Methods for forming photosensitive elements and photoresist patterns

Abstract

The present invention provides a photosensitive element comprising a support film and a photosensitive layer containing a photosensitive resin composition; the aforementioned photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having ethylene unsaturated double bonds, and (C) a biimidazole photopolymerization initiator; the aforementioned component (C) comprises 5.0% by mass or more relative to all solid components of the photosensitive resin composition; the absorbance (Y) of the aforementioned photosensitive layer at a wavelength of 365 nm with a film thickness of 25 μm is 0.35 or less; the contribution (X) of the absorbance of the aforementioned component (C) to the aforementioned absorbance (Y) is 40% or more; the aforementioned contribution (X) is calculated by formula (1). X (%) = 100 × εc / absorbance (Y) of the photosensitive layer ･･･ (1)

Description

Technical Field

[0001] This invention relates to a photosensitive element and a method for forming a photoresist pattern. Prior Technology

[0002] Printed wiring boards are generally manufactured using photolithography. Photolithography refers to a method of forming a desired wiring pattern on a substrate through the following steps: First, a coating composed of a photosensitive resin is formed on the substrate. This coating is then exposed to a pattern and developed to form a photoresist pattern. Next, a conductor pattern is formed through etching or plating. Finally, the photoresist pattern on the substrate is removed to form the desired wiring pattern.

[0003] In recent years, with the miniaturization and high density of electronic devices, wiring boards have been required to form finer wiring than ever before. MSAP (Modified Semi Additive Process) and SAP (Semi Additive Process) have attracted attention as manufacturing methods for wiring boards that meet these requirements. In these methods, to form fine wiring, it is desirable to form photoresist patterns with excellent adhesion and resolution below 7 μm. Regarding this requirement, Patent Document 1 discloses a photosensitive resin composition containing an anthracene sensitizer, and an adhesive polymer having hydroxyalkyl (meth)acrylate units and a specific amount of styrene or styrene derivative units. In the embodiment of Patent Document 1, a biimidazole photopolymerization initiator is used as the photopolymerization initiator. [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] International Publication No. 2021 / 193232 Summary of the Invention

[0005] [The technical problem that the invention aims to solve] However, when this photosensitive resin composition is exposed to an exposure device with a wavelength of 365nm and the resulting photoresist pattern is observed, the following problems are found: insufficient resolution; difficulty in forming patterns smaller than 7μm; and room for improvement in adhesion. As described in Patent Document 1, conventional photosensitive resin compositions often contain relatively large amounts of biimidazole photopolymerization initiators. Such photosensitive resin compositions, when stored under yellow light, experience sensitivity changes, which easily deteriorates the storage stability of the photosensitive layer. In particular, based on the total amount of all solid components in the photosensitive resin composition, if it contains more than 5% by mass of biimidazole photopolymerization initiator, a significant deterioration in storage stability often occurs. That is, achieving adhesion, resolution, and storage stability has been difficult in conventional photosensitive elements.

[0006] This invention is proposed in view of the above-mentioned circumstances. That is, the object of this invention is to provide a photosensitive element with excellent adhesion, resolution and preservation stability, and a method for forming a photoresist pattern. [Technical means]

[0007] One embodiment of the present invention is as follows. [1] A photosensitive element comprising a support film and a photosensitive layer containing a photosensitive resin composition; The aforementioned photosensitive resin composition contains the following components: (A) Alkali-soluble polymers, (B) Compounds containing ethylene-like unsaturated double bonds, (C) Biimidazole photopolymerization initiator; The aforementioned component (C) contains 5.0% by mass or more of the total solid components of the aforementioned photosensitive resin composition; The absorbance (Y) of the aforementioned photosensitive layer with a film thickness of 25 μm and a wavelength of 365 nm is below 0.35; The contribution (X) of the absorbance of the aforementioned component (C) to the absorbance (Y) is more than 40%; The aforementioned contribution (X) is calculated using the following formula (1): X(%) = 100×εc / absorbance of photosensitive layer (Y) ･･･ (1) ε: (C) Change in absorbance per 1% by mass of component c: The content (mass %) of component (C) among all solid components in the photosensitive resin composition. [2] The photosensitive element as described in Project 1, wherein the aforementioned component (C) contains 5.5% by mass or more relative to all solid components of the aforementioned photosensitive resin composition. [3] The photosensitive element as described in Item 1 or 2, wherein the aforementioned component (C) contains 6.0% by mass or more relative to all solid components of the aforementioned photosensitive resin composition. [4] The photosensitive element described in any of items 1 to 3, wherein the aforementioned contribution (X) is 55% or more. [5] The photosensitive element described in any one of items 1 to 4, wherein the aforementioned contribution (X) is 65% or more. [6] The photosensitive element described in any of items 1 to 5, wherein the aforementioned contribution (X) is 85% or more. [7] The photosensitive element as described in any one of items 1 to 6, wherein the aforementioned absorbance (Y) is 0.30 or less. [8] The photosensitive element as described in any one of items 1 to 7, wherein the aforementioned absorbance (Y) is 0.25 or less. [9] The photosensitive element as described in any one of items 1 to 8, wherein the aforementioned photosensitive resin composition further contains at least one selected from the group consisting of diphenyl ketone compounds, pyrazoline compounds, anthracene compounds, and coumarin compounds as (D) other photopolymerization initiators and / or sensitizers.

[10] The photosensitive element as described in any one of items 1 to 9, wherein the aforementioned photosensitive resin composition further contains at least one selected from the group consisting of diphenyl ketone compounds and pyrazoline compounds as (D) other photopolymerization initiators and / or sensitizers.

[11] The photosensitive element as described in any one of items 1 to 10, wherein the aforementioned component (A) contains styrene as a monomer component, and Based on the total mass of all monomer components in component (A) above, the proportion of constituent units derived from the aforementioned styrene is 35% by mass or more.

[12] The photosensitive element as described in any one of items 1 to 11, wherein the aforementioned component (A) contains styrene as a monomer component, and Based on the total mass of all monomer components in component (A) above, the proportion of constituent units derived from the aforementioned styrene is 50% by mass or more.

[13] The photosensitive element as described in any one of items 1 to 12, wherein the aforementioned component (A) contains styrene as a monomer component, and Based on the total mass of all monomer components in component (A) above, the proportion of constituent units derived from the aforementioned styrene is 60% by mass or more.

[14] The photosensitive element as described in any of items 1 to 13, wherein the aforementioned component (B) contains a compound represented by the following general formula (II): [Chemistry 1] (In the formula, R2 is individually and independently a hydrogen atom or a methyl group; X2O and Y2O are individually and independently oxyethyl or oxypropyl; m3, m4, n2, and n3 are individually and independently integers from 0 to 40; m3+m4 is from 1 to 40; and n2+n3 is from 0 to 20); The content of the compound represented by the aforementioned formula (II), based on the total amount of component (B), is 50% by mass or more.

[15] The photosensitive element as described in any one of items 1 to 14, wherein the aforementioned photosensitive resin composition further contains (E) a polymerization inhibitor.

[16] The photosensitive element as described in any one of items 1 to 15, wherein the absorbance of the aforementioned support film at 365 nm is less than 0.1.

[17] The photosensitive element as described in any one of items 1 to 16, wherein it further comprises a protective film.

[18] A method for forming a photoresist pattern, comprising using a photosensitive element as described in any one of claims 1 to 17; The aforementioned method includes the following steps: The step of laminating a photosensitive element onto a substrate; The steps of exposing the photosensitive layer of the previously deposited photosensitive element; and The process of developing the photosensitive layer after exposure is described above. [Invention Effects]

[0008] The present invention provides a photosensitive element with excellent adhesion, resolution and storage stability, and a method for forming a photoresist pattern using the same. Simple Explanation of the Diagram

[0009] [Figure 1] is a plan view illustrating one example of the "foreign object" assumed in this implementation. Implementation

[0010] The following describes an embodiment of the present invention (hereinafter referred to as "this embodiment"). The present invention is not limited to this embodiment, and various modifications can be implemented within its scope. In this specification, the upper and lower limits of each numerical range can be arbitrarily combined, and can also be replaced with the values ​​described in the embodiments. Furthermore, in this specification, the numerical range indicated by "~" includes both the upper and lower limits.

[0011] [Implementation Type 1] The photosensitive element of this embodiment comprises a support film and a photosensitive layer containing a photosensitive resin composition; The photosensitive resin composition contains the following components: (A) Alkali-soluble polymers, (B) Compounds containing ethylene-like unsaturated double bonds, (C) Biimidazole photopolymerization initiator; The above-mentioned component (C) contains 5.0% by mass or more relative to all the solid components of the aforementioned photosensitive resin composition. In this specification, (A) to (C) will sometimes be referred to as "(A) ingredient" to "(C) ingredient". The same applies to "(D)" and "(E)" mentioned later.

[0012] In this embodiment, the absorbance (Y) at 365 nm for a photosensitive layer with a film thickness of 25 μm is 0.35 or less; and the contribution (X) of the absorbance (C) component of the absorbance (Y) is 40% or more. This results in excellent adhesion, resolution, and storage stability. Here, the contribution (X) is calculated using the following formula (1): X(%) = 100×εc / absorbance of photosensitive layer (Y) ･･･ (1) ε: (C) Change in absorbance per 1% by mass of component c: The content (mass %) of component (C) among all solid components in the photosensitive resin composition. The absorbance (Y) coefficient must be greater than 0.

[0013] The photosensitive resin composition of this embodiment contains 1 to n (C) components. n is a positive integer, preferably 5, and more preferably 3.

[0014] <Supporting membrane> A support film is a layer or film used to support the photosensitive layer, preferably a transparent substrate film that allows active light to pass through.

[0015] Transparent substrate films include those made from synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate (PET) is preferred due to its moderate flexibility and strength.

[0016] From the perspective of improving the adhesion of photoresist patterns, the absorbance of the support film at a wavelength of 365nm is preferably below 0.3, more preferably below 0.2, even more preferably below 0.1, and most preferably below 0.08 (e.g., 0.080). The above absorbance is acceptable as long as it is above 0.

[0017] Among these, it is preferable to use films with fewer internal foreign matter, that is, high-quality films. Specifically, high-quality films are preferably: PET films synthesized using Ti-based catalysts, PET films with small diameters and low amounts of lubricants, PET films containing lubricants only on one side of the film, thin PET films, PET films that have undergone smoothing treatment on at least one side, and PET films that have undergone roughening treatment such as plasma treatment on at least one side. This allows the light from exposure to reach the photosensitive layer without being blocked by internal foreign objects, thereby improving the resolution of the photosensitive element.

[0018] The thickness of the support film is preferably 5~25μm, more preferably 6~20μm. A thinner support film tends to have fewer internal foreign objects, thus preventing a decrease in resolution. On the other hand, if the film thickness is less than 5μm, elongation deformation in the direction of tension winding is more likely to occur during the coating and winding processes, or the film may crack due to minor damage. As a result, the film strength may be insufficient, making it prone to wrinkles during lamination.

[0019] At least one side of the support film can be smoothed using a calendering apparatus or the like. This reduces the surface roughness of one side of the support film, especially the side in contact with the photosensitive layer, making it easier to achieve the effects of the present invention.

[0020] From the viewpoint of improving the parallelism of light irradiating the photosensitive layer and obtaining high resolution, the haze of the support film is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01% to 0.95%.

[0021] <Photosensitive layer> The photosensitive layer contains a photosensitive resin composition. This photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound with vinyl unsaturated double bonds, and (C) a biimidazole photopolymerization initiator. The photosensitive resin composition may also contain (D) other photopolymerization initiators and / or (E) polymerization inhibitors.

[0022] (A) Component: Alkali-soluble polymer (A) Component, preferably having a repeating unit composed of at least one of the first monomers described later, more preferably having a repeating unit composed of at least one of the first monomers and at least one of the second monomers described later.

[0023] The first monomer is a monomer having a carboxyl group and at least one polymerizable unsaturated group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half-ester. From the viewpoint of excellent adhesion and resolution, (meth)acrylic acid is preferred, and methacrylic acid is even more preferred. Furthermore, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid; "(meth)acrylic acid" means acrylonitrile or methacrylic acid; and "(meth)acrylate" means "acrylate" or "methacrylate".

[0024] The copolymerization ratio of the first monomer, based on the total mass of all monomer components, is preferably 10 to 50% by mass. A copolymerization ratio of 10% by mass or more is preferred from the viewpoint of excellent adhesion and resolution; more preferably 15% by mass or more; further preferably 18% by mass or more; even more preferably 21% by mass or more; particularly preferably 23% by mass or more; and most preferably 25% by mass or more. A copolymerization ratio of 50% by mass or less is preferred from the viewpoint of excellent adhesion and resolution; more preferably 35% by mass or less; further preferably 30% by mass or less; particularly preferably 29% by mass or less; and most preferably 27% by mass or less. When using two or more first monomers, it is preferable that the total copolymerization ratio of each monomer is within the range mentioned above.

[0025] The second monomer is a non-acidic monomer that has at least one polymerizable unsaturated group in its molecule. The second monomer can be a monomer having a polymerizable unsaturated group in its molecule. From the viewpoint of resolution and adhesion, it is preferable to contain a compound having an aromatic structure. By having a building block derived from this compound, swelling of the photosensitive layer during development is easily suppressed, thereby making it easier to obtain a hardened film with excellent adhesion and resolution. The copolymerization ratio of the monomer derived from the aromatic compound is preferably 10 to 90% by mass, based on the total mass of all monomer components. This copolymerization ratio is preferably 10% by mass or more from the viewpoint of excellent adhesion and resolution, more preferably 30% by mass or more, further preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more. The copolymerization ratio is preferably 90% by mass or less from the viewpoint of excellent resolution, and more preferably 80% by mass or less. When two or more aromatic compounds are used as the second monomer, it is preferable that the total proportion of the individual copolymerizations is within the range described above.

[0026] Examples of compounds with aromatic structures include: benzyl (meth)acrylate, styrene, methylstyrene, vinyltoluene, tributoxystyrene, acetoxystyrene, styrene dimers and trimers, and styrene derivatives such as 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate.

[0027] As a compound having an aromatic structure, benzyl (meth)acrylate or styrene is preferred, and styrene is even more preferred. For example, the copolymerization ratio of styrene, from the viewpoint of excellent adhesion and resolution, is preferably 10 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass, based on the total mass of all monomer components.

[0028] Furthermore, using alkali-soluble polymers with a high copolymerization ratio of compounds with aromatic structures (e.g., styrene) can easily reduce the number of foreign matter in the photosensitive element. Examples of foreign matter include precipitates of several to tens of μm in size (as shown in Figure 1, precipitate 11), or bubbles of tens of μm in size forming around a precipitate of several μm in size (as shown in Figure 1, bubble 12). Foreign matter can be observed with the naked eye or under an optical microscope.

[0029] Examples of foreign matter in the photosensitive resin composition are shown in Figure 1. In the figure, the photosensitive layer is indicated by the number "1"; the foreign matter is indicated by the number "10". Among the foreign matter 10, precipitates with a size of several to tens of μm are indicated by the symbol "11"; bubbles with a size of tens of μm are indicated by the symbol "12". Given the current trend in development, it is generally believed that the photosensitive resin composition will contain a relatively large amount of (C) component. On the other hand, a high content of (C) component can easily worsen the compatibility with other components in the photosensitive resin composition. Therefore, this foreign matter 10 is considered to be generated in the photosensitive layer 1 during film formation. If a base-soluble polymer with a high copolymerization ratio of aromatic compounds (e.g., styrene) and a high aromatic ring ratio is used, the compatibility between the (C) bimidazole photopolymerization initiator and the photosensitive resin composition can be easily improved. Therefore, it can be considered that even if the photosensitive resin composition is designed to contain a relatively large amount of (C) component, the generation of (C) component in the photosensitive resin composition can be easily prevented, thus easily reducing the number of foreign matter.

[0030] The compound having an aromatic structure is preferably a compound containing both styrene and benzyl (meth)acrylate. The copolymerization ratio of benzyl (meth)acrylate, based on the total mass of all monomer components, is preferably 1 to 60% by mass, more preferably 1 to 30% by mass, and even more preferably 1 to 20% by mass.

[0031] The second monomer is preferably a compound containing hydroxyl groups. By having building blocks derived from this compound, the developability of the photosensitive layer is easily controlled, thus making it easier to obtain a hardened film with excellent adhesion and resolution. The second monomer may also contain both a compound with an aromatic structure and a compound containing hydroxyl groups.

[0032] The aforementioned compounds containing hydroxyl groups are preferably hydroxyalkyl (meth)acrylates or dihydroxyalkyl (meth)acrylates. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of dihydroxyalkyl (meth)acrylates include glycerol mono(meth)acrylate. The aforementioned compounds containing hydroxyl groups are more preferably 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate. These are relatively easy to obtain, have easily controllable developability, and easily achieve photoresist patterns with excellent adhesion and resolution.

[0033] (A) The proportion of compounds containing hydroxyl groups in the composition, based on the total mass of all monomer components, is preferably 1.0 to 20% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 6% by mass, from the viewpoint of developability and adhesion. When using two or more compounds containing hydroxyl groups, it is preferable that the total proportion of the individual copolymers is within the above range.

[0034] The second monomer may further contain polymeric compounds that are neither aromatic nor hydroxyl-containing. Examples of polymeric compounds that are neither aromatic nor hydroxyl-containing include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenoxyethyl methacrylate, isobornyl methacrylate, and nonyl methacrylate. Phenoxy polyethylene glycol esters, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane acetal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, and other (meth)acrylate esters; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile, etc.

[0035] (A) The weight average molecular weight (Mw) of the component is preferably 10,000 to 60,000. A weight average molecular weight (Mw) of 60,000 or less is preferable from the viewpoint of achieving flexibility, resolution, and developability of the photoresist pattern; from the same viewpoint, it is more preferably 55,000 or less, and even more preferably less than 50,000. From the same viewpoint, the weight average molecular weight (Mw) is preferably 10,000 or more, more preferably 14,000 or more, and even more preferably 25,000 or more.

[0036] (A) The polydispersity of the component is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0037] From the viewpoint of developability and resolution, component (A) can be a copolymer composed solely of monomers containing a single polymeric unsaturated group. That is, component (A) may not contain any polymeric unsaturated groups.

[0038] (A) Components may include copolymers containing polymerizable unsaturated groups. A copolymer containing polymerizable unsaturated groups may be obtained, for example, by adding glycidyl (meth)acrylate to a copolymer having carboxyl groups. The photosensitive resin composition includes: in the case of a copolymer containing polymeric unsaturated groups, which is component (A) or component (B), for example, can be distinguished by the following methods. A copolymer containing a monomer having a carboxyl group and at least one polymerizable unsaturated group as a copolymer component can be classified as component (A). A non-copolymer compound, and a copolymer not containing a monomer having a carboxyl group and at least one polymerizable unsaturated group as a copolymer component, can be classified as component (B).

[0039] In this embodiment, component (A) can be used alone or in combination with two or more other components. When two or more other components are used in combination, it is preferable to select the monomer content, molecular weight, and polydispersity of the plurality of components (A) such that the weighted average of the content ratios falls within the ranges described above.

[0040] (A) The synthesis of the component is preferably carried out as follows: a solution of the single or multiple monomers described above is diluted with a solvent such as acetone, methyl ethyl ketone, or isopropanol; a free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is added appropriately; and the mixture is heated and stirred. Alternatively, synthesis may be carried out while a portion of the mixture is added dropwise to the reaction solution. Alternatively, after the reaction is complete, a solvent is added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used. Furthermore, synthesis may also be carried out using living radical polymerization.

[0041] (A) The proportion of the component relative to the mass of all solid components in the photosensitive resin composition may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. Alternatively, it may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0042] It is preferable from the viewpoint of controlling development time that the content of component (A) relative to the mass of all solid components in the photosensitive resin composition is 90% by mass or less; it is preferable from the viewpoint of controlling the exudation of the photosensitive layer from the end face of the film to 10% by mass or more.

[0043] (B) Components: Compounds containing ethylene-like unsaturated double bonds. (B) Component, preferably containing (meth)acrylic acid, more preferably containing a compound with two or more functions (a compound with two or more functions having ethylene unsaturated double bonds). "A compound with two or more functions having ethylene unsaturated double bonds" means a compound having two or more ethylene unsaturated double bonds in one molecule.

[0044] The compound having an ethylene unsaturated double bond is preferably a (meth)acrylate compound. The compound having an ethylene unsaturated double bond can be a compound containing only two functional groups, a compound containing two functional groups, or a compound containing three or more functional groups. For example, the compound having a ethylene unsaturated double bond can contain four, five, or six functional groups.

[0045] Examples of difunctional compounds with ethylene-like unsaturated bonds include alkyl di(meth)acrylates, 1,3-bis(meth)acryloyloxy-2-propanol, and polyalkylene glycol di(meth)acrylates represented by the following general formula (I). [Chemistry 2] (In the formula, R1 is individually a hydrogen atom or a methyl group; X1O and Y1O are individually oxyethyl, oxypropyl, or oxybutenyl groups; (X1O)m1, (X1O)m2, and (Y1O)n1 are (poly)oxyethylene chains, (poly)oxypropylene chains, or (poly)oxybutene chains; m1, m2, and n1 are individually integers from 0 to 40; m1+m2 are from 1 to 40; and n1 is from 0 to 20.) Tricyclodecyl di(meth)acrylate, and bisphenol A type di(meth)acrylate represented by the following general formula (II), etc.

[0046] General Form (II) [Chemistry 3] (In the formula, R2 is a hydrogen atom or a methyl group; X2O and Y2O are oxyethyl or oxypropyl groups; m3, m4, n2 and n3 are integers from 0 to 40; m3+m4 is from 1 to 40; and n2+n3 is from 0 to 20).

[0047] Examples of polyalkylene glycol di(meth)acrylate represented by the aforementioned formula (I) include vinyl compounds with R1=methyl, m1+m2=6 (average), n1=12 (average), X1O being oxyethyl, and Y1O being oxypropyl (manufactured by Hitachi Chemical Industry Co., Ltd., product name "FA-024M").

[0048] Examples of bisphenol A type di(meth)acrylate compounds represented by the aforementioned general formula (II) include BPE-200 (R2=methyl, X2O=oxyethyl, m3+m4=4, n2=n3=0), BPE-500 (R2=methyl, X2O=oxyethyl, m3+m4=10, n2=n3=0), BPE-900 (R2=methyl, X2O=oxyethyl, m3+m4=17, n2=n3=0) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name), FA-321M (R2=methyl, X2O=oxyethyl, m3+m4=10, n2=n3=0), FA-P321M (R2=methyl, X2O=oxypropyl, m3+m4=10, n2=n3=0) (manufactured by Hitachi Chemical Industry Co., Ltd., product name), etc. These can be used individually or in any combination of two or more types.

[0049] Component (B) is preferably a bisphenol A type di(meth)acrylate compound represented by the aforementioned general formula (II) from the viewpoints of adhesion, resolution, and reduction of foreign matter. The content of the bisphenol A type di(meth)acrylate compound represented by the aforementioned general formula (II), based on the total amount of component (B), is preferably 1% by mass or more, more preferably 20% by mass or more, further preferably 50% by mass or more, and particularly preferably 80% by mass or more. Using a bisphenol A type di(meth)acrylate compound represented by the aforementioned general formula (II) with a high aromatic ring ratio easily improves the compatibility between the photosensitive resin composition and component (C). Therefore, the formation of component (C) in the photosensitive resin composition is easily prevented, thus making it easier to reduce the number of foreign matter.

[0050] The average value of n2+n3+m3+m4 in the bisphenol A type di(meth)acrylate compound represented by the aforementioned general formula (II) is preferably 20 or less, and more preferably 10 or less, from the viewpoint of resolution and adhesion. Further preferably, it includes the aforementioned bisphenol A type di(meth)acrylate containing an average value of n2+n3+m3+m4 greater than 5 and less than 10, and the aforementioned bisphenol A type di(meth)acrylate containing an average value of n2+n3+m3+m4 less than 5. The average value of n2+n3+m3+m4 can be 2 or more. Furthermore, the number of oxyethyl or oxypropyl structural units represents an integer value in a single molecule and a rational number representing the average value in an aggregate of complex molecules.

[0051] Commercially available compounds containing difunctional ethylene-type unsaturated double bonds include, for example: NK ESTER (registered trademark) A-HD-N, NK ESTER A-NOD-N, NK ESTER A-DOD-N, NK ESTER A-NPG, NK ESTER 701A, NK ESTER A-200, NK ESTER A-400, NK ESTER A-600, NK ESTER A-1000, NK ESTER APG-200, NK ESTER APG-400, NK ESTER APG-700, NK ESTER A-PTMG65, NK ESTER A-DCP, NK ESTER ABE-300, NK ESTER A-BPE-4, NK ESTER A-BPE-10, NK ESTER A-BPE-20, NK ESTER HD-N, NK ESTER NOD-N, NK ESTER DOD-N, NK ESTER A-HD-N, NK ESTER A-NOD-N, NK ESTER A-DOD-N, NK ESTER A-NPG, NK ESTER A-200, NK ESTER A-200, NK ESTER A-NOD-N, NK ESTER A-DOD-N, NK ESTER A-NPG, NK ESTER A-200, NK ESTER A-DOD-N, NK ESTER A-NPG ... NK ESTER NPG, NK ESTER 701, NK ESTER 2G, NK ESTER 3G, NK ESTER 4G, NK ESTER 9G, NK ESTER 14G, NK ESTER 23G, NK ESTER 9PG, NK ESTER DCP, NK ESTER BPE-80N, NK ESTER BPE-100, NK ESTER BPE-200, NK ESTER BPE-500, NK ESTER BPE-900, NK ESTER BPE-1300N, NK OLIGO (registered trademark) UA-4200, NK OLIGO UA-160TM, NK OLIGO UA-290TM, NK OLIGO UA-W2A, NK OLIGO UA-4400, NK OLIGO UA-122P, NK OLIGO U-200PA (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.);LIGHT ACRYLATE (registered trademark) 3EG-A, LIGHT ACRYLATE 4EG-A, LIGHT ACRYLATE 9EG-A, LIGHT ACRYLATE 14EG-A, LIGHT ACRYLATE PTMGA-250, LIGHT ACRYLATE NP-A, LIGHT ACRYLATE MPD-A, LIGHT ACRYLATE 1.6HX-A, LIGHT ACRYLATE 1.9ND-A, LIGHT ACRYLATE DCP-A, LIGHT ACRYLATE BP-4EAL, LIGHT ACRYLATE BP-4PA, LIGHT ACRYLATE HPP-A, LIGHT ESTER G-201P (above, manufactured by Gyoeisha Chemical Co., Ltd.); FANCRYL (registered trademark) FA-124AS, FANCRYL FA-023M, FANCRYL FA-121M, FANCRYL FA-124M, FANCRYL FA-125M, FANCRYL FA-129AS, FANCRYL FA-137M, FANCRYL FA-220M, FANCRYL FA-222A, FANCRYL FA-240A, FANCRYL FA-240M, FANCRYL FA-320M, FANCRYL FA-3218M, FANCRYL FA-321A, FANCRYL FA-321M, FANCRYL FA-324A, FANCRYL FA-731A, FANCRYL FA-P240A, FANCRYL FA-P270A, FANCRYL FA-PTG9A, FANCRYL FA-PTG9M, FANCRYL FA-PTG28A, FANCRYL FA-PTG49A (and above, manufactured by Showa Denko Materials Co., Ltd.); DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (and above, manufactured by Daicel-Allnex Co., Ltd.);SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema Inc.); KAYARAD (registered trademark) NPGDA, KAYARAD PEG400DA, KAYARAD FM-400, KAYARAD R-167, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0052] The proportion of functional compounds with ethylene unsaturated double bonds, based on the total amount of component (B), is preferably 20% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, from the viewpoint of peelability, resolution, and adhesion.

[0053] Examples of compounds with trifunctional or higher ethylene-like unsaturated double bonds include trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, isocyanurate tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, bis(trimethylolpropane (tetra / penta / hexa)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0054] Furthermore, compounds with trifunctional or higher vinyl unsaturated double bonds can be obtained by adding an alcohol with three or more groups that form a central skeleton within the molecule and are capable of adding an oxidized alkenyl group, such as an oxyvinyl, oxypropylene, or oxybutenyl group, to an (meth)acrylic acid to form a (meth)acrylate. Examples include trimethylolpropane-modified tri(meth)acrylate, glycerol-modified tri(meth)acrylate, epoxide-modified pentaerythritol (tri / tetra)(meth)acrylate, epoxide-modified bis(trimethylolpropane)(tetra / penta / hexa)(meth)acrylate, epoxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and epoxide-modified isocyanurate tri(meth)acrylate.

[0055] As a compound with trifunctional or higher ethylene unsaturated double bonds, from the viewpoint of imaging properties, it may also contain epoxide-modified pentaerythritol (tris / tetra) (meth)acrylate.

[0056] Commercially available compounds with trifunctional or higher ethylene unsaturated double bonds include, for example: NK ESTER (registered trademark) A-TMPT, NK ESTER A-TMPT-9EO, NK ESTER AT-20E, NK ESTER A-GLY-3E, NK ESTER A-GLY-9E, NK ESTER A-GLY-20E, NK ESTER A-9300, NK ESTER A-9200YN, NK ESTER A-TMM-3, NK ESTER A-TMM-3L, NK ESTER A-TMM-3LM-N, NK ESTER A-TMMT, NK ESTER ATM-35E, NK ESTER AD-TMP, NK ESTER A-DPH, NK ESTER A-9550, NK ESTER A-DPH-12E, NK ESTER TPOA-50, NK OLIGO (registered trademark) UA-7100, NK... OLIGO UA-1100H, NK OLIGO U-6LPA, NK OLIGO UA-33H, NK OLIGO U-10HA, NK OLIGO U-10PA, NK OLIGO U-15HA (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); LIGHT ACRYLATE (registered trademark) TMP-A, cPE-3A, LIGHT ACRYLATE PE-4A, LIGHT ACRYLATE DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.); FA-731A (manufactured by Showa Denko Materials Co., Ltd.); TMPTA, EBECRRYL 160S, OTA 480, PETIA, PETRA, EBECRRYL 40, PETA, EBECRRYL 140, EBECRRYL 1140, EBECRRYL 1142, DPHA, EBECRRYL 895, EBECRRYL 896, EBECRRYL TMPTMA (manufactured by Daicel-Allenex Corporation); SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (manufactured by Arkema Corporation);KAYARAD (registered trademark) GPO-303, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA-330, KAYARAD PET-30, KAYARAD T-1420(T), KAYARAD RP-1040, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD D-310, KAYARAD DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0057] From the viewpoint of adhesion and reproducibility, the proportion of trifunctional compounds with ethylene unsaturated double bonds, based on the total amount of component (B), can be 1 to 50% by mass, 1 to 25% by mass, and 1 to 15% by mass.

[0058] The proportion of component (B) relative to the total mass of all solid components in the photosensitive resin composition is preferably 30% by mass or more, and more preferably 35% by mass or more, from the viewpoints of sensitivity, viscosity, and followability. Furthermore, from the viewpoints of edge melt resistance, viscosity, and resolution, it is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 42% by mass or less.

[0059] From the viewpoints of edge melt resistance, viscosity, and resolution, the value of the ratio of the mass of solid component (A) to the mass of solid component (B) (i.e., the ratio of the mass of solid component (B) to the mass of solid component (A)) is preferably 1.4 or less, more preferably 1.3, further preferably 1.2, and particularly preferably 1.1 or less. The lower limit is preferably 0.7 or more, more preferably 0.8 or more, further preferably 0.9 or more, and particularly preferably 1.0 or more.

[0060] In this specification, resistance to edge melting refers to the property of photoresist being exposed from the end face of the photosensitive element roller, especially the property of photoresist being exposed from that end face when the photosensitive element roller is stored; the less photoresist exposed, the better. Furthermore, tackiness refers to the adhesiveness of the photosensitive resin composition. From the perspective of suppressing poor lamination to the substrate and poor peeling of the protective film and the support film, moderate tackiness of the photosensitive resin composition is preferable. Conversely, by appropriately controlling the tackiness of the photosensitive resin composition, poor lamination to the substrate can be easily suppressed, and poor peeling of the protective film and the support film can also be easily suppressed.

[0061] The number of vinyl unsaturated double bonds per 100g of solid component in the photosensitive resin composition is preferably 0.1 to 0.3 moles. With a concentration of 0.1 moles or more, it is easier to prevent the photosensitive resin component from leaching from the hardened photoresist pattern during the post-development washing step, and even to prevent contamination during the washing step. With a concentration of 0.3 moles or less, damage or even detachment of the hardened photoresist pattern becomes less likely to occur during the post-development washing step, thus easily preventing contamination during the washing step.

[0062] The number of vinyl unsaturated double bonds per 100g of the solid component of the photosensitive resin composition is preferably 0.1 mol or more, more preferably 0.11 mol or more, further preferably 0.12 mol or more, and especially preferably 0.13 mol or more. Furthermore, it is preferably 0.3 mol or less, more preferably 0.28 mol or less, further preferably 0.25 mol or less, especially preferably 0.22 mol or less, 0.20 mol or less, or 0.18 mol or less, and most preferably 0.15 mol or less. Furthermore, the number of vinyl unsaturated double bonds per 100g of the solid component of the photosensitive resin composition is preferably 0.1 to 0.25 mol, more preferably 0.1 to 0.2 mol, even more preferably 0.11 to 0.2 mol, and most preferably 0.11 to 0.15 mol.

[0063] (C) Component: Biimidazole photopolymerization initiator (C) component is a photopolymerization initiator with a biimidazole structure. (C) The content of the component, relative to the total mass of all solid components of the photosensitive resin composition, may be 5.0% by mass or more, and from the viewpoint of sensitivity and adhesion, it is preferably 5.25% by mass or more, more preferably 5.5% by mass or more, further preferably 6.0% by mass or more, and most preferably 7.0% by mass or more. Furthermore, from the viewpoint of reducing the number of foreign matter, it is preferably 10% by mass or less, more preferably 9.0% by mass or less, and further preferably 8.0% by mass or less.

[0064] As component (C), examples include, for instance, phenanthrene dimers, namely, dimers of 2,4,5-triarylimidazolium. Phenylphenanthrene dimers, i.e., dimers of 2,4,5-triarylimidazolium, include, for example, dimers of 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 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, and 2-(o-chlorophenyl)-bis- 4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2, 6-Difluorophenyl)-4,4',5,5'-Tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc.

[0065] From the viewpoint of high sensitivity, resolution and adhesion, (C) biimidazole photopolymerization initiator is preferably a phenanthrene dimer, wherein, more preferably, it is a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0066] (D) Components: Other photopolymerization initiators and / or sensitizers (D) refers to a photopolymerization initiator or sensitizer other than (C). In this specification, a photopolymerization initiator is a compound that initiates the polymerization of (B) by irradiation with light of a specific wavelength. For example, a photopolymerization initiator may be a free radical polymerization initiator. In this specification, a sensitizer is a compound that promotes the polymerization of (B) by irradiation with light of a specific wavelength. Compounds that function as both photopolymerization initiators and sensitizers may also be included as (D).

[0067] Here, there are cases where a compound that can be used as component (C) has the function of component (D), and there are also cases where a compound that can be used as component (D) has the function of component (C). On the other hand, if a specific photopolymerization initiator is used as component (C), then other photopolymerization initiators can be considered as component (D). For example, if a pyrophenone dimer is present in 5.0% by mass or more of all solid components of the photosensitive resin composition as component (C), then other photopolymerization initiators besides the pyrophenone dimer can be considered as component (D).

[0068] Examples of components (D) include N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acetophosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylamino benzoate compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, ester compounds of N-aryl amino acids, coumarin derivatives, and halogen compounds.

[0069] Examples of aromatic ketone compounds include diphenyl ketones. Examples of diphenyl ketone compounds include diphenyl ketone, milchnerone [4,4'-bis(dimethylamino)diphenyl ketone], and 4-methoxy-4'-dimethylaminodiphenyl ketone. From the viewpoint of sensitizing effect and adhesion, 4,4'-bis(diethylamino)diphenyl ketone or 4-(dimethylamino)diphenyl ketone are preferred aromatic ketone compounds.

[0070] In this specification, the term "anthracene derivative" means both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and 10-phenyl-9-anthraboronic acid. From the viewpoint of sensitizing effect and adhesion, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraboronic acid are preferred, and 9,10-diphenylanthracene and 10-phenyl-9-anthraboronic acid are particularly preferred.

[0071] From the viewpoint of adhesion and the rectangularity of the photoresist pattern, 1-phenyl-3-(4-tri-butyl-styryl)-5-(4-tri-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tri-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tri-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline are preferred as pyrazoline derivatives.

[0072] From the viewpoint of preservation stability, the photosensitive layer containing component (D) is preferably containing at least one of a diphenyl ketone compound, a pyrazoline compound, anthracene compound, and a coumarin compound; more preferably, it contains at least one of a diphenyl ketone compound and a pyrazoline compound; and even more preferably, it contains a diphenyl ketone compound.

[0073] The content of component (D) is preferably 0~0.5% by mass, more preferably 0~0.1% by mass, further preferably 0~0.05% by mass, and especially preferably 0~0.025% by mass. By adjusting the content of component (D) within the above range, it is easy to reduce the absorbance in areas outside the exposure wavelength, and thus easy to improve storage stability.

[0074] (E) Component: Polymerization inhibitor Examples of components (E) include phenothiazine, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tributylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], aluminum salts of nitrosophenylhydroxylamine (e.g., aluminum salts of 3-mol nitrosophenylhydroxylamine), diphenylnitrosamine, etc. Preferred components are triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salts of 3-mol nitrosophenylhydroxylamine. These can be used alone or in combination of two or more.

[0075] (E) Component, from the viewpoint of preservation stability, is preferably one of phenothiazine, p-methoxyphenol, tributylcatechol, or 2,6-di-tributyl-p-cresol.

[0076] (E) The content of the component, from the point of view of resolution, is preferably 10 to 5000 ppm, more preferably 50 to 1000 ppm, and even more preferably 50 to 500 ppm, relative to the total mass of all solid components of the photosensitive resin composition.

[0077] Other ingredients Photosensitive resin compositions may contain other components (antioxidants, stabilizers, base dyes, plasticizers, etc.) as desired.

[0078] Examples of base dyes include Basic Green 1 [CAS No. (hereinafter the same): 633-03-4] (e.g., trade name Aizen Diamond Green GH, manufactured by Hodogaya Chemical Industry), Magenta [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., trade name Aizen Victoria Pure Blue BOH, manufactured by Hodogaya Chemical Industry), Rose Red B [81-88-9], Rose Red 6G [989-38-8], and Basic Yellow 2 [2465-27-2]. Among these, Basic Green 1 is preferred from the viewpoint of improving tinting strength, hue stability, and exposure contrast. These can be used alone or in combination of two or more.

[0079] The content of the base dye is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and even more preferably 0.04 to 1% by mass. From the viewpoint of obtaining good colorfastness, the content of the base dye is preferably above the lower limit mentioned above, and from the viewpoint of maintaining the sensitivity of the photosensitive layer, it is preferably below the upper limit mentioned above.

[0080] Examples of antioxidants include triphenyl phosphite (e.g., manufactured by ADEKA, trade name: TPP), benzo(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA, trade name: 2112), benzo(mononylphenyl) phosphite (e.g., manufactured by ADEKA, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA, trade name: 329K). These can be used alone or in combination of two or more.

[0081] The content of the antioxidant, relative to the total mass of all solid components of the photosensitive resin composition, is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.3% by mass. From the viewpoint of achieving good hue stability in the photoresist pattern and improving the sensitivity of the photosensitive resin layer, the content of the antioxidant is preferably at or above the aforementioned lower limit. On the other hand, from the viewpoint of simultaneously suppressing the color development of the photoresist pattern while achieving good hue stability and improving adhesion, it is preferably at or below the aforementioned upper limit.

[0082] From the viewpoint of improving the thermal stability of photosensitive resin compositions, stabilizers can be used. Examples of stabilizers include at least one of epoxy alkyl compounds having glycidyl groups and benzotriazole compounds. These can be used alone or in combination of two or more.

[0083] Examples of epoxide compounds containing a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-molar adduct diglycidyl ether (e.g., Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These can be used alone or in combination of two or more.

[0084] Examples of benzotriazole compounds include carboxybenzotriazole, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-benzotriazole, 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-tolyltriazole, 1-(N,N-bis-2-hydroxyethyl)aminomethyl)-1,2,3-benzotriazole, and 1-(N,N-bis(2-ethylhexyl)aminomethyl)-5-carboxy-1,2,3-benzotriazole.

[0085] The total content of antioxidants, glycidyl alkyl oxide compounds, and benzotriazole compounds in the photosensitive resin composition is preferably 0.001 to 3% by mass, more preferably 0.05 to 1% by mass.

[0086] In this embodiment, the photosensitive resin layer may contain a color-developing dye that develops color upon light irradiation. Known color-developing dyes include combinations of leuco dyes and halogen compounds. Examples of leuco dyes include trimethyl(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet] and trimethyl(4-dimethylamino-2-methylphenyl)methane [leuco malachite green]. Examples of halogen compounds include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, benzyl bromide, dibromomethane, tribromomethylphenyl sulfonate, carbon tetrabromide, trimethyl(2,3-dibromopropane) phosphate, trichloroacetylamine, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane.

[0087] In this embodiment, additives such as plasticizers may be included in the photosensitive layer as needed. Examples of additives include phthalates such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ethers, and polypropylene glycol alkyl ethers.

[0088] <Composition of the Photosensitive Layer> The thickness of the photosensitive layer is preferably 3~100μm, with specific preferred thicknesses including 7μm, 15μm, 25μm, 40μm, and 60μm. An even higher upper limit is 50μm. The closer the thickness is to 3μm, the easier it is to improve resolution; the closer it is to 100μm, the easier it is to improve film strength. Therefore, it can be appropriately selected according to the application. When the formed photoresist pattern is used in the deposition process, the film thickness is preferably 10~30μm, more preferably 15~25μm.

[0089] In this embodiment, the absorbance (γ) at a wavelength of 365 nm for a photosensitive layer with a film thickness of 25 μm is 0.35 or less. This provides excellent preservation stability and the rectangularity of the photoresist pattern, and also facilitates good adhesion. From the same viewpoint, the absorbance is preferably 0.3 or less, more preferably 0.2 or less, even more preferably 0.18 or less, and particularly preferably 0.16 or less. The absorbance can be 0 or more; furthermore, from the viewpoint of obtaining a photosensitive layer resin composition with good photoreactivity and excellent sensitivity, it is preferably 0.11 or more.

[0090] Generally, the absorbance of the photosensitive layer can be measured using a spectrophotometer with the substrate forming the photosensitive layer disposed on the reference layer side. Alternatively, absorbance can generally be measured according to JIS K 0115 (2004). When using a spectrophotometer, the absorbance of the photosensitive layer can be calculated by converting the result measured using only the substrate as the reference layer. In the case of the photosensitive element described later, a support film can be used as the substrate. The absorbance measured by the above method is a value derived from the amount of light scattered by the photosensitive layer and the substrate. In this embodiment, "absorbance" refers to the value derived using the method described in the <Absorbance> section of the embodiments.

[0091] In this implementation, the contribution (X) is calculated using the following formula (1): X(%) = 100×εc / absorbance of photosensitive layer (Y) ･･･ (1) ε: (C) Change in absorbance per 1% by mass of component c: The content (mass %) of component (C) among all solid components in the photosensitive resin composition.

[0092] ε can be obtained by the following method. Photosensitive resin compositions with varying amounts of component (C) were prepared relative to 100 parts by mass of components (A) and (B). These compositions were then coated onto substrates to form films with a thickness of 25 μm, and the absorbance of the resulting photosensitive layers was measured. A graph was plotted with the content (mass %) of component (C) as the X-axis and the absorbance (Y) of the photosensitive layer as the Y-axis. A linear approximation was made to the obtained data, resulting in a straight line with a predetermined slope. The slope of this line corresponds to the change in absorbance ε per 1% mass of component (C) in that content. As for component (A) used at this time, it is preferable to contain methacrylic acid, styrene, benzyl methacrylate, 2-hydroxymethacrylate, and methyl methacrylate in any proportion. As for component (B), it is preferable to be a bisphenol A type di(meth)acrylate compound such as FA-321M. These components, due to their low absorbance at 365 nm, are suitable for accurately determining the change in absorbance ε per 1% by mass of component (C).

[0093] From the perspective of preservation stability, the contribution rate (X) is preferably 45% or higher, even better is 55% or higher, further better is 65% or higher, and best is 85% or higher. The higher the value (X), the easier it is to suppress the sensitizing effect of additives other than component (C), and therefore it becomes easier to reduce the reactivity to long-wavelength light such as yellow light, thus it is considered to have a tendency to improve preservation stability.

[0094] As a means to increase contribution (X), examples include increasing the content of component (C), decreasing the content of component (D), and decreasing the content of other components that have absorption at 365nm.

[0095] The contribution (X) of the photosensitive resin composition containing multiple (C) components is obtained as follows. That is, as component (C), in the case of containing components (C-1) to (Cn) (n is an integer greater than 2), the change value of absorbance per 1% mass ε1 to εn, the content of each component (C) c1 to cn, and even the contribution (X-1) to (Xn) are derived respectively. Next, the sum of the obtained contribution values ​​(X-1) to (Xn) is taken as the contribution value (X) of this implementation.

[0096] <Protective film> The photosensitive element of this embodiment may have a protective film. A support film, a photosensitive layer, and a protective film may be sequentially laminated. The protective film can be deposited on the photosensitive layer side of the laminate of the support film and the photosensitive layer, and it functions as a protective layer.

[0097] When the adhesion between the photosensitive layer and the protective film is sufficiently less than the adhesion between the photosensitive layer and the support film, the protective film can be easily peeled off from the photosensitive layer. For example, polyethylene film, polypropylene film, stretched polypropylene film, polyester film, etc., can be preferably used as the protective film. In addition, a release layer can also be set on the surface of the protective film.

[0098] The thickness of the protective film is preferably 10~100μm, more preferably 10~50μm. Examples of suitable protective films include: ALPHAN (registered trademark) EM-501, ALPHAN E-200, ALPHAN E-201F, ALPHAN FG-201, ALPHAN MA-411 (all manufactured by Prince Aifute Co., Ltd.); TORAYFAN (registered trademark) KW37, TORAYFAN 2578, TORAYFAN 2548, TORAYFAN 2500, TORAYFAN YM17S; CERAPEEL (registered trademark) PJ271, CERAPEEL PJ111, CERAPEEL HP2, CERAPEEL PJ101, CERAPEEL WZ, CERAPEEL MDA, CERAPEEL MFA, CERAPEEL TK07, CERAPEEL BKE, CERAPEEL BX8A, and CERAPEEL... SY (manufactured by Toray Industries, Inc.); GF-18, GF-818, GF-858 (manufactured by Tamapony Corporation, Inc.), etc.

[0099] [Photosensitive element roller] The photosensitive element can be in the shape of a long ruler, or it can be a long ruler-shaped photosensitive element wound around a core in the shape of a roller.

[0100] [Methods for forming photoresist patterns] The method for forming a photoresist pattern using the photosensitive element of this embodiment preferably includes the following steps in sequence: The step of laminating a photosensitive element onto a substrate; The step of exposing the photosensitive layer of the deposited photosensitive element; and The step of developing the exposed photosensitive layer.

[0101] (Layering steps) In the lamination process, specifically, if the photosensitive element contains a protective film, the protective film is peeled off from the photosensitive element, and then a photosensitive layer is heated and pressed onto the surface of a support (e.g., a substrate) using a laminator, performing one or more laminations. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is generally 40°C to 160°C. Heating and pressing can be performed using a laminator equipped with rollers, or by repeatedly passing the substrate and photosensitive layer lamination through rollers several times. Heating and pressing can be performed under reduced pressure, if desired.

[0102] (Exposure Steps) In the exposure step, an exposure machine is used to expose the photosensitive layer. Exposure can ideally be performed after the support has been peeled off. When exposing with a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and can also be measured using a photometer. Direct imaging exposure can also be performed in the exposure step. In direct imaging exposure, the substrate is exposed without a photomask using a direct drawing device. The light source is a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350~410nm. When the pattern is drawn using computer control, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0103] The light irradiation method used in the exposure step is preferably selected from at least one of the following: projection exposure, proximity exposure, contact exposure, direct imaging exposure, and direct electron beam lithography. It is more preferably performed by projection exposure or direct imaging exposure.

[0104] A heating step may also be included between the exposure and development steps. The heating temperature is preferably about 30 to about 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. Implementing this heating step can improve resolution and adhesion. Heating can be achieved using a furnace, thermostatic bath, heating plate, hot air dryer, infrared dryer, or far-infrared heating method, such as a hot air furnace, infrared dryer, or heating roller.

[0105] The elapsed time from the exposure step to the heating step, or more precisely, the elapsed time from the end of exposure to the start of heating, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The elapsed time from the start of heating to the end of heating is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0106] (Developing step) In the developing step, a developing apparatus is used to remove the unexposed or exposed areas from the exposed photosensitive layer using a developing solution. If a support film exists on the photosensitive layer after exposure, it is removed. Then, a developing solution made of an alkaline aqueous solution is used to further remove the unexposed or exposed areas, resulting in a photoresist image.

[0107] The preferred alkaline aqueous solution is an aqueous solution of Na₂CO₃, K₂CO₃, or tetramethylammonium hydroxide. The choice of alkaline aqueous solution is based on the characteristics of the photosensitive layer; however, a Na₂CO₃ aqueous solution with a concentration of 0.2% to 2% by mass is generally used. Surfactants, defoamers, and small amounts of organic solvents to promote development can also be added to the alkaline aqueous solution. The temperature of the developing solution during the developing step is preferably maintained within the range of 20 to 40°C.

[0108] The developing step preferably includes a water washing step to remove the developer contained in the photoresist pattern after development. The washing water can be pure water, industrial water, or other suitable options depending on the characteristics of the photosensitive layer. However, to improve resolution and the shape of the photoresist pattern, a polyvalent metal salt such as MgSO4 at a concentration of 0.001 to 1% by mass can also be added. The temperature of the washing water in the water washing step is preferably maintained within the range of 20 to 40°C.

[0109] The photoresist pattern obtained through the above steps can, as desired, be further heated at 60°C to 300°C. This heating step improves the photoresist pattern's chemical resistance. The heating process can utilize hot air, infrared radiation, or a far-infrared heating furnace.

[0110] In order to obtain a conductor pattern, a conductor pattern forming step can also be performed after the development step or the heating step, which involves etching or plating a substrate with a photoresist pattern.

[0111] The method for manufacturing conductor patterns is as follows: using a metal plate or metal film insulating plate as a substrate, a photoresist pattern is formed by the above-described photoresist pattern forming method, followed by a conductor pattern forming step. In the conductor pattern forming step, the conductor pattern is formed on the substrate surface (e.g., copper surface) exposed by development using a known etching or plating method.

[0112] Furthermore, after manufacturing the conductor pattern using the above-described conductor pattern manufacturing method, a stripping step is performed by using an aqueous solution with stronger alkalinity than the developer to peel off the photoresist pattern from the substrate, thereby obtaining a wiring board (e.g., a printed wiring board) with the desired wiring pattern.

[0113] Regarding the alkaline aqueous solution (hereinafter also referred to as "stripping solution") used for stripping, there are no particular restrictions, but generally an aqueous solution of NaOH or KOH with a concentration of 2-5% by mass, or an organic amine-based stripping solution, is used. A small amount of 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 in the range of 40-70°C.

[0114] In this embodiment, the photosensitive element can be used for: manufacturing printed wiring boards; manufacturing lead frames for IC chip mounting; precision metal foil processing such as metal mask manufacturing; manufacturing packages such as ball grid arrays (BGA) and chip-scale packages (CSP); manufacturing tape substrates such as chip-on-film (COF) and tape auto-bonding (TAB); manufacturing semiconductor bumps; and manufacturing partitions for flat panel displays such as ITO electrodes, addressing electrodes, and electromagnetic shielding covers. Furthermore, unless otherwise stated, the values ​​of the above parameters are determined in accordance with the measurement methods described in the embodiments. [Example]

[0115] The following examples and comparative examples illustrate this embodiment. However, this embodiment is not limited to the following examples as long as it does not depart from its spirit. The physical properties in the examples were determined by the following methods.

[0116] <(A) Synthesis of Components> The monomers (copolymer components) shown in Table 1 were mixed with azobisisobutyronitrile (AIBN) in the proportions shown in Table 1 (unit: parts by mass) to prepare solution (a). In a flask equipped with a stirrer, reflux cooler, thermometer, dropping funnel, and nitrogen inlet tube, 200g of methyl ethyl ketone (MEK) and 100g of ethanol were added. Nitrogen gas was blown into the flask while stirring, and the temperature was raised to 80°C. 300g of solution (a) was added dropwise over 4 hours at a constant rate to the mixture in the flask, and the mixture was stirred at 80°C for 2 hours.

[0117] Next, 0.5 parts by mass of azobisisobutyronitrile (azobisisobutyronitrile) were dissolved in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone (MEK) and 20 parts by mass of ethanol to prepare solution (b). 50 g of solution (b) was added dropwise to the solution in the flask over 10 minutes at a controlled rate, and the solution was stirred at 80°C for 3 hours. Further, the solution in the flask was heated to 90°C over 30 minutes and held at 90°C for 2 hours. Then, stirring was stopped, and the solution was cooled to room temperature (25°C). This yielded solutions of alkali-soluble polymers A1 to A9. The weight-average molecular weights (Mw) of the alkali-soluble polymers A1 to A9 are shown in Table 1.

[0118] The weight-average molecular weight was determined by gel permeation chromatography (GPC) and derived by conversion using a calibration curve for standard polystyrene. The GPC conditions are as follows. (GPC conditions) Pump: Japan Spectrometer PU-980 Tubing: 2 in total Shodex KF-80Y / KF-806M Dissolution solution: Tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05 mL / min Detector: RI-1530 (Japan Spectrophotometer)

[0119] [Preparation of Evaluation Samples] The evaluation samples are prepared as follows.

[0120] <Fabrication of Photosensitive Elements> The components shown in Tables 1 and 2 were mixed according to the proportions shown in Tables 3 to 6 (the numbers for each component indicate the proportion of solid components (unit: parts by mass)). Further, metered methyl ethyl ketone was added until the solid component concentration reached 60%, and the mixture was thoroughly stirred and mixed to obtain a formulation of the photosensitive resin composition. The proportions (parts by mass) refer to the mass of the non-volatile components (mass of the solid component). As a support film, a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., QS71) was used, and the formulation was uniformly coated onto its surface using a doctor blade coater. Next, it was dried in a dryer at 95°C for 2 minutes and 30 seconds to form a 25 μm thick photosensitive layer.

[0121] Next, a 19μm polyethylene film (protective film, manufactured by Tamapori Corporation, GF-818) is laminated as a protective film onto the surface of the photosensitive layer on the side where the polyethylene terephthalate film is not deposited. This yields a photosensitive resin element.

[0122] <Face trimming> The surface of a copper-clad laminate with 18μm rolled copper foil and a thickness of 0.4mm, which serves as the substrate for evaluating image quality, was washed with a 10% by mass H2SO4 aqueous solution.

[0123] Lamination While peeling off the polyethylene film (protective film) from the photosensitive element, a photosensitive resin laminate is laminated onto a copper-clad laminate preheated to 50°C using a hot roller laminator (manufactured by Asahi Kasei Corporation, AL-700) at a roller temperature of 105°C. The air pressure is set to 0.35 MPa, and the lamination speed is 1.5 m / min.

[0124] <Exposure> The evaluation substrate, after lamination for 2 hours, was exposed using a projection exposure machine (Ushio Electric Co., Ltd. UX-2003SM-AGG01) at a wavelength of 365nm with a predetermined projection exposure mask pattern.

[0125] <Heating> The evaluation substrate, which had been exposed for 1 minute, was heated for 30 seconds using a constant temperature thermostat (manufactured by Daiwa Scientific Corporation, DKM600) with a pre-set airflow temperature of 60°C.

[0126] <Development> The polyethylene terephthalate film (support film) is peeled off from the photosensitive layer. Then, using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., dry film developer), development is performed at a spray pressure of 0.15 Pa using a 1% (w / w) Na₂CO₃ aqueous solution at 30°C for a predetermined time. The development spray time is set to twice the shortest development time, and the post-development water wash spray time is also set to twice the shortest development time. The shortest time required for the unexposed portions of the photosensitive layer to completely dissolve is defined as the "shortest development time."

[0127] [evaluate] <Sensitivity (Optimal Exposure)> Evaluation was performed using a photomask pattern with a linewidth (L) / pitch width (S) (hereinafter referred to as "L / S") of 8 / 8 (unit: μm). That is, on a substrate that has undergone the aforementioned surface trimming and lamination, the sensitivity (optimal exposure) was evaluated using this photomask pattern, with the exposure amount (unit: mJ / cm²) at which the linewidth of the pattern formed on the substrate is 8 μm. A lower optimal exposure indicates higher sensitivity.

[0128] <Adhesion> Evaluation was performed using a photomask pattern with an L / S ratio of x / 3x (x = 1~20 (varying in 1μm intervals)) (unit: μm). That is, on a substrate that has undergone the aforementioned surface trimming and lamination, the photomask pattern was used, and exposure was performed with the optimal exposure amount. Then, the aforementioned heating and development processes were performed to form a photoresist pattern. The photoresist pattern was observed using an optical microscope at 100x magnification to obtain an image. Adhesion was evaluated by the minimum linewidth in the exposed areas (the areas without serpentine lines or defects). A smaller value indicates better adhesion. Adhesion below 7 μm was considered acceptable. In a single-state sample, adhesion below 5 μm was considered excellent.

[0129] <resolution> Evaluation was performed using a photomask pattern with an L / S ratio of x / x (x = 1~20 (varying in 1μm intervals)) (unit: μm). That is, on a substrate that has undergone the aforementioned surface trimming and lamination, the photomask pattern was used, and exposure was performed with the optimal exposure amount. Then, the aforementioned heating and development processes were performed to form a photoresist pattern. The photoresist pattern was observed using an optical microscope at 100x magnification to obtain the observed image. The resolution was evaluated by the minimum linewidth removed from the exposed areas (line portions) without serpentine lines or defects and from the unexposed areas (space portions) without residue. A smaller value indicates better resolution. Resolution below 7 μm was considered acceptable. For a single-state sample, a resolution below 5 μm was considered excellent.

[0130] <Maintaining Stability> On the aforementioned surface-trimmed substrate, a photosensitive element was laminated and left to stand for 100 hours under ambient temperature, 55% humidity, and yellow light. The optimal exposure was then evaluated. The difference in optimal exposure before and after the standing period was considered as storage stability. For storage stability, a small change in optimal exposure, below 10 mJ / cm², was considered acceptable. In a single sample, a change of 0 mJ / cm² was considered excellent.

[0131] <Number of Foreign Objects> Prepare a 2m × 2m photosensitive element (test piece). Use an optical microscope to examine the photosensitive layer through the supporting film, and count the number of foreign objects with a longest outer diameter of 50μm or more. A number of 10 or fewer foreign objects is considered acceptable. A number of 3 or fewer foreign objects is considered excellent.

[0132] <Absorbance> After peeling off the protective film from the photosensitive element, a spectrophotometer U-3010 (manufactured by Hitachi High Technology Co., Ltd.) was used, with a 16μm thick polyethylene terephthalate film (support film, manufactured by Toray Industries, Inc., QS71) as the reference layer, to measure the absorbance of the photosensitive layer at a wavelength of 365nm. The measurement was performed with the slit width set at 4nm and the scan speed at 600nm / min.

[0133] <Contribution of absorbance of component (C-1) (X)> The components were mixed in the proportions specified in Table 7 to obtain photosensitive resin compositions B1 to B5. Using photosensitive resin compositions B1 to B5, photosensitive elements with a film thickness of 25 μm were obtained by the method described above. Next, the absorbance of these photosensitive layers at 365 nm was measured by the method described above. The content of component (C-1) is represented by the X-axis, and the absorbance of the photosensitive layer is represented by the Y-axis. The results are plotted in a graph, resulting in a straight line with a slope of 2.146. Based on this, ε(change in absorbance per 1% mass of component (C)) = 2.146 is obtained. The contribution (X) of the absorbance of the (C-1) component to the absorbance of each photosensitive element is calculated by using the following formula (1). X(%) = 100×εc / Absorbance of photosensitive layer (Y) ･･･ (1) ε: (C) Change in absorbance per 1% by mass of component c: (C) Content (mass %) of the photosensitive resin component

[0134] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7]

[0135] As confirmed by the table, in the embodiments, the adhesion, resolution, and storage stability are all good.

[0136] While the above description describes the present invention, the invention is not limited to the above description. Appropriate modifications may be made as long as they do not depart from the spirit of the invention. [Industrial Utilization]

[0137] The photosensitive element of this invention can produce photoresist patterns with good adhesion, resolution, and preservation stability. This photosensitive element can be widely used as a photosensitive element for forming photoresist patterns in printed wiring boards and other applications.

[0138] 1: Photosensitive layer 10: Foreign object 11: Precipitates 12: Bubbles

Claims

1. A photosensitive element comprising a support film and a photosensitive layer containing a photosensitive resin composition; the photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer, (B) a compound having ethylene unsaturated double bonds, and (C) a biimidazole photopolymerization initiator; the (C) component comprising 5.0% by mass or more relative to all solid components of the photosensitive resin composition; the absorbance (Y) of the photosensitive layer at a wavelength of 365 nm with a film thickness of 25 μm being 0.35 or less; the contribution (X) of the absorbance of the (C) component to the absorbance (Y) being 55% or more; the contribution (X) being calculated by the following formula (1): X (%) = 100 × εc / absorbance (Y) of the photosensitive layer ･･･ (1) ε: Absorbance change per 1% by mass of component (C); c: Content (by mass%) of component (C) in all solid components of the photosensitive resin composition; Component (C) is a dimer of 2,4,5-triarylimidazolium containing 5.0% by mass or more of the solid components of the photosensitive resin composition; and the photosensitive element is used by exposure to a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350–410 nm.

2. The photosensitive element as described in claim 1, wherein, The (C) component contains 5.5% by mass or more of the total solid components of the photosensitive resin composition.

3. The photosensitive element as described in claim 1 or 2, wherein, The (C) component contains 6.0% by mass or more of all solid components of the photosensitive resin composition.

4. The photosensitive element as described in claim 1 or 2, wherein, The contribution rate (X) is over 65%.

5. The photosensitive element as described in claim 1 or 2, wherein, The contribution rate (X) is over 85%.

6. The photosensitive element as described in claim 1 or 2, wherein, The absorbance (Y) is below 0.

30.

7. The photosensitive element as described in claim 1 or 2, wherein, The absorbance (Y) is below 0.

25.

8. The photosensitive element as described in claim 1 or 2, wherein, The photosensitive resin composition selectively contains component (D): other photopolymerization initiators and / or sensitizers; the content of component (D) is 0 to 0.1% by mass.

9. The photosensitive element as described in claim 1 or 2, wherein, The photosensitive resin composition further contains at least one selected from the group consisting of diphenyl ketone compounds, pyrazoline compounds, anthracene compounds, and coumarin compounds as (D) other photopolymerization initiators and / or sensitizers.

10. The photosensitive element as described in claim 1 or 2, wherein, The photosensitive resin composition further contains at least one selected from the group consisting of diphenyl ketone compounds and pyrazoline compounds as (D) other photopolymerization initiators and / or sensitizers.

11. The photosensitive element as described in claim 1 or 2, wherein, The photosensitive resin composition does not contain component (D): other photopolymerization initiators and / or sensitizers; or contains more than 0 and less than 0.1% by mass of component (D), and component (D) contains at least one of a diphenyl ketone compound and a pyrazoline compound.

12. The photosensitive element as described in claim 1 or 2, wherein, The (A) component contains styrene as a monomer component, and the proportion of the constituent units derived from the styrene is more than 35% by mass, based on the total mass of all monomer components in the (A) component.

13. The photosensitive element as described in claim 1 or 2, wherein, The (A) component contains styrene as a monomer component, and based on the total mass of all monomer components in the (A) component, the proportion of the constituent units derived from the styrene is 50% or more by mass.

14. The photosensitive element as described in claim 1 or 2, wherein, The (A) component contains styrene as a monomer component, and based on the total mass of all monomer components in the (A) component, the proportion of the constituent units derived from the styrene is 60% or more by mass.

15. The photosensitive element as described in claim 1 or 2, wherein, The component (B) contains a compound represented by the following general formula (II): [Chemical 1] (where R2 is individually and independently a hydrogen atom or a methyl group; X2O and Y2O are individually and independently oxyethyl or oxypropyl; m3, m4, n2, and n3 are individually and independently integers from 0 to 40; m3+m4 are from 1 to 40; and n2+n3 are from 0 to 20); the amount of the compound represented by formula (II) is 50% by mass or more, based on the total amount of component (B).

16. The photosensitive element as described in claim 1 or 2, wherein, The photosensitive resin composition further contains: (E) polymerization inhibitor.

17. The photosensitive element as described in claim 1 or 2, wherein, The absorbance of the support film at 365nm is below 0.

1.

18. The photosensitive element as described in claim 1 or 2, wherein, It further possesses a protective film.

19. A method for forming a photoresist pattern, which uses a photosensitive element as described in claim 1 or 2; the method comprises the following steps: a step of depositing a photosensitive element on a substrate; a step of exposing a photosensitive layer of the deposited photosensitive element; and a step of developing the exposed photosensitive layer.

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