in this order, a support film (A), a photosensitive resin composition layer (B), and a protective film (C), wherein the surface roughness Rz of the support film (A) on the side in contact with the photosensitive resin composition layer (B) as specified in JIS B0601-2001 is A1 (nm), surface roughness Rz of the opposite side A2 (nm), surface roughness Rz of the surface of the protective film (C) on the side in contact with the photosensitive resin composition layer (B) C1 (nm), surface roughness Rz of the opposite side C2 (nm) satisfies the following (1) to (3): (1) 1 <Rz A1 <100, (2) 300 <Rz C1 <600, (3) 40 <Rz C2 / Rz A2 .

Description

Technical Field

[0001] The present invention relates to a photosensitive element and a method for forming a resist pattern. Background Art

[0002] Printed wiring boards and the like are used in electronic devices such as personal computers and mobile phones for mounting components and semiconductors. As resists for the production of printed wiring boards and the like, photosensitive elements (photosensitive resin laminates) have been used, which are formed by laminating a photosensitive resin composition layer on a support film and, if necessary, laminating a protective film on the photosensitive resin composition layer. These so-called dry film resists have been used (for example, see Patent Documents 1 and 2).

[0003] In order to improve the resolution of such a photosensitive element, it is preferable to use a high-quality film having few internal foreign matter that blocks light for exposure as a support film.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2004-191648

[0007] Patent Document 2: Japanese Patent Application Publication No. 2019-188612 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] However, since high-quality films have low surface roughness, when a photosensitive resin composition layer and a protective film are laminated and wound into a roll, the friction force at the interface with the protective film is too high, causing wrinkles.

[0010] The present invention has been made in view of such conventional circumstances, and an object of the present invention is to provide a photosensitive element and a method for forming a resist pattern that achieve both improvement in resolution and prevention of wrinkles during winding.

[0011] Solutions for solving problems

[0012] The present inventors have discovered that the above-mentioned problems can be solved by the following technical means.

[0013] [1] A photosensitive element, characterized in that:

[0014] It has a support film (A), a photosensitive resin composition layer (B) and a protective film (C) in this order,

[0015] Surface roughness Rz of the surface of the support film (A) on the side in contact with the photosensitive resin composition layer (B) as specified in JIS B0601-2001 A1(nm), surface roughness Rz of the opposite side A2 (nm), the surface roughness Rz of the surface of the protective film (C) on the side in contact with the photosensitive resin composition layer (B) C1 (nm), and the surface roughness Rz of the opposite side C2 (nm) satisfies the following (1) to (3):

[0016] (1)1 <Rz A1 <100

[0017] (2)300 <Rz C1 <600

[0018] (3)40 <Rz C2 / Rz A2 . [2]

[0020] The photosensitive element according to [1], wherein 1 <Rz A2 <200. [3]

[0022] The photosensitive element according to [1] or [2], wherein 1.1 <Rz A2 / Rz A1 <7. [4]

[0024] The photosensitive element according to any one of [1] to [3], wherein 1.1 <Rz C2 / Rz C1 <10. [5]

[0026] The photosensitive element according to any one of [1] to [4], wherein 50 <Rz C2 / Rz A2 <100. [6]

[0028] The photosensitive element according to any one of [1] to [5], wherein the number of particles having a diameter of 2 μm or more and 5 μm or less contained in the supporting film (A) is 30 particles / 30 mm. 2 the following. [7]

[0030] The photosensitive element according to any one of [1] to [6], wherein the number of particles having a diameter of 2 μm or more and 5 μm or less contained in the supporting film (A) is 15 particles / 30 mm. 2 the following. [8]

[0032] The photosensitive element according to any one of [1] to [7], wherein the number of particles having a diameter of 2 μm or more and 5 μm or less contained in the supporting film (A) is 10 particles / 30 mm. 2 the following. [9]

[0034] The photosensitive element according to any one of [1] to [8], wherein the content of the titanium element contained in the supporting film (A) is 1 ppm or more and 20 ppm or less.

[10]

[0036] The photosensitive element according to any one of [1] to [9], wherein at least one surface of the support film (A) is subjected to a smoothing treatment.

[11]

[0038] The photosensitive element according to any one of [1] to

[10] , wherein the support film (A) has a thickness of 5 μm to 12 μm.

[12]

[0040] The photosensitive element according to any one of [1] to

[11] , wherein the surface of the protective film (C) is formed of a polypropylene resin.

[13]

[0042] A wound body of a photosensitive element, which is formed by winding the photosensitive element described in any one of [1] to

[12] .

[14]

[0044] A method for forming a resist pattern, comprising:

[0045] a lamination step of laminating the photosensitive element according to any one of [1] to

[12] on a substrate,

[0046] an exposure step of exposing the photosensitive resin composition layer of the photosensitive element, and

[0047] A developing step of developing and removing the unexposed portion of the photosensitive resin composition layer.

[15]

[0049] The method for forming a resist pattern according to

[14] , wherein the exposure step is performed by a projection exposure method.

[0050] Effects of the Invention

[0051] According to the present invention, a photosensitive element and a method for forming a resist pattern that achieve both improvement in resolution and prevention of wrinkles during winding can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1This is a cross-sectional view schematically showing a structural example of the photosensitive element of the present invention. DETAILED DESCRIPTION

[0053] Hereinafter, embodiments for implementing the present invention will be described in detail.

[0054] [Photosensitive element]

[0055] Figure 1 This is a cross-sectional view schematically showing a structural example of the photosensitive element of the present invention.

[0056] The photosensitive element of the present invention is characterized in that it comprises a support film (A), a photosensitive resin composition layer (B), and a protective film (C) in this order.

[0057] Surface roughness Rz of the surface of the support film (A) on the side in contact with the photosensitive resin composition layer as specified in JIS B0601 A1 (nm), surface roughness Rz of the opposite side A2 (nm), surface roughness Rz of the surface of the protective film (C) on the side in contact with the photosensitive resin composition layer C1 (nm), and the surface roughness Rz of the opposite side C2 (nm) satisfies the following (1) to (3):

[0058] (1)1 <Rz A1 <100

[0059] (2)300 <Rz C1 <600

[0060] (3)40 <Rz C2 / Rz A2 .

[0061] In order to improve the resolution of the photosensitive element, it is preferable to use a high-quality film having few internal foreign matter that blocks light for exposure as the support film (A).

[0062] High-quality films are characterized by low surface roughness, particularly on the side in contact with the photosensitive resin composition layer (B). However, when these films are used to produce photosensitive element rolls (dry film rolls), the friction with the protective film (C) becomes excessively high, causing wrinkles when the roll is wound up. Therefore, to prevent wrinkles during roll winding, the surface roughness of the protective film (C) on the side in contact with the support film (A) can be increased.

[0063] In order to achieve both of the above-mentioned issues (improvement in resolution and prevention of wrinkles during winding), it is important for the support film (A) to have a low surface roughness and a smoother surface on the side in contact with the photosensitive resin composition layer (B); and it is important for the protective film (C) to have a smooth surface on the side in contact with the photosensitive resin composition layer (B) and a roughened surface on the other side. Specifically, the present inventors have determined that a layer structure in which the support film (A) and the protective film (C) are smooth to a certain extent and each has a roughened surface on one side is ideal.

[0064] Therefore, the present inventors have achieved a photosensitive element that achieves both improved resolution and prevention of wrinkles when wound into a roll by making the surfaces of the supporting film (A) and the protective film (C) smooth to a certain extent and providing a difference in surface roughness between the supporting film (A) and the protective film (C).

[0065] In the present invention, the above-mentioned structure is defined by equations (1) to (3). By satisfying all of equations (1) to (3), the photosensitive element of the present invention has good resolution and is suitably prevented from wrinkling when wound into a roll.

[0066] In this specification, surface roughness refers to the maximum height Rz measured by the method specified in JIS B0601-2001. Surface roughness can be measured using a conventional surface roughness measuring instrument such as a laser, stylus, optical section, or optical interferometer.

[0067] Support film (A)

[0068] The supporting film (A) of the present embodiment is a layer or film for supporting the photosensitive resin composition layer (B), and is preferably a transparent base film that transmits active light.

[0069] Examples of the transparent base film include films made of synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. In general, polyethylene terephthalate (PET) is preferably used because it has appropriate flexibility and strength.

[0070] Among these, it is preferable to use a high-quality film with few internal foreign matter. Specifically, PET films synthesized using a Ti-based catalyst; PET films with a small diameter and low lubricant content; PET films containing a lubricant only on one side of the film; thin PET films; PET films with smoothing treatment applied to at least one side; and PET films with roughening treatment such as plasma treatment applied to at least one side are more preferable as high-quality films.

[0071] Thereby, the light for exposure can be irradiated to the photosensitive resin composition layer (B) without being blocked by internal foreign matter, and the resolution of the photosensitive element can be improved.

[0072] The number of particles with a diameter of 2 μm or more and 5 μm or less contained in the supporting film (A) as internal foreign matter is preferably 30 particles / 30 mm. 2 Less than, more preferably 15 / 30mm 2 Below, more preferably 10 / 30mm 2 the following.

[0073] The titanium (Ti) content in the supporting film (A) is preferably from 1 ppm to 20 ppm, more preferably from 2 ppm to 12 ppm. A titanium content of 20 ppm or less can reduce the number of internal foreign matter originating from titanium-containing aggregates and prevent a decrease in resolution.

[0074] The thickness of the supporting film (A) is preferably from 5 μm to 16 μm, more preferably from 6 μm to 12 μm. A thinner supporting film reduces the number of internal foreign matter, thus preventing a decrease in resolution. However, a film thickness of less than 5 μm can cause elongation deformation in the winding direction due to tension during the coating / winding process, rupture due to minor defects, and insufficient film strength, leading to wrinkles during lamination.

[0075] Preferably, at least one surface of the support film (A) is smoothed using a calender or the like. This reduces the surface roughness of one surface of the support film (A), particularly the surface in contact with the photosensitive resin composition layer (B), thereby further enhancing the effects of the present invention.

[0076] From the viewpoint of improving the parallelism of light irradiating the photosensitive resin composition layer (B) and obtaining higher resolution after exposure and development of the photosensitive element, the haze of the support film (A) is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01 to 0.95%.

[0077] Furthermore, in the photosensitive element of the present embodiment, the surface roughness of both surfaces of the support film (A) satisfies the following formula (1).

[0078] (1)1 <Rz A1 <100

[0079] Here, Rz A1 The surface roughness (nm) and Rz of the surface of the support film (A) on the side in contact with the photosensitive resin composition layer (B) are shown. A2 It shows the surface roughness (nm) of the opposite surface.

[0080] In the formula (1), although both surfaces of the support film (A) are smooth, one surface is specified to be a roughened surface. This allows the photosensitive element to have excellent resolution.

[0081] Rz A1 and Rz A2 There are no particular restrictions as long as the above formula (1) is satisfied, but Rz is more preferably A1 10nm~70nm. Rz A2 Compared with Rz A1 The size of Rz is irrelevant as long as it is a small value. A2 Preferably 1 nm <Rz A2 <200nm, preferably 40nm to 100nm, more preferably 50nm to 90nm. A2 / Rz A1 Preferably 1.1 <Rz A2 / Rz A1 <7, more preferably 1.2 to 5.

[0082] <Photosensitive resin composition layer (B)>

[0083] The photosensitive resin composition layer (B) is laminated on the support film (A). A known photosensitive resin composition layer can be used as the photosensitive resin composition layer (B) of this embodiment. Typically, the photosensitive resin composition layer is formed from a photosensitive resin composition containing the following components: (i) an alkali-soluble polymer, (ii) a component containing an ethylenically unsaturated double bond (e.g., an ethylenically unsaturated addition-polymerizable monomer), and (iii) a photopolymerization initiator.

[0084] The alkali-soluble polymer as component (i) preferably has a carboxyl group from the viewpoint of alkali solubility and preferably has an aromatic group in its side chain from the viewpoint of cured film strength and coatability of the photosensitive resin composition.

[0085] The acid equivalent of the alkali-soluble polymer is preferably 100 or greater from the viewpoint of the development resistance of the photosensitive resin composition layer and the development resistance, resolution, and adhesion of the resist pattern, and is preferably 600 or less from the viewpoint of the developability and releasability of the photosensitive resin composition layer. It is more preferably 250 to 550, and even more preferably 300 to 500.

[0086] From the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to a developer, the weight average molecular weight of the alkali-soluble polymer is preferably within the range of 5,000 to 500,000, more preferably 10,000 to 200,000, and even more preferably 18,000 to 100,000.

[0087] In this specification, the weight average molecular weight refers to the weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. The dispersity of the alkali-soluble polymer is preferably 1.0 to 6.0.

[0088] Examples of the alkali-soluble polymer include carboxylic acid-containing vinyl copolymers and carboxylic acid-containing cellulose.

[0089] The carboxylic acid-containing vinyl copolymer is a compound obtained by vinyl copolymerization of at least one first monomer selected from α- and β-unsaturated carboxylic acids and at least one second monomer selected from alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, (meth)acrylamide and compounds in which the hydrogen on the nitrogen is substituted with an alkyl or alkoxy group, styrene and styrene derivatives, (meth)acrylonitrile, and glycidyl (meth)acrylate.

[0090] Examples of the first monomer used in the carboxylic acid-containing vinyl copolymer include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester, etc. These first monomers can be used alone or in combination of two or more.

[0091] The content ratio of the structural unit of the first monomer in the carboxylic acid-containing vinyl copolymer is 15% to 40% by mass, preferably 20% to 35% by mass, based on the mass of the copolymer. If this ratio is less than 15% by mass, development with an alkaline aqueous solution becomes difficult. If this ratio exceeds 40% by mass, the first monomer becomes insoluble in the solvent during polymerization, making it difficult to synthesize the copolymer.

[0092] Specific examples of the second monomer used in the carboxylic acid-containing vinyl copolymer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, cyclohexyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, (meth)acrylamide, N-hydroxymethyl acrylamide, N-butoxymethyl acrylamide, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, (meth)acrylonitrile, and glycidyl (meth)acrylate. These second monomers can be used alone or in combination of two or more.

[0093] The content ratio of the structural unit of the second monomer in the carboxylic acid-containing vinyl copolymer is 60% by mass or more and 85% by mass or less, preferably 65% by mass or more and 80% by mass or less, based on the mass of the copolymer.

[0094] From the perspective of introducing an aromatic group into the side chain, it is more preferable to include a structural unit of styrene or a styrene derivative such as α-methylstyrene, p-methylstyrene, or p-chlorostyrene in the carboxylic acid-containing vinyl copolymer as the second monomer. In this case, the content of the structural unit of styrene or a styrene derivative in the carboxylic acid-containing vinyl copolymer is preferably 5% by mass to 35% by mass, and more preferably 15% by mass to 30% by mass, based on the mass of the copolymer.

[0095] The weight average molecular weight of the carboxylic acid-containing vinyl copolymer is within the range of 10,000 to 200,000, preferably 18,000 to 100,000. If the weight average molecular weight is less than 10,000, the strength of the cured film is reduced. If the weight average molecular weight exceeds 200,000, the viscosity of the photosensitive resin composition is too high, and its coating properties are reduced.

[0096] Carboxylic acid-containing vinyl copolymers are preferably synthesized by adding an appropriate amount of a free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution prepared by diluting a mixture of various monomers with a solvent such as acetone, methyl ethyl ketone, or isopropyl alcohol, followed by superheated stirring. Synthesis is sometimes performed while a portion of the mixture is dropwise added to the reaction solution. Alternatively, after the reaction is complete, further solvent is added to adjust the desired concentration. Synthesis methods include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.

[0097] Examples of carboxylic acid-containing cellulose include cellulose acetate phthalate and hydroxyethyl / carboxymethyl cellulose. The content of the alkali-soluble polymer (A) is preferably in the range of 30% by mass or more and 80% by mass or less, and more preferably in the range of 40% by mass or more and 65% by mass or less, based on the total mass of the photosensitive resin composition. If the content is less than 30% by mass, the dispersibility in the alkaline developer is reduced and the development time is significantly prolonged. If the content exceeds 80% by mass, the photocuring of the photosensitive resin composition layer is insufficient and the resistance as a resist is reduced. The alkali-soluble polymer can be used alone or in combination of two or more.

[0098] As the ethylenically unsaturated addition-polymerizable monomer as the component (ii), known compounds can be used. Examples of the ethylenically unsaturated addition-polymerizable monomer include 2-hydroxy-3-phenoxypropyl acrylate, phenoxytetraethylene glycol acrylate, β-hydroxypropyl-β'-(acryloyloxy)propyl phthalate, 1,4-tetramethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, heptapropylene glycol di(meth)acrylate, glycerol (meth)acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylate, glycerol tri(meth)acrylate, and a compound containing at least one of an oxyethylene chain, an oxypropylene chain, and an oxytetramethylene chain in the molecule of trimethylolpropane tri(meth)acrylate; a compound containing at least one of an oxyethylene chain, an oxypropylene chain, and an oxytetramethylene chain in the molecule of dipentaerythritol penta(meth)acrylate; and dipentaerythritol hexa(meth)acrylate. Compounds containing at least one of an oxidized ethylene chain, an oxidized propylene chain, and an oxidized tetramethylene chain in the molecule of an acrylate, trimethylolpropane triglycidyl ether tri(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, diallyl phthalate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 4-n-octylphenoxypentapropylene glycol acrylate, bis(triethylene glycol methacrylate)nonapropylene glycol, bis(tetraethylene glycol methacrylate)polypropylene glycol, bis(triethylene glycol methacrylate)polypropylene glycol, bis(diethylene glycol acrylate)polypropylene glycol, 4-n-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, phenoxytetrapropylene glycol tetraethylene glycol (meth)acrylate, compounds containing at least one of an oxidized ethylene chain, an oxidized propylene chain, and an oxidized tetramethylene chain in the molecule of a bisphenol A-based (meth)acrylate monomer, and the like. The ethylenically unsaturated addition polymerizable monomer may be a compound other than the above compounds exemplified for the purpose of containing at least one of an oxyethylene chain, an oxypropylene chain, and an oxytetramethylene chain, or may contain an oxyalkylene chain of at least one of an oxyethylene chain, an oxypropylene chain, and an oxytetramethylene chain.

[0099] In addition, as ethylenically unsaturated addition polymerizable monomers, polyisocyanate compounds such as hexamethylene diisocyanate and tolylene diisocyanate, and urethanized compounds of hydroxy acrylate compounds such as 2-hydroxypropyl (meth)acrylate, oligoethylene glycol mono(meth)acrylate, and oligopropylene glycol mono(meth)acrylate can also be used. These ethylenically unsaturated addition polymerizable monomers can be used alone or in combination of two or more.

[0100] The content of the ethylenically unsaturated addition-polymerizable monomer is preferably 20% to 70% by mass, more preferably 30% to 60% by mass, based on the total mass of the photosensitive resin composition. If the content is less than 20% by mass, the photosensitive resin will not cure sufficiently, resulting in insufficient strength as a resist. On the other hand, if the content exceeds 70% by mass, when the photosensitive element is stored in a roll, the photosensitive resin composition layer or the photosensitive resin composition may slowly overflow from the end of the roll, a phenomenon known as edge fusion.

[0101] Examples of the photopolymerization initiator as the component (iii) include benzyldimethylketal, benzyldiethylketal, benzyldipropylketal, benzyldiphenylketal, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4'-bis(dimethylamino)benzophenone [Michler's ketone], 4,4'-bis(diethylamino)benzophenone, 2,2-dimethoxy Aromatic ketones such as 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer; biimidazole compounds such as 9-phenylacridine; aromatic initiators such as α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; N-aryl amino acids such as phenylglycine and N-phenylglycine; oxime esters such as 1-phenyl-1,2-propanedione-2-o-benzoyl oxime and 2,3-dioxo-3-phenylpropionic acid ethyl ester-2-(o-benzoylcarbonyl)-oxime; p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and p-diisopropylaminobenzoic acid, as well as their esters with alcohols, and p-hydroxybenzoic acid esters. Among them, a combination of 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer and Michler's ketone or 4,4'-(diethylamino)benzophenone is preferred.

[0102] The content of the photopolymerization initiator is preferably from 0.01% to 20% by mass, more preferably from 1% to 10% by mass, based on the total mass of the photosensitive resin composition. If the content is less than 0.01% by mass, the sensitivity may be insufficient. If the content exceeds 20% by mass, the ultraviolet absorption rate may increase, resulting in insufficient curing of the bottom portion of the photosensitive resin composition layer.

[0103] In order to improve the thermal stability and / or storage stability of the photosensitive resin composition layer (B) of the present embodiment, it is preferred that the photosensitive resin composition or the photosensitive resin composition layer contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include TEMPO derivatives such as 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxybenzoate radical, 2,2,6,6-tetramethylpiperidinyl-1-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl; phenothiazine, N,N-diethylhydroxylamine, naphthylamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, and 4,4'-dicumyl-diphenylamine; catechols such as 4-tert-butylpyrocatechol; quinones such as p-benzoquinone, hydroquinone, 2-hydroxy-1,4-naphthoquinone, tert-butylhydroquinone, methylhydroquinone, and 2,5-di-tert-butylhydroquinone; quinone methides such as di-tert-butyl-7-phenylquinone methide; cupferroniol; copper(II) dibutyldithiocarbamate; N-nitroso- Chelates such as N-phenylhydroxylamine aluminum, 2-tert-butyl-4,6-dimethylphenol, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, octyl-3,5-di-tert-butyl-4 -Hydroxy-hydrocinnamic acid, 2,2-bis[[[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]oxy]methyl]propane-1,3-diol 1,3-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], p-methoxyphenol, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) and other phenol derivatives, pyrogallol, cuprous chloride, etc.

[0104] In this embodiment, the photosensitive resin composition layer (B) may contain a coloring material such as a dye or pigment. Examples of the coloring material include fuchsin, phthalocyanine green, auramine base, alkoxide green S, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, malachite green, basic blue 20, and salicylic acid oxaline green.

[0105] In the present embodiment, a color-developing dye that develops color by light irradiation can be contained in the photosensitive resin composition layer (B). As a color-developing dye, for example, a combination of a leuco dye and a halogen compound is known. As a leuco dye, for example, tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leuco malachite green], etc. can be listed. As a halogen compound, for example, bromopentane, bromoisopentane, isobutylene bromide, vinyl bromide, diphenylmethane, dibromotoluene, dibromomethane, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, etc. can be listed.

[0106] In this embodiment, additives such as plasticizers may be contained in the photosensitive resin composition layer (B) as needed. Examples of the additives include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

[0107] The thickness of the photosensitive resin composition layer (B) is preferably 3 to 100 μm, with a more preferred upper limit of 50 μm. A thickness closer to 3 μm improves resolution, while a thickness closer to 100 μm improves film strength, so the thickness can be appropriately selected depending on the intended use.

[0108] <Protective film (C)>

[0109] The protective film (C) is laminated on the photosensitive resin composition layer (B) side of the laminate of the support film (A) and the photosensitive resin composition layer (B), and functions as a protective layer.

[0110] The adhesion between the photosensitive resin composition layer (B) and the protective film (C) is sufficiently smaller than the adhesion between the photosensitive resin composition layer (B) and the supporting film (A), so that the protective film (C) can be easily peeled off from the photosensitive resin composition layer (B). For example, polyethylene film, polypropylene film, stretched polypropylene film, etc. can be preferably used as the protective film (C). More preferably, at least the surface of the protective film (C) is formed of a polypropylene resin.

[0111] The thickness of the protective film (C) is preferably 10 to 100 μm, more preferably 10 to 50 μm. Examples of the protective film (C) include EM-501, E-200, E-201F, FG-201, and MA-411 manufactured by Oji F-Tex Co., Ltd.; KW37, 2578, 2548, 2500, and YM17S manufactured by Toray Industries, Inc.; and GF-18, GF-818, and GF-858 manufactured by Tamapoli Co., Ltd.

[0112] Furthermore, in the photosensitive element of this embodiment, the surface roughness of both surfaces of the protective film (C) satisfies the following formula (2).

[0113] (2)300 <Rz C1 <600

[0114] Here, Rz C1 The surface roughness (nm) of the surface of the protective film (C) on the side in contact with the photosensitive resin composition layer (B) is shown.

[0115] Formula (2) stipulates that the surface roughness of the protective film (C) on the side in contact with the photosensitive resin composition layer (B) is small. This allows the photosensitive element to have excellent resolution.

[0116] More preferably, 1.1 <Rz C2 / Rz C1 <10.

[0117] Here, Rz C2 The surface roughness (nm) of the surface of the protective film (C) opposite to the side in contact with the photosensitive resin composition layer (B) is shown.

[0118] Rz C1 and Rz C2 There is no particular limitation as long as the above formula (2) is satisfied. Specifically, Rz C1 Preferably, it is 350nm to 550nm. C2 It is preferably 400nm to 5500nm, more preferably 450nm to 4500nm. C2 / Rz C1 More preferably, it is 1.5 to 9.0.

[0119] Furthermore, in the photosensitive element of this embodiment, the surface roughness of both surfaces of the support film (A) and the protective film (C) satisfies the following formula (3).

[0120] (3)40 <Rz C2 / Rz A2

[0121] Here, RzA2 The surface roughness (nm) of the surface of the support film (A) opposite to the side in contact with the photosensitive resin composition layer (B) is represented by Rz. C2 The surface roughness (nm) of the surface of the protective film (C) opposite to the side in contact with the photosensitive resin composition layer (B) is shown.

[0122] Formula (3) stipulates that the surface roughness of the support film (A) and the surface roughness of the protective film (C) on the surface opposite to the side in contact with the photosensitive resin composition layer (B) differ by a certain amount or more. This effectively prevents wrinkles from forming when the photosensitive element is wound into a roll.

[0123] Rz C2 / Rz A2 The upper limit value is preferably less than 100, more preferably 50 <Rz C2 / Rz A2 <100. Rz C2 / Rz A2 More preferably, it is 40 to 80.

[0124] By satisfying all of the above-mentioned formulas (1) to (3), the photosensitive element of the present invention has good resolution and can suitably prevent wrinkles from occurring when the element is wound into a roll.

[0125] [Photosensitive element roll]

[0126] A photosensitive element roll obtained by winding the above-described photosensitive element is also one embodiment of the present invention.

[0127] The photosensitive element is wound onto a core in a long strip and used in a roll. The roll length is not particularly limited, but is preferably 320 m or less from the perspectives of roll weight and ease of handling. Efficiency improves when more substrates can be laminated using a single roll of the photosensitive element. Therefore, from the perspective of productivity, a roll length of 100 m or more is preferred.

[0128] (Core)

[0129] The winding core is sometimes also referred to as a core. Its shape is not particularly limited, and it can be cylindrical or columnar. Since the photosensitive element is used as an etching or plating resist and a permanent pattern in electronic materials, it is preferably subjected to dust-free processing and is preferably made of plastic resin. The raw material of the plastic resin is preferably a light, strong, and dust-free raw material. As such a plastic resin, for example, polypropylene (PP) resin, acrylonitrile butadiene styrene (ABS) resin, nylon resin, polyvinyl chloride resin, etc. can be used, preferably ABS resin. The diameter of the winding core is not particularly limited. When the photosensitive element is wound and mounted on a laminating device, it is preferably 2 to 5 inches, more preferably 3 inches in diameter so that it can be mounted on the device. The length of the winding core (the axial length when a cylindrical or columnar winding core is used) can be the same as or shorter than the width of the photosensitive element. In particular, the length of the winding core is preferably greater than the width of the photosensitive element so that appropriate protrusions can be ensured on both sides when the photosensitive element is wound. The annular sheet is preferably installed so as to be inserted into the protrusion. Furthermore, by fitting a bearing called a core holder into the protruding portion, the photosensitive element roll can be stored in a suspended state so as not to move.

[0130] The photosensitive element roll may be arranged so that the roll end surface protection member contacts the end surface of the wound photosensitive element (the width direction end side of the strip-shaped photosensitive element).

[0131] In particular, the surface roughness of both the supporting film (A) and the protective film (C) of the photosensitive element roll of this embodiment is specified as described above, thereby effectively preventing wrinkles during winding. Furthermore, by maintaining the friction between the supporting film (A) and the protective film (C) within an appropriate range, the roll is less likely to shift when stored vertically relative to the ground. Furthermore, during use, the roll surface is less likely to become electrically charged due to excessive friction, thereby easily preventing the adhesion of dust and debris.

[0132] The method for forming a resist pattern using the photosensitive element or a roll thereof according to the present embodiment preferably includes the following steps in order:

[0133] a lamination step of laminating a photosensitive element on a substrate;

[0134] an exposure step of exposing the photosensitive resin composition layer of the photosensitive element; and

[0135] A development step of developing and removing the unexposed portion of the photosensitive resin composition layer.

[0136] In the lamination process, specifically, after the protective film (C) is peeled off from the photosensitive element, the photosensitive resin composition layer is heated and pressed onto the surface of the support (e.g., substrate) using a laminating device, and laminated once or multiple times. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. The heating temperature during lamination is generally 40°C to 160°C. The heating and pressing can be performed by a two-stage laminating device having two continuous rollers, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the rollers several times.

[0137] In the exposure process, an exposure machine is used to expose the photosensitive resin composition layer to active light. Exposure can be performed after peeling off the support body as needed. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and can be measured using a light meter. In the exposure process, direct imaging exposure can also be performed. In direct imaging exposure, exposure is directly performed on the substrate using a drawing device without using a photomask. As a light source, a semiconductor laser with a wavelength of 350nm to 410nm or an ultra-high pressure mercury lamp is used. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the movement speed of the substrate.

[0138] The light irradiation method used in the exposure process is preferably at least one method selected from the group consisting of projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct drawing, and more preferably projection exposure.

[0139] In the development step, a developer is used in a developing device to remove the unexposed or exposed areas of the photosensitive resin composition layer after exposure using a developer. After exposure, if a support film is present on the photosensitive resin composition layer, it is removed. Subsequently, a developer containing an aqueous alkaline solution is used to develop and remove the unexposed or exposed areas, thereby forming a resist image.

[0140] The aqueous alkaline solution is preferably an aqueous solution of Na2CO3, K2CO3, or the like. The aqueous alkaline solution is selected based on the characteristics of the photosensitive resin composition layer; typically, a Na2CO3 aqueous solution with a concentration of 0.2% to 2% by mass is used. The aqueous alkaline solution may contain surfactants, defoaming agents, and a small amount of an organic solvent to promote development. The developer temperature during the development step is preferably maintained constant within the range of 20°C to 40°C.

[0141] After obtaining a resist pattern through the above steps, a heating step at 60°C to 300°C may be further performed as needed. This heating step can improve the chemical resistance of the resist pattern. The heating step can be performed using a heating furnace utilizing hot air, infrared rays, or far infrared rays.

[0142] In order to obtain a conductive pattern, a conductive pattern forming step of etching or plating the substrate on which the resist pattern is formed may be performed after the developing step or the heating step.

[0143] The method for producing a conductive pattern is performed, for example, by using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern using the aforementioned resist pattern forming method, and then performing a conductive pattern forming step. In the conductive pattern forming step, a conductive pattern is formed on the substrate surface (e.g., the copper surface) exposed by development using a known etching method or plating method.

[0144] Furthermore, after the conductor pattern is manufactured by the above-mentioned conductor pattern manufacturing method, a stripping process is performed to peel the resist pattern from the substrate using an aqueous solution having a stronger alkalinity than the developer, thereby obtaining a wiring board (such as a printed wiring board) having a desired wiring pattern.

[0145] The alkaline aqueous solution used for stripping (hereinafter referred to as the "stripping solution") is not particularly limited; however, aqueous solutions of NaOH or KOH with a concentration of 2% to 5% by mass, or organic amine-based stripping solutions, are generally used. A small amount of a water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohols. The temperature of the stripping solution during the stripping step is preferably within the range of 40°C to 70°C.

[0146] In this embodiment, the photosensitive element or its roll can be used in the manufacture of printed wiring boards; manufacture of lead frames for IC chip loading; precision processing of metal foil such as metal mask manufacturing; manufacture of packages such as ball grid array (BGA) and chip size package (CSP); manufacture of strip substrates such as chip on film (COF) and tape automated bonding (TAB); manufacture of semiconductor bumps; and manufacture of partition walls for flat panel displays such as ITO electrodes, addressing electrodes, and electromagnetic wave shielding.

[0147] It should be noted that the values of the above parameters were measured according to the measurement methods in the Examples described later unless otherwise specified.

[0148] Example

[0149] Next, the present embodiment will be described in more detail with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it deviates from the gist of the present embodiment. The physical properties in the examples were measured by the following methods.

[0150] [Measurement of surface roughness]

[0151] The surface roughness of the support film and the protective film was measured. After a drop of water was dropped on a glass plate, each film was attached with the measurement surface facing upward to prepare a measurement sample.

[0152] Surface roughness was measured according to the method specified in JIS B0601-2001 using a laser microscope (trade name "LEXT OLS4100" manufactured by OLYMPUS CORPORATION). The average of the Rz values measured at 10 random locations with a measurement length of 258 μm was taken as the maximum height Rz (nm). The measurement temperature was set at 23 to 25°C.

[0153] The surface roughness of the support film on the side in contact with the photosensitive resin composition layer is defined as Rz A1 The surface roughness of the opposite side is Rz A2 The surface roughness of the protective film on the side in contact with the photosensitive resin composition layer is defined as Rz C1 The surface roughness of the opposite side is Rz C2 .

[0154] [Measurement of the number of particles with a diameter of 2 μm or more and 5 μm or less]

[0155] A polarizing filter (OLS4000-QWP) is inserted into the upper part of the objective lens of a laser microscope, i.e., the product name "LEXT OLS4100" manufactured by OLYMPUS CORPORATION. Then, a porous adsorption plate "65F-HG" manufactured by UNIVERSALGIKEN CO., LTD. and a vacuum pump are used on the stage of the laser microscope to horizontally fix the support film sample cut into 30mm×30mm. The support film fixed by suction is observed using a laser light amount of 60 (laser wavelength is 405nm) at 50 times the objective lens. At this time, the area of 2μm in the center of the thickness direction of the support film is defined as the measurement interval in such a way that no halo is generated on the front and back surfaces of the support film due to reflected light. Then, the measurement is performed with a measurement area of 260μm×260μm and 49 measurement locations. The measurement is repeated 9 times at any different location.

[0156] The measured image was processed under the conditions of Binarization = Threshold Value, Threshold 1 = 10%, Small Particle Removal = 15, and Hole Filling = 20 to create a histogram. The number of particles with a diameter of 2 μm or more and 5 μm or less was calculated by summing the number of particles with a maximum diameter (μm) of 2 or more and 5 or less in the histogram.

[0157] [Determination of titanium content]

[0158] The titanium content in the supporting film was determined using the "XRF-1800" manufactured by Shimadzu Corporation, a fluorescent X-ray analyzer, under the following conditions: quantitative molecular TiO2, X-ray tube target Rh (4.0kW), voltage 40kV, current 95kA, spectroscopic crystal LiF, detector SC, 2θ = 86.14deg, and a measurement time of 40 seconds.

[0159] [Method for preparing evaluation samples]

[0160] Evaluation samples were prepared as follows.

[0161] <Production of Photosensitive Elements>

[0162] (Examples 1 to 7, Comparative Examples 1 to 8)

[0163] The components shown in Table 1 described later (wherein the numbers of each component represent the amount of compounding (parts by mass) based on the solid content) and methyl ethyl ketone measured in a manner of 55% solid content concentration are fully stirred and mixed to obtain a photosensitive resin composition prepared liquid. Detailed descriptions of the components shown in Table 1 are shown in Table 2. Then, a solution of the photosensitive resin composition prepared liquid is applied to the surface of a support film having a width of 500 mm, and dried with hot air at 90°C for 1 minute to form a photosensitive resin composition layer. At this time, the thickness of the heated photosensitive resin composition layer becomes 5 μm. Furthermore, a protective film is attached to the surface of the side of the photosensitive resin composition layer on which the support film is not laminated, thereby obtaining a photosensitive element. Furthermore, the photosensitive element is wound on a cylindrical plastic tube having an outer diameter of 3.5 inches, and a pressure roller arranged parallel to the width direction of the winding shaft is used to apply linear pressure to the plastic tube, and 500 m is wound at a tension of 7 kg to obtain a roll of the photosensitive element.

[0164] Table 3 shows the types and physical properties of the supporting films used in Examples and Comparative Examples, and Table 4 shows the types and physical properties of the protective films used in Examples and Comparative Examples.

[0165] <Entire substrate>

[0166] As a substrate for evaluating image properties, a 0.4 mm thick copper-clad laminate on which a 35 μm rolled copper foil was laminated was immersed in MECETCHBOND CZ-8101 (manufactured by MEC Co., Ltd.) and roughened until the etching amount became 1 μm.

[0167] <Lamination>

[0168] While peeling the protective film from the photosensitive element, the photosensitive element was laminated onto an image evaluation substrate preheated to 50°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105°C to obtain a photosensitive element laminate. The air pressure was 0.35 MPa and the lamination speed was 1.5 m / min.

[0169] <Exposure>

[0170] Two hours after lamination, the support film surface side of the photosensitive element stack was exposed using a split projection exposure apparatus (UX7-Square70, manufactured by USHIO INC.) using an exposure mask having a line pattern with a width ratio of 1:1 between the exposed and unexposed areas. Exposure and development were performed using the line pattern with a width ratio of 1:1 between the exposed and unexposed areas. The exposure was performed at an exposure dose such that the width of the exposed and unexposed areas of the photosensitive resin composition pattern after development was 5 μm at a location where the exposed area of the exposure mask was equal to the unexposed area, and the width of the exposed and unexposed areas was 5 μm.

[0171] <Development>

[0172] After peeling the support film from the photosensitive element stack, the film was developed using an alkali developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer) by spraying a 1% by mass aqueous solution of NaCO at 30°C for a predetermined time. The development spray time was set to twice the minimum development time, and the post-development water rinse spray time was set to twice the minimum development time. The minimum development time was the shortest time required for complete dissolution of the unexposed portion of the photosensitive resin composition layer.

[0173] [evaluate]

[0174] The obtained photosensitive element was evaluated for wrinkles during winding and resolution as follows.

[0175] Wrinkles during winding

[0176] The obtained roll of the photosensitive element was visually observed and evaluated based on the following criteria.

[0177] Excellent: No wrinkles on the roll

[0178] Good: Although there are wrinkles on the roll, they disappear after 3 days of storage.

[0179] Pass: Although there are wrinkles on the roll, they disappear after 7 days of storage

[0180] Fail: The roll has wrinkles that do not disappear even after 7 days of storage

[0181] Resolution

[0182] In the exposure step described above, exposure is performed using an exposure mask having a line pattern with a 1:1 ratio of exposed and unexposed widths. Development is performed according to the above-described development conditions. The minimum line width required to form a normal cured resist line without overexposure or collapse is evaluated using an optical microscope according to the following criteria. A score of at least passing is considered acceptable.

[0183] Excellent: 3μm or less

[0184] Good: more than 3μm and less than 4μm

[0185] Pass: more than 4μm and less than 5μm

[0186] Fail: more than 5μm

[0187] The evaluation results of the photosensitive elements of the respective Examples are shown in Table 5, and the evaluation results of the photosensitive elements of the respective Comparative Examples are shown in Table 6.

[0188] [Table 1]

[0189] Compound Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 A-1 57 57 A-2 57 57 A-3 57 B-1 17 15 20 15 20 B-2 6 8 6 6 6 B-3 11 11 7 14 9 B-4 5 5 5 5 5 C-1 3 3 3 3 3 C-2 0.1 C-3 0.1 C-4 0.1 0.1 0.1 D-1 0.2 0.2 0.2 0.2 0.2 D-2 0.3 0.3 0.3 0.3 0.3 count 99.1 99.1 98.1 100.1 100.1

[0190] [Table 2]

[0191]

[0192] [Table 3]

[0193]

[0194] [Table 4]

[0195]

[0196] [Table 5]

[0197]

[0198] [Table 6]

[0199]

[0200] As can be seen from Table 5, the examples satisfying all of the above-mentioned formulae (1) to (3) have excellent resolution and can suitably prevent wrinkles from occurring when the roll is wound.

[0201] On the other hand, as shown in Table 6, when the formula (1) is not satisfied, that is, Rz A1 When it is greater than 100, the resolution is reduced.

[0202] In addition, if the formula (2) is not satisfied, that is, Rz C1When it is 300 or less or 600 or more, the resolution is insufficient and wrinkles are observed during winding.

[0203] In addition, if the formula (3) is not satisfied, that is, Rz C2 / Rz A2 When the value is 40 or less, the resolution is insufficient and wrinkles are observed during winding.

[0204] While the embodiments of the present invention have been described above, the present invention is not limited thereto and can be appropriately modified without departing from the spirit of the invention.

[0205] Industrial applicability

[0206] By using the photosensitive element provided by the present invention, both improvement in resolution and prevention of wrinkles during winding are achieved, and the photosensitive element can be widely used as a dry film resist for forming a resist pattern.

Claims

1. A photosensitive element, characterized in that: It has a support film (A), a photosensitive resin composition layer (B) and a protective film (C) in this order, The surface roughness Rz of the surface of the support film (A) on the side in contact with the photosensitive resin composition layer (B) as specified in JIS B0601-2001 A1 , surface roughness Rz of the opposite side A2 , the surface roughness Rz of the surface of the protective film (C) on the side in contact with the photosensitive resin composition layer (B) C1 , and the surface roughness Rz of the opposite side C2 Satisfy the following (1) to (3): (1)1<Rz A1 <100 (2)300<Rz C1 <600 (3)40<Rz C2 / Rz A2 , And meet 400 <Rz C2 <5500 and 1 <Rz A2 , Wherein, the Rz A1 , the Rz A2 , the Rz C1 and the Rz C2 The unit is nm, The surface roughness is the maximum height Rz measured according to the method specified in JIS B0601-2001.

2. The photosensitive element according to claim 1, wherein Rz A1 Below 73.

3. The photosensitive element according to claim 1 or 2, wherein Rz A1 It is 10 to 70.

4. The photosensitive element according to claim 1 or 2, wherein Rz A1 18 and above.

5. The photosensitive element according to claim 1 or 2, wherein Rz C1 350 to 550.

6. The photosensitive element according to claim 1 or 2, wherein Rz C1 Below 500.

7. The photosensitive element according to claim 1 or 2, wherein Rz A2 It is 40 to 100.

8. The photosensitive element according to claim 1 or 2, wherein Rz A2 It is 50 to 90.

9. The photosensitive element according to claim 1 or 2, wherein 1.1<Rz A2 / Rz A1 <7。 10. The photosensitive element according to claim 1 or 2, wherein Rz A2 / Rz A1 It is 1.2 to 5.

11. The photosensitive element according to claim 1 or 2, wherein 1.1<Rz C2 / Rz C1 <10。 12. The photosensitive element according to claim 1 or 2, wherein Rz C2 / Rz C1 It is 1.5 to 9.

0.

13. The photosensitive element according to claim 1 or 2, wherein Rz C2 / Rz A2 Above 43.

5.

14. The photosensitive element according to claim 1 or 2, wherein 50<Rz C2 / Rz A2 <100。 15. The photosensitive element according to claim 1 or 2, wherein Rz C2 / Rz A2 Below 75.

5.

16. The photosensitive element according to claim 1 or 2, wherein Rz C2 / Rz A2 It is 40 to 80.

17. The photosensitive element according to claim 1 or 2, wherein The number of particles with a diameter of 2 μm or more and 5 μm or less contained in the supporting film (A) is 30 particles / 30 mm. 2 the following.

18. The photosensitive element according to claim 1 or 2, wherein The number of particles with a diameter of 2 μm or more and 5 μm or less contained in the supporting film (A) is 15 particles / 30 mm. 2 the following.

19. The photosensitive element according to claim 1 or 2, wherein The number of particles with a diameter of 2 μm or more and 5 μm or less contained in the supporting film (A) is 10 particles / 30 mm. 2 the following.

20. The photosensitive element according to claim 1 or 2, wherein The content of the titanium element contained in the supporting film (A) is 1 ppm or more and 20 ppm or less.

21. The photosensitive element according to claim 1 or 2, wherein The content of titanium element contained in the supporting film (A) is 2 ppm or more and 12 ppm or less.

22. The photosensitive element according to claim 1 or 2, wherein At least one surface of the supporting film (A) is subjected to a smoothing treatment.

23. The photosensitive element according to claim 1 or 2, wherein The supporting film (A) has a thickness of 5 μm or more and 16 μm or less.

24. The photosensitive element according to claim 1 or 2, wherein The supporting film (A) has a thickness of 5 μm or more and 12 μm or less.

25. The photosensitive element according to claim 1 or 2, wherein The haze of the supporting film (A) is 0.01% to 1.5%.

26. The photosensitive element according to claim 1 or 2, wherein The haze of the supporting film (A) is 0.01% to 1.2%.

27. The photosensitive element according to claim 1 or 2, wherein The support film (A) has a haze of 0.01 to 0.95%.

28. The photosensitive element according to claim 1 or 2, wherein The thickness of the photosensitive resin composition layer (B) is 3 to 100 μm.

29. The photosensitive element according to claim 1 or 2, wherein The surface of the protective film (C) is formed of a polypropylene resin.

30. The photosensitive element according to claim 1 or 2, wherein The protective film (C) is a polyethylene film or a polypropylene film.

31. The photosensitive element according to claim 1 or 2, wherein The thickness of the protective film (C) is 10 to 100 μm.

32. The photosensitive element according to claim 1 or 2, wherein The photosensitive resin composition layer (B) contains: (i) alkali-soluble polymers; (ii) an ethylenically unsaturated double bond-containing component; and (iii) Photopolymerization initiator.

33. The photosensitive element according to claim 32, wherein The (i) alkali-soluble polymer is a carboxylic acid-containing vinyl copolymer containing 15% to 40% by mass of structural units of at least one monomer selected from α- and β-unsaturated carboxylic acids, based on the mass of the copolymer.

34. The photosensitive element according to claim 32, wherein The (i) alkali-soluble polymer is a carboxylic acid-containing vinyl copolymer containing 5% by mass or more and 60% by mass or less of a structural unit of styrene or a styrene derivative, based on the mass of the copolymer.

35. The photosensitive element according to claim 34, wherein The (i) alkali-soluble polymer is a carboxylic acid-containing vinyl copolymer containing 5% by mass or more and 35% by mass or less of a structural unit of styrene or a styrene derivative, based on the mass of the copolymer.

36. The photosensitive element according to claim 32, wherein The content of the (i) alkali-soluble polymer is 30% by mass or more and 80% by mass or less based on the total mass of the photosensitive resin composition.

37. The photosensitive element according to claim 32, wherein (ii) Content of the component containing an ethylenically unsaturated double bond is 20 mass % or more and 70 mass % or less based on the total mass of the photosensitive resin composition.

38. The photosensitive element according to claim 32, wherein (iii) The content of the photopolymerization initiator is 0.01% by mass or more and 20% by mass or less based on the total mass of the photosensitive resin composition.

39. A wound body of a photosensitive element, wherein the photosensitive element according to any one of claims 1 to 38 is wound.

40. A method for forming a resist pattern, comprising: a lamination step of laminating the photosensitive element according to any one of claims 1 to 38 on a substrate, an exposure step of exposing the photosensitive resin composition layer of the photosensitive element, and A developing step of developing and removing the unexposed portion of the photosensitive resin composition layer.

41. The method for forming a resist pattern according to claim 40, wherein The exposure process is performed by a projection exposure method.

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