CN116830037A

CN116830037A - Photosensitive element, method for producing cured product pattern, and method for producing circuit board

Info

Publication number: CN116830037A
Application number: CN202180038977.0A
Authority: CN
Inventors: 粂壮和; 黑泽刚; 贺口阳介; 岩下健一; 成田真生; 加藤哲也
Original assignee: Lishennoco Co ltd
Current assignee: Lishennoco Co ltd
Priority date: 2020-11-13
Filing date: 2021-11-10
Publication date: 2023-09-29
Also published as: KR20230107474A; TW202225837A; WO2022102101A1; WO2022102675A1; JPWO2022102675A1

Abstract

A photosensitive element (1) is provided with a support film (10) and a photosensitive layer (20) disposed on the support film (10), wherein the number of defects having a maximum diameter of 1 [ mu ] m or more in the support film (10) is 0.225mm per unit ² The photosensitive layer (20) contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator, wherein the number of the photopolymerizable compound is 100 or less.

Description

Photosensitive element, method for producing cured product pattern, and method for producing circuit board

Technical Field

The present invention relates to a photosensitive element, a method for producing a cured product pattern, a method for producing a wiring board, and the like.

Background

Conventionally, as a resist material used for etching, plating, and the like in the field of manufacturing circuit boards (for example, printed wiring boards), the field of precision machining of metals, and the like, a layer composed of a support film and a photosensitive resin composition (hereinafter, referred to as a "photosensitive layer") and a photosensitive element composed of a protective film have been widely used.

For example, a wiring board is manufactured as follows. First, after the protective film of the photosensitive element is peeled off from the photosensitive layer, the photosensitive layer is laminated on the substrate. Next, after pattern exposure is performed on the photosensitive layer, the unexposed portions are removed by a developer, and a resist (resist pattern) is formed. Then, an etching treatment or a plating treatment is performed through the resist, thereby forming a wiring board.

As support films for photosensitive elements, support films having a specific haze value, support films having a specific lubricant particle size, and the like are known (for example, refer to patent documents 1 and 2 below).

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 2001-13681

Patent document 2: japanese patent laid-open publication No. 2014-74764

Disclosure of Invention

Technical problem to be solved by the invention

In the production of circuit boards and the like, it is necessary to suppress the occurrence of defects in the resist (for example, defects such as dishing of the resist). If such defects of the resist are generated, a defective opening during etching or a defective short circuit during plating tends to occur, and the manufacturing yield of the wiring board or the like tends to be lowered. In contrast, with the higher resolution of the finer lines, it is necessary to further suppress the occurrence of defects in the resist.

An object of one aspect of the present invention is to provide a photosensitive element capable of suppressing occurrence of defects in a resist. Another object of the present invention is to provide a method for producing a cured product, a method for producing a cured product pattern, and a method for producing a circuit board, each using such a photosensitive element.

Means for solving the technical problems

According to patent document 2, particles having a diameter of 5 μm or more and aggregates having a diameter of 5 μm or more contained in the support film cause defects in the resist. On the other hand, the present inventors have found that small defects having a maximum diameter of 1 μm increase the number of defects in the resist as defects contained in the support film, and have found that the occurrence of defects in the resist can be suppressed by reducing the number of defects having a maximum diameter of 1 μm or more.

One aspect of the present invention relates to a photosensitive element comprising a support film and a photosensitive layer disposed on the support film, wherein the number of defects having a maximum diameter of 1 μm or more in the support film is 0.225mm per one ² The photosensitive layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator, wherein the number of the photopolymerizable compound is 100 or less.

According to the photosensitive element of the aspect of the present invention, occurrence of defects in the resist can be suppressed.

Another aspect of the present invention relates to a method for producing a cured product, comprising: and an exposure step of irradiating the photosensitive layer with active light through the support film in a state where the photosensitive elements are laminated on the substrate to obtain a cured product.

Another aspect of the present invention relates to a method for producing a cured product pattern, comprising: and removing at least a part of the photosensitive layer other than the cured product after the exposure step in the method for producing a cured product.

Another aspect of the present invention relates to a method for manufacturing a wiring board, including: and a step of performing an etching treatment or a plating treatment on the laminate having the cured product pattern obtained by the method for producing a cured product pattern on the substrate.

Effects of the invention

According to one aspect of the present invention, a photosensitive element capable of suppressing occurrence of defects in a resist can be provided. Further, according to another aspect of the present invention, a method for producing a cured product pattern, and a method for producing a circuit board using such a photosensitive element can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element.

Fig. 2 is a view showing the observation result of the surface of the support film.

Fig. 3 is a graph relating to evaluation of defects in the inside of the support film.

Fig. 4 is a diagram relating to evaluation of defects in a resist.

Detailed Description

The mode for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

In the present specification, the numerical range indicated by the term "to" means a range including numerical values described before and after the term "to" as a minimum value and a maximum value, respectively. The term "a or more" in the numerical range means a and a range exceeding a. The term "a or below" in the numerical range means a and a range smaller than a. In the numerical ranges described in stages in the present specification, the upper limit value or the lower limit value of the numerical range in one stage may be arbitrarily combined with the upper limit value or the lower limit value of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. The "a or B" may include either one of a and B, or both of them. The materials exemplified in the present specification can be used singly or in combination of 1 or more than 2, unless otherwise specified. When a plurality of substances corresponding to the respective components are present in the composition, the content of the respective components in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified. The term "layer" and "film" include a structure having a shape formed in a part of the entire surface, as well as a structure having a shape formed in the entire surface when seen in a plan view. The term "process" includes not only an independent process but also the term if the intended function of the process is achieved even if the process cannot be clearly distinguished from other processes. The "(meth) acrylate" means at least one of an acrylate and a methacrylate corresponding thereto. The same applies to other similar expressions such as "(meth) acrylic acid". "EO" refers to ethylene oxide, and "EO-modified" compounds refer to compounds having an oxyethylene group. "PO" means propylene oxide, and "PO modified" refers to a compound having an oxypropylene group.

< photosensitive element >)

The photosensitive element according to the present embodiment includes a support film and a photosensitive layer disposed on the support film, and the number of defects having a maximum diameter of 1 μm or more in the support film is 0.225mm per one ² The photosensitive layer contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, wherein the number of the photopolymerizable compound is 100 or less.

According to the photosensitive element of the present embodiment, occurrence of defects in the resist after exposure and development of the photosensitive layer can be suppressed, and occurrence of defects in the resist can be suppressed even when a high-resolution exposure machine is used. According to the photosensitive element of the present embodiment, excellent resolution and adhesion (development resistance) can be obtained, and occurrence of defects in the resist can be suppressed. According to one embodiment of the photosensitive element according to the present embodiment, as described later, it is possible to reduce the minimum development time, reduce the exposure amount (increase in sensitivity), suppress the residue, and the like.

Defects in the support film can cause defects in the resist after development by causing light scattering when the photosensitive layer is exposed to light through the support film. In particular, when a high-resolution exposure machine is used, the influence of light scattering is large, and defects in the resist are likely to occur after development. If such defects of the resist are generated, a defective opening during etching or a defective short circuit during plating tends to occur, and the production yield of the wiring board tends to be lowered. In order to suppress the occurrence of defects in the resist, a support film having a haze value of 0.01 to 3.0% is considered, but it is insufficient to suppress the occurrence of defects in the resist. In contrast, according to the findings of the present inventors, since the number of defects of the resist increases due to small defects having a maximum diameter of 1 μm, the occurrence of defects of the resist can be suppressed by reducing the number of defects having a maximum diameter of 1 μm or more.

Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. The photosensitive element 1 shown in fig. 1 includes a support film 10 and a photosensitive layer 20. The photosensitive layer 20 is provided on the 1 st principal surface 10a of the support film 10. The support film 10 has a 2 nd main surface 10b on the opposite side of the 1 st main surface 10 a.

From the viewpoint of easily suppressing occurrence of defects of the resist, the number of defects having a maximum diameter of 1 μm or more in the inside of the support film may be 0.225mm each ² 80 or less, 50 or less, 30 or less, 20 or less, 18 or less, 16 or less, 15 or less, 10 or less, 8 or less, 5 or less, 3 or less, 2 or less, or 1 or less. The number of defects may be 0. The number of defects can be reduced by selectively removing a component that can generate defects, for example, defects can be reduced by filtering a composition for film formation of the support film before film formation, or the like. The number of defects in the support film was every 0.225mm ² (0.150 mm. Times.0.150 mm) number of defects. The number of defects is an average of a plurality of measured values. For example, the average value can be obtained as an average value of measurement values of 50 total areas obtained by performing an operation of measuring the number of defects of an arbitrary 10-point area in the support film 5 times. A unit area of 0.225mm in relation to the number of defects ² Is the area of the surface parallel to the main surface of the support film.

The defect in the support film is, for example, a light shielding material, and is presumably caused by a component having a refractive index different from that of a constituent material that is a main component of the support film. Examples of the factors that form the light-shielding material include a gel-like material of a polymer; monomers as raw materials; a catalyst used in the production; inorganic particles (lubricants, etc.), organic particles, aggregates of particles, etc. for producing the support film. Examples of the inorganic component of the inorganic particles include monomers such as calcium, magnesium, and silica; a compound containing at least one of these, and the like. The light shielding material shields light from active light rays during exposure.

According to the findings of the present inventors, the number of defects in the support film has a great influence on the generation of defects of the resist. The number of defects in the support film is the number of defects (for example, the number of light-shielding materials) in the support film measured using a confocal microscope (confocal microscop e). The conditions under which the inside of the support film can be appropriately observed can be adjusted according to whether or not the photosensitive layer is formed. When the support film has a layer (lubricant layer or the like) containing particles in the surface layer portion, the surface layer portion is excluded and the inner layer portion of the support film is evaluated in order to evaluate the number of defects in the support film. For example, when the lubricant layer is formed on the surface layer portion on both sides, the region (inner layer portion) between the portion having a depth of 0.5 μm from one side and the portion having a depth of 0.5 μm from the other side can be measured. That is, when the support film has a lubricant layer on the surface, the number of defects in the support film is the number of defects in the support film excluding the lubricant layer. According to the findings of the present inventors, defects may occur in the support film due to the influence of the lubricant layer provided in the surface layer portion.

As the confocal microscope, a HYBRID laser microscope OPTELICS HYBRID (Lasert ec Corporation, product name) or the like can be used. The observation by the confocal microscope is a measurement method in which reflected light from an observation target is detected by a light receiving unit. When the object to be observed is in focus (at the time of focusing), reflected light can be strongly obtained, and the intensity of light (which is often observed in white) can be strongly observed. When the object to be observed is out of focus (defocused), the intensity of light is observed to be weak (black observation is often performed).

The aperture number (Na) of the objective lens for observation may be 0.8 from the viewpoint of easy and effective observation with high accuracy. When the aperture number is 0.8, the contact between the lens and the observation object is easily suppressed to contaminate the microscope, and the excessive increase in magnification is suppressed, compared with the case where the aperture number exceeds 0.8, so that the decrease in the light quantity of the field of view is easily suppressed to reduce the detection level. Further, when the aperture number (Na) is 0.8, it is difficult to add an error to the size detection of the observation target because the resolution is suppressed from decreasing, compared with the case where the aperture number is smaller than 0.8, and thus it is easy to perform high-precision measurement.

In the observation under a confocal microscope, the measurement magnification may be 50 times, and the digital zoom on the software may be 2 times. When the measurement magnification is 50 times, the decrease in the light quantity of the visual field is suppressed as compared with when the measurement magnification exceeds 50 times, and the decrease in the detection level is easily suppressed, and the size of the defect is easily and accurately measured as compared with when the measurement magnification is less than 50 times. When the digital zoom is 2 times, the decrease in the light quantity of the field of view is suppressed compared to when the digital zoom is equal (not set), and the decrease in the detection level is easily suppressed.

Examples of the constituent material of the support film include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene 2, 6-naphthalate (PEN); polyolefins such as polypropylene and polyethylene. The support film may be a polyester film or a PET film from the viewpoint of easily suppressing occurrence of defects in the resist. The support film may be a transparent resin film.

The support film may be a single layer or multiple layers. The support film may have a lubricant layer disposed on at least one surface of the inner layer portion (for example, a film of the constituent material of the support film). For example, the support film may have a polyester film and a lubricant layer disposed on at least one side of the polyester film. The lubricant layer can be formed by a known method such as a roll coater, a flow coater, a spray coater, a curtain flow coater, a dip coater, or a slot die coater.

The haze value of the support film may be 0.01% or more, 0.05% or more, 0.1% or more, 0.3% or more, 0.5% or more, or 0.7% or more, from the viewpoint of easiness in improving the operability when the photosensitive element is laminated on the substrate, the operability when the photosensitive layer is formed on the support film, and the like. The haze value of the support film may be 3.0% or less, 1.5% or less, 0.8% or less, or 0.7% or less from the viewpoint of easy obtaining of good sensitivity and resolution. From these viewpoints, the haze value of the support film may be 0.01 to 3.0%, 0.01 to 1.5%, 0.01 to 0.8%, or 0.01 to 0.7%. "haze value" refers to haze. The haze value of the support film can be measured according to a method prescribed in JIS K7105 using a commercially available haze meter (nephelometer, for example, NIPPON DENSHOKU INDUSTRIES co., ltd. Product name "NDH-5000").

The light transmittance of the support film (for example, the light transmittance in the entire range of wavelengths 380 to 780 nm) may be in the following range. The light transmittance of the support film may be 80% or more, 85% or more, 87% or more, 88% or more, or 89% or more. The light transmittance of the support film may be 95% or less, 93% or less, 90% or less, or 89% or less. From these viewpoints, the light transmittance of the support film may be 80 to 95%. The light transmittance of the support film can be measured using a commercially available haze meter (for example, NIPPON DENSHOKU INDUSTRIES co., ltd. Product name "NDH-5000").

The thickness of the support film or the thickness of the polyester film may be in the following range. The thickness may be 5 μm or more, 10 μm or more, 11 μm or more, 12 μm or more, 15 μm or more, or 16 μm or more from the viewpoint that the support film is less likely to break when the support film is peeled from the photosensitive element. The thickness may be 200 μm or less, 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 18 μm or less from the viewpoint of easily securing a focus margin at the time of exposure. From these viewpoints, the thickness may be 5 to 200. Mu.m, 11 to 100. Mu.m, 12 to 50. Mu.m, or 15 to 40. Mu.m.

The photosensitive layer is a layer composed of a photosensitive resin composition. The photosensitive layer and the photosensitive resin composition constituting the photosensitive layer contain (A) a binder polymer ((A) component), (B) a photopolymerizable compound having an ethylenically unsaturated bond ((B) component) and (C) a photopolymerization initiator ((C) component). For example, the photosensitive layer can be obtained by removing at least a part of the solvent in the film-forming resin composition (photosensitive resin composition). The photosensitive layer and the photosensitive resin composition constituting the photosensitive layer have negative photosensitivity.

Examples of the constituent materials of the binder polymer of the component (a) include acrylic resins, styrene resins, epoxy resins, amide epoxy resins, alkyd resins, phenolic resins, and the like. From the viewpoint of easy obtaining of good alkali developability, the component (a) may contain an acrylic resin. As the component (a), a binder polymer used in a conventional photosensitive resin composition can be used.

(A) The component (c) can be obtained by polymerizing a polymerizable monomer (for example, radical polymerization). That is, the component (A) has a polymerizable monomer as a monomer unit. Examples of the polymerizable monomer include (meth) acrylic acid, alkyl (meth) acrylates such as methyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, styrene compounds such as styrene and styrene derivatives (vinyltoluene, α -methylstyrene, etc.), and maleic acid. Substituents may be bonded to the aromatic ring of benzyl (meth) acrylate.

The component (a) may have a carboxyl group in the molecule from the viewpoint of easy availability of good alkali developability. The binder polymer having a carboxyl group can be obtained by polymerizing (for example, radical polymerization) a polymerizable monomer having a carboxyl group. From the viewpoint of easy availability of good alkali developability, the component (a) may have a polymerizable monomer containing a carboxyl group as a monomer unit, and may have (meth) acrylic acid as a monomer unit.

When the component (a) has (meth) acrylic acid as a monomer unit (structural unit derived from (meth) acrylic acid), the content of the monomer unit of (meth) acrylic acid may be in the following range based on the total amount of monomer units constituting the component (a) from the viewpoint of easy obtainment of good resist peeling characteristics (ease of peeling of a cured product of a photosensitive layer relative to a substrate) and developability. The content of the monomer unit of (meth) acrylic acid may be 10 mass% or more, 15 mass% or more, 20 mass% or more, or 25 mass% or more. The content of the monomer unit of (meth) acrylic acid may be 40 mass% or less, 35 mass% or less, or 30 mass% or less. From these viewpoints, the content of the monomer unit of (meth) acrylic acid may be 10 to 40 mass%, 15 to 35 mass%, 20 to 35 mass%, or 20 to 30 mass%.

From the viewpoint of easy availability of good alkali developability and resist stripping characteristics, the component (a) may have an alkyl (meth) acrylate as a monomer unit (a structural unit derived from an alkyl (meth) acrylate), or may have (meth) acrylic acid and an alkyl (meth) acrylate as monomer units. The alkyl (meth) acrylate may contain methyl (meth) acrylate from the viewpoint of easy availability of good alkali developability and resist stripping characteristics.

When the component (A) has an alkyl (meth) acrylate as a monomer unit, the content of the monomer unit of the alkyl (meth) acrylate may be in the following range based on the total amount of the monomer units constituting the component (A). The content of the monomer unit of the alkyl (meth) acrylate may be 1 mass% or more, 3 mass% or more, or 5 mass% or more from the viewpoint of easy obtaining of good resist stripping characteristics. The content of the monomer unit of the alkyl (meth) acrylate may be 40 mass% or less, 30 mass% or less, 20 mass% or less, 10 mass% or less, 8 mass% or less, or 5 mass% or less from the viewpoint of easy obtaining of good resolution and adhesion. From these viewpoints, the content of the monomer unit of the alkyl (meth) acrylate may be 1 to 40 mass%, 3 to 30 mass%, or 5 to 20 mass%.

From the viewpoint of easy obtaining of good adhesion and resist stripping characteristics, the component (a) may have benzyl (meth) acrylate as a monomer unit (a structural unit derived from benzyl (meth) acrylate). In this case, the content of the monomer unit of benzyl (meth) acrylate may be in the following range based on the total amount of monomer units constituting the component (a) from the viewpoint of easy obtaining of good adhesion and resist release characteristics. The content of the monomer unit of benzyl (meth) acrylate may be 10 mass% or more, 15 mass% or more, or 20 mass% or more. The content of the monomer unit of benzyl (meth) acrylate may be 60 mass% or less, 55 mass% or less, 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, 30 mass% or less, or 25 mass% or less. From these viewpoints, the content of the monomer unit of benzyl (meth) acrylate may be 10 to 60 mass%, 15 to 55 mass%, 15 to 35 mass%, or 20 to 30 mass%.

From the viewpoint of easy obtaining of good resolution and adhesion, the component (a) may have a styrene compound as a monomer unit (structural unit derived from the styrene compound). In this case, the content of the monomer units of the styrene compound may be in the following range based on the total amount of the monomer units constituting the component (a). The content of the monomer unit of the styrene compound may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, or 45 mass% or more from the viewpoint of easy obtaining of good resolution. The content of the monomer unit of the styrene compound may be 60 mass% or less, 50 mass% or less, or 45 mass% or less from the viewpoint of easy obtaining of good resist stripping characteristics. From these viewpoints, the content of the monomer unit of the styrene compound may be 10 to 60 mass%, 10 to 50 mass%, 20 to 45 mass%, 30 to 45 mass%, or 40 to 45 mass%.

The weight average molecular weight (Mw) of the component (a) may be 10000 or more, 20000 or more, 25000 or more, 30000 or more, 35000 or more, 40000 or more, or 45000 or more from the viewpoint of easy obtaining of good adhesion. The weight average molecular weight of the component (a) may be 80000 or less, 50000 or less, or 45000 or less from the viewpoint of easy obtaining of good developability. From these viewpoints, the weight average molecular weight of the component (a) may be 10000 to 80000, 20000 to 50000, or 25000 to 45000.

(A) The dispersity (Mw/Mn) of the components may be 1.5 or more or 2.0 or more. The dispersity (Mw/Mn) of the component (A) may be 3.5 or less or 3.3 or less from the viewpoint of easy obtaining of good adhesion and resolution.

The weight average molecular weight (Mw) and the dispersity (Mw/Mn) can be measured by, for example, gel Permeation Chromatography (GPC), and obtained by conversion using a calibration curve of standard polystyrene. More specifically, the measurement can be performed by the method described in the examples. For a compound having a low molecular weight, when it is difficult to determine by this determination method, the molecular weight can also be determined by other methods and the average value thereof can be calculated.

The acid value of component (A) may be 60mgKOH/g or more, 65mgKOH/g or more, 70mgKOH/g or more, 75mgKOH/g or more, 80mgKOH/g or more, 85mgKOH/g or more, 90mgKOH/g or more, 95mgKOH/g or more, 100mgKOH/g or more, or 105mgKOH/g or more from the viewpoint of easy obtaining of good developability. The acid value of component (A) may be 250mgKOH/g or less, 240mgKOH/g or less, 230mgKOH/g or less, 200mgKOH/g or less, 150mgKOH/g or 120mgKOH/g or less from the viewpoint of easy obtaining of good adhesion. From these viewpoints, it may be 60 to 250mgKOH/g, 65 to 250mgKOH/g, 70 to 240mgKOH/g or 75 to 230 mgKOH/g. (A) The acid value of the component (a) can be adjusted by the content of the monomer unit constituting the component (a) (for example, the monomer unit of (meth) acrylic acid).

(A) The content of the component (c) may be in the following range based on the total amount of the photosensitive layer or the total amount of the solid content of the photosensitive resin composition. The content of the component (a) may be 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, 45 mass% or more, 50 mass% or more, or 55 mass% or more from the viewpoint of easy obtainment of good film formability and easy suppression of embrittlement of the cured product. The content of the component (a) may be 90 mass% or less, 85 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, or 60 mass% or less from the viewpoint of easy obtaining of good sensitivity and resolution. From these viewpoints, the content of the component (a) may be 20 to 90 mass%, 30 to 80 mass%, or 40 to 65 mass%.

(A) The content of the component (a) may be within the following range with respect to 100 parts by mass of the total amount of the component (B). The content of the component (a) may be 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more from the viewpoint of easy obtainment of good film formability and easy suppression of embrittlement of the cured product. The content of the component (a) may be 95 parts by mass or less, 90 parts by mass or less, 85 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or 60 parts by mass or less, from the viewpoint of easy obtaining of good sensitivity and resolution. From these viewpoints, the content of the component (a) may be 30 to 95 parts by mass, 30 to 70 parts by mass, 35 to 70 parts by mass, 40 to 65 parts by mass, or 50 to 60 parts by mass.

(B) The component (photopolymerizable compound having an ethylenically unsaturated bond) may be any compound having an ethylenically unsaturated bond and being photopolymerizable.

The component (B) may contain a bisphenol a-type di (meth) acrylate compound from the viewpoint of easy availability of good alkali developability, resolution, adhesion, and resist stripping characteristics. The bisphenol a type di (meth) acrylate compound may be modified with alkylene oxide, and may have polyoxyalkylene group (polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, etc.).

Examples of the bisphenol a-type di (meth) acrylate compound include 2, 2-bis (4- ((meth) acryloxypolyethoxy) phenyl) propane (2, 2-bis (4- ((meth) acryloxypentaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolypropoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolybutoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolyethoxypropoxy) phenyl) propane, and the like.

From the viewpoint of easy availability of good resolution, adhesion and resist stripping characteristics, the component (B) may contain 2, 2-bis (4- ((meth) acryloxypolyethoxy) phenyl) propane, and may contain at least one selected from the group consisting of 2, 2-bis (4- ((meth) acryloxypentaethoxy) phenyl) propane and 2, 2-bis (4- ((meth) acryloxydiethoxy) phenyl) propane, and 2, 2-bis (4- ((meth) acryloxypentaethoxy) phenyl) propane and 2, 2-bis (4- ((meth) acryloxydiethoxy) phenyl) propane may also be used in combination.

The component (B) may contain, as the bisphenol a-type di (meth) acrylate compound having a polyoxyalkylene group, a bisphenol a-type di (meth) acrylate compound having a number of oxyalkylene groups in a polyoxyalkylene chain (number of oxyalkylene groups in one molecule) in the following range from the viewpoint of easily suppressing occurrence of defects in the resist, from the viewpoint of easily shortening the minimum development time, and from the viewpoint of easily obtaining good resolution and adhesion. The number of oxyalkylene groups in the polyoxyalkylene chain of the bisphenol a-type di (meth) acrylate compound having a polyoxyalkylene group in the component (B) contained in the photosensitive layer or the photosensitive resin composition (average value in the whole of the component (B) contained in the photosensitive layer or the photosensitive resin composition) may be in the following range from the viewpoint of easily suppressing occurrence of defects in the resist, from the viewpoint of easily shortening the minimum development time, and from the viewpoint of easily obtaining good resolution and adhesion. The number of oxyalkylene groups may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more. The number of oxyalkylene groups may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less. From these viewpoints, the number of oxyalkylene groups may be 1 to 20.

The content of the bisphenol a di (meth) acrylate compound may be in the following range based on the total amount of the photosensitive layer or the total amount of the solid content of the photosensitive resin composition from the viewpoint of easy achievement of good resolution and easy suppression of residues. The content of the bisphenol a-type di (meth) acrylate compound may be 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 36 mass% or more, or 38 mass% or more. The content of the bisphenol a-type di (meth) acrylate compound may be 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, 50 mass% or less, 45 mass% or less, 40 mass% or less, 38 mass% or less, or 36 mass% or less. From these viewpoints, the content of the bisphenol a-type di (meth) acrylate compound may be 10 to 80 mass%.

The content of the bisphenol a-type di (meth) acrylate compound may be within the following range based on the total amount of the component (B) from the viewpoint of easy achievement of good resolution and easy suppression of residues. The content of the bisphenol a-type di (meth) acrylate compound may be 50 mass% or more, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, 80 mass% or more, 85 mass% or more, or 90 mass% or more. The content of the bisphenol a-type di (meth) acrylate compound may be 99 mass% or less, 95 mass% or less, or 90 mass% or less. From these viewpoints, the content of the bisphenol a-type di (meth) acrylate compound may be 50 to 99 mass% or 60 to 99 mass%.

The content of the bisphenol a-type di (meth) acrylate compound may be within the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (B) from the viewpoint of easy achievement of good resolution and easy suppression of residues. The content of the bisphenol a-type di (meth) acrylate compound may be 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. The content of the bisphenol a-type di (meth) acrylate compound may be 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less. From these viewpoints, the content of the bisphenol a-type di (meth) acrylate compound may be 10 to 80 parts by mass, 20 to 60 parts by mass, or 30 to 50 parts by mass.

(B) The component (c) may contain a (meth) acrylate compound having a skeleton derived from dipentaerythritol (hereinafter, referred to as a "(meth) acrylate compound a"), and may contain a (meth) acrylate compound a and a bisphenol a-type di (meth) acrylate compound. On the other hand, the photosensitive layer and the photosensitive resin composition constituting the photosensitive layer may not contain the (meth) acrylate compound a. The present inventors have found that by adjusting the content of the (meth) acrylate compound a, the generation of residues when exposing and developing the photosensitive layer can be suppressed (in particular, the generation of residues can be suppressed even if the development time is shortened).

The content of the (meth) acrylate compound a may be in the following range based on the total amount of the photosensitive layer or the total amount of the solid content of the photosensitive resin composition. From the viewpoint of easy residue suppression, the content of the (meth) acrylate compound a may be 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, 6 mass% or less, 5 mass% or less, 4 mass% or less, 3 mass% or less, 2 mass% or less, 1 mass% or less, or 0.1 mass% or less. The content of the (meth) acrylate compound a may be 0 mass% or more, more than 0 mass%, 0.1 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, or 4 mass% or more. From these viewpoints, the content of the (meth) acrylate compound a may be 0 to 20 mass%, more than 0 mass% and 20 mass% or less, 0 to 3 mass% or more than 0 mass% and 3 mass% or less.

The content of the (meth) acrylate compound a may be in the following range based on the total amount of the component (B). From the viewpoint of easy residue suppression, the content of the (meth) acrylate compound a may be 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, 6 mass% or less, 5 mass% or less, 3 mass% or less, 1 mass% or less, or 0.1 mass% or less. The content of the (meth) acrylate compound a may be 0 mass% or more, more than 0 mass%, 0.1 mass% or more, 1 mass% or more, 3 mass% or more, 5 mass% or more, 6 mass% or more, 8 mass% or more, or 10 mass% or more. From these viewpoints, the content of the (meth) acrylate compound a may be 0 to 30 mass%, more than 0 mass% and 30 mass% or less, 0 to 8 mass% or more than 0 mass% and 8 mass% or less.

The content of the (meth) acrylate compound a may be within the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (B). From the viewpoint of easy residue suppression, the content of the (meth) acrylate compound a may be 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, or 0.1 part by mass or less. The content of the (meth) acrylate compound a may be 0 part by mass or more, more than 0 part by mass, 0.1 part by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more. From these viewpoints, the content of the (meth) acrylate compound a may be 0 to 20 parts by mass, more than 0 parts by mass and 20 parts by mass or less, 0 to 3 parts by mass or more than 0 parts by mass and 3 parts by mass or less.

The component (B) may contain a compound represented by the following general formula (B1) from the viewpoint of easily suppressing occurrence of defects in the resist, from the viewpoint of easily shortening the minimum development time, and from the viewpoint of easily obtaining good resolution and adhesion. From the viewpoint of easy obtaining of good resolution and adhesion, n in the general formula (b 1) may be 1 to 40, 1 to 30, 1 to 20, 5 to 20, or 10 to 20.

(wherein R is ¹ R is R ² Each independently represents a hydrogen atom or a methyl group, AO represents an oxyalkylene group (oxyethylene group, oxypropylene group, oxybutylene group, etc.), n represents the number of oxyalkylene groups, and represents an integer of 1 to 50. )

The content of the compound represented by the general formula (b 1) may be within the following range based on the total amount of the photosensitive layer or the total amount of the solid content of the photosensitive resin composition, from the viewpoint of easy obtaining of good resolution and adhesion. The content of the compound represented by the general formula (b 1) may be 0 mass% or more, more than 0 mass%, 0.1 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, or 4 mass% or more. The content of the compound represented by the general formula (b 1) may be 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, 5 mass% or less, 4 mass% or less, 3 mass% or less, 2 mass% or less, 1 mass% or less, or 0.1 mass% or less. From these viewpoints, the content of the compound represented by the general formula (b 1) may be 0 to 20% by mass or more than 0% by mass and 20% by mass or less.

The content of the compound represented by the general formula (B1) may be within the following range based on the total amount of the component (B) from the viewpoint of easy obtaining of good resolution and adhesion. The content of the compound represented by the general formula (b 1) may be 0 mass% or more, more than 0 mass%, 0.1 mass% or more, 1 mass% or more, 3 mass% or more, 5 mass% or more, 8 mass% or more, 10 mass% or more, or 11 mass% or more. The content of the compound represented by the general formula (b 1) may be 40 mass% or less, 35 mass% or less, 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, 12 mass% or less, 11 mass% or less, 10 mass% or less, 8 mass% or less, 5 mass% or less, 3 mass% or less, 1 mass% or less, or 0.1 mass% or less. From these viewpoints, the content of the compound represented by the general formula (b 1) may be 0 to 40 mass% or more than 0 mass% and 40 mass% or less.

The content of the compound represented by the general formula (B1) may be within the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (B) from the viewpoint of easy obtaining of good resolution and adhesion. The content of the compound represented by the general formula (b 1) may be 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 13 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, or 0.1 part by mass or less. The content of the compound represented by the general formula (b 1) may be 0 part by mass or more, more than 0 part by mass, 0.1 part by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 12 parts by mass or more, or 13 parts by mass or more. From these viewpoints, the content of the compound represented by the general formula (b 1) may be 0 to 30 parts by mass or more than 0 parts by mass and 30 parts by mass or less.

The component (B) may contain at least one compound X selected from the group consisting of trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate and these alkylene oxide modifications from the viewpoint of easily suppressing occurrence of defects in the resist, of easily shortening the minimum development time, and of easily obtaining good resist stripping characteristics, adhesion, and flexibility. Examples of the alkylene oxide modified products of trimethylolpropane tri (meth) acrylate and tetramethylolmethane tri (meth) acrylate include EO modified products, PO modified products, EO and PO modified products, and the like.

The content of the compound X or the content of the alkylene oxide modified form of trimethylolpropane tri (meth) acrylate may be in the following range based on the total amount of the component (B). The content may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 8 mass% or more, or 10 mass% or more from the viewpoint of easy obtaining of good developability, adhesion, and pattern shape. From the viewpoint of easy obtaining of good resist stripping characteristics, the content may be 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, 5 mass% or less, 3 mass% or less, 1 mass% or less, or 0.1 mass% or less. From these viewpoints, the content of the compound X may be 0 to 30 mass%, more than 0 mass% and 30 mass% or less, 1 to 30 mass%.

(B) The content of the component (c) may be in the following range based on the total amount of the photosensitive layer or the total amount of the solid content of the photosensitive resin composition. The content of the component (B) may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, or 40 mass% or more from the viewpoint of easy obtaining of good sensitivity and resolution. The content of the component (B) may be 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, 50 mass% or less, or 45 mass% or less from the viewpoint of easy obtainment of good film formability and easy suppression of embrittlement of the cured product. From these viewpoints, the content of the component (B) may be 1 to 70 mass%.

(B) The content of the component (a) may be within the following range with respect to 100 parts by mass of the total amount of the component (B). The content of the component (B) may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more from the viewpoint of easy obtaining of good sensitivity and resolution. The content of the component (B) may be 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less from the viewpoint of easy obtainment of good film formability and easy suppression of embrittlement of the cured product. From these viewpoints, the content of the component (B) may be 5 to 70 parts by mass, 30 to 65 parts by mass, 30 to 60 parts by mass, 35 to 60 parts by mass, or 40 to 50 parts by mass.

Examples of the photopolymerization initiator as the component (C) include imidazole compounds, aromatic ketones (excluding compounds corresponding to benzophenone compounds), quinone compounds, benzoin compounds, acridine compounds, N-phenylglycine compounds, benzyl derivatives, and the like. Examples of the imidazole compound include 2,4, 5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer. Examples of the aromatic ketone include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoethyl-1. Examples of the quinone compound include alkylanthraquinone. Examples of the benzoin compound include benzoin, alkylbenzoin, and benzoin ether compound (benzoin alkyl ether, etc.). The acridine compound includes acridine derivatives such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane. Examples of the N-phenylglycine compound include N-phenylglycine and N-phenylglycine derivatives. Examples of the benzyl derivative include benzyl dimethyl ketal and the like. The component (C) may contain an imidazole compound and may contain a 2,4, 5-triarylimidazole dimer from the viewpoint of easy obtaining of good adhesion and sensitivity.

(C) The content of the component (c) may be in the following range based on the total amount of the photosensitive layer or the total amount of the solid content of the photosensitive resin composition. The content of the component (C) may be 0.1 mass% or more, 0.2 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, or 2.5 mass% or more from the viewpoint of easy obtaining of good sensitivity. The content of the component (C) may be 20 mass% or less, 10 mass% or less, 5 mass% or less, or 3 mass% or less from the viewpoint of suppressing an excessive increase in light absorption at the surface of the photosensitive layer at the time of exposure and facilitating sufficient curing of the inside of the photosensitive layer. From these viewpoints, the content of the component (C) may be 0.1 to 20% by mass, 0.2 to 10% by mass, or 0.5 to 5% by mass. The occurrence of defects in the resist can be suppressed by adjusting the content of the component (C).

(C) The content of the component (a) may be within the following range with respect to 100 parts by mass of the total amount of the component (B). The content of the component (C) may be 0.1 part by mass or more, 0.2 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, or 2.5 parts by mass or more from the viewpoint of easy obtaining of good sensitivity. The content of the component (C) may be 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less from the viewpoint of suppressing an excessive increase in light absorption at the surface of the photosensitive layer at the time of exposure and facilitating sufficient curing of the inside of the photosensitive layer. From these viewpoints, the content of the component (C) may be 0.1 to 20 parts by mass, 0.2 to 10 parts by mass, or 0.5 to 5 parts by mass. The occurrence of defects in the resist can be suppressed by adjusting the content of the component (C).

The photosensitive layer and the photosensitive resin composition constituting the photosensitive layer may contain a sensitizer. Examples of the sensitizer include pyrazoline compounds, benzophenone compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, and triarylamine compounds. The sensitizer may contain at least one selected from the group consisting of pyrazoline compounds, benzophenone compounds, anthracene compounds, and coumarin compounds from the viewpoint of easily suppressing occurrence of defects in the resist, of easily shortening the minimum development time, and of easily obtaining good sensitivity, resolution, and adhesion. That is, the sensitizer may be a system including a pyrazoline compound, a system including a benzophenone compound, a system including an anthracene compound, or a system including a coumarin compound.

As the pyrazoline compound, there may be mentioned 1-phenyl-3- (4-isopropylphenyl-vinyl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxystyryl) -pyrazoline, 1-phenyl-3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxystyryl) -pyrazoline, 4- [ [3- (4-chlorophenyl) -4, 5-dihydro-1H-pyrazol ] -1-yl ] benzenesulfonamide, and the like. The sensitizer may contain 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline from the viewpoint of easy obtaining of good resolution and adhesion.

Examples of the benzophenone compound include benzophenone; n, N, N ', N ' -tetraalkyl-4, 4' -diaminobenzophenones such as N, N, N ', N ' -tetramethyl-4, 4' -diaminobenzophenone (alias: michaelis ketone), N, N, N ', N ' -tetraethyl-4, 4' -diaminobenzophenone; and dialkylaminobenzophenones such as 4-methoxy-4' -dimethylaminobenzophenone. The sensitizer may contain N, N '-tetraalkyl-4, 4' -diaminobenzophenone from the viewpoint of easy obtaining of good resolution and adhesion.

Examples of the anthracene compound include 9, 10-dialkoxyanthracene such as 9, 10-dimethoxy anthracene, 9, 10-diethoxy anthracene, 9, 10-dipropoxy anthracene, 9, 10-dibutoxy anthracene, and 9, 10-dipentyloxy anthracene. The sensitizer may contain 9, 10-dialkoxyanthracene from the viewpoint of easy obtaining of good sensitivity.

Examples of the coumarin compound include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-aminocyclopenta [ c ] coumarin, 7-dimethylaminocyclopenta [ c ] coumarin, 7-diethylamino [ c ] coumarin, 4, 6-dimethyl-7-dimethylaminocoumarin, 4, 6-dimethyl-7-ethylamino-coumarin, 4, 6-dimethyl-7-diethylamino-coumarin, 4, 6-diethyl-7-dimethylaminocoumarin, 4, 6-diethyl-7-ethylamino-coumarin, 4, 6-diethyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylamino-coumarin, 3' -carbonylbis (7-diethylamino-coumarin), 2,3,6, 7-tetrahydro-9-methyl-1H, 5H,11H- [1] benzopyran [6, 8-quinolizin, 11-j and the like. From the viewpoint of easy obtaining of good sensitivity, the sensitizer may contain 2,3,6, 7-tetrahydro-9-methyl-1H, 5H,11H- [1] benzopyran [6,7,8-ij ] quinolizin-11-one.

The content of the sensitizer, the content of the pyrazoline compound, the content of the benzophenone compound, the content of the anthracene compound, or the content of the coumarin compound may be in the following range based on the total amount of the photosensitive layer or the total amount of the solid content of the photosensitive resin composition. From the viewpoint of easy obtaining of good sensitivity, resolution and adhesion, the content may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.015 mass% or more, 0.018 mass% or more, 0.019 mass% or more, 0.02 mass% or more, 0.05 mass% or more, more than 0.05 mass%, 0.1 mass% or more, 0.15 mass% or more, 0.18 mass% or more, 0.19 mass% or more, 0.2 mass% or more, 0.25 mass% or more, 0.3 mass% or more, 0.35 mass% or more, 0.4 mass% or more, or 0.45 mass% or more. From the viewpoint of easy obtaining of good sensitivity, resolution and adhesion, the content may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.45 mass% or less, 0.4 mass% or less, 0.35 mass% or less, 0.3 mass% or less, 0.25 mass% or less, 0.2 mass% or less, 0.19 mass% or less, 0.18 mass% or less, 0.15 mass% or less, 0.1 mass% or less, 0.05 mass% or less, less than 0.05 mass%, 0.02 mass% or less, or 0.019 mass% or less. From these viewpoints, the content may be 0.001 to 5% by mass.

The content of the sensitizer, the content of the pyrazoline compound, the content of the benzophenone compound, the content of the anthracene compound, or the content of the coumarin compound may be in the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (B). From the viewpoint of easy obtaining of good sensitivity, resolution and adhesion, the content may be 0.001 part by mass or more, 0.005 part by mass or more, 0.01 part by mass or more, 0.015 part by mass or more, 0.02 part by mass or more, 0.03 part by mass or more, 0.05 part by mass or more, 0.1 part by mass or more, more than 0.1 part by mass, 0.15 part by mass or more, 0.2 part by mass or more, 0.25 part by mass or more, 0.3 part by mass or more, 0.35 part by mass or more, 0.4 part by mass or more, or 0.45 part by mass or more. From the viewpoint of easy obtaining of good sensitivity, resolution and adhesion, the content may be 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.5 parts by mass or less, 0.45 parts by mass or less, 0.4 parts by mass or less, 0.35 parts by mass or less, 0.3 parts by mass or less, 0.25 parts by mass or less, 0.2 parts by mass or less, 0.15 parts by mass or less, 0.1 parts by mass or less, less than 0.1 parts by mass, 0.05 parts by mass or less, 0.03 parts by mass or less, or 0.02 parts by mass or less. From these viewpoints, the content may be 0.001 to 5 parts by mass.

The photosensitive layer and the photosensitive resin composition constituting the photosensitive layer may contain, as components (a), (B), (C) and components other than the sensitizer, a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule (oxetane compound or the like), a cationic polymerization initiator, a dye (malachite green or the like), a photocolor developer (tribromophenyl sulfone, leuco crystal violet or the like), a thermal coloring inhibitor, a plasticizer (p-toluenesulfonamide or the like), a polymerization inhibitor (4-t-butylcatechol or the like), a pigment, a filler, an antifoaming agent, a flame retardant, a stabilizer, an adhesion imparting agent, a leveling agent, a peeling accelerator, an antioxidant (dibutylhydroxytoluene (alias: 2, 6-di-t-butyl-p-cresol or the like), a perfume, a developer, a thermal crosslinking agent or the like, as required. The content of these additives may be 0.01 to 20 parts by mass, respectively, relative to 100 parts by mass of the total amount of the component (a) and the component (B). The photosensitive layer and the photosensitive resin composition constituting the photosensitive layer may contain an antioxidant (dibutylhydroxytoluene) from the viewpoint of easily suppressing occurrence of defects in the resist and from the viewpoint of easily shortening the minimum development time.

The photosensitive resin composition can be prepared by dissolving the constituent components of the photosensitive layer in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent of these solvents, as required, to give a solution having a solid content of about 30 to 60 mass%.

The photosensitive layer can be formed by removing the solvent after coating the photosensitive resin composition on the support film. As the coating method, for example, a known method such as roll coating, corner-cut wheel coating, gravure coating, air knife coating, die coating, bar coating, or the like can be used. The removal of the solvent can be performed by, for example, treating at 70 to 150 ℃ for about 5 to 30 minutes. The amount of the organic solvent remaining in the photosensitive layer may be 2 mass% or less from the viewpoint of easily preventing diffusion of the organic solvent in the subsequent process.

The thickness of the photosensitive layer may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more from the viewpoint of easy obtaining of good resolution and adhesion. The thickness of the photosensitive layer may be 300 μm or less, 200 μm or less, 100 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 25 μm or less from the viewpoint of easy availability of a resist suitable for etching treatment or plating treatment. From these viewpoints, the thickness of the photosensitive layer may be 1 to 300 μm.

The photosensitive element according to the present embodiment may include a protective film on a side opposite to the support film of the photosensitive layer. As the protective film, a film in which the adhesion between the photosensitive layer and the protective film is smaller than the adhesion between the support film and the photosensitive layer can be used. As the protective film, a film with low fish eyes (fish eye) may be used. Examples of the protective film include an inert polyolefin film (polyethylene film, polypropylene film, etc.). The protective film may be a polyethylene film from the viewpoint of easy obtainment of good peeling property from the photosensitive layer. The thickness of the protective film may be about 1 to 100 μm depending on the application.

The photosensitive element according to the present embodiment may further include an intermediate layer or a protective layer such as a buffer layer, an adhesive layer, a light absorbing layer, or a gas barrier layer, in addition to the support film, the photosensitive layer, and the protective film.

The photosensitive element according to the present embodiment may be stored in an original state, or may be stored in a state of being wound around a cylindrical winding core by laminating a protective film on a photosensitive layer. At this time, the support film may be wound into a roll so as to be the outermost layer.

Method for producing cured product and method for producing cured product pattern

The method for producing a cured product according to the present embodiment includes a curing step of curing a photosensitive layer of a photosensitive element to obtain a cured product (photo-cured product). The method for producing a cured product according to the present embodiment may include, as the curing step, an exposure step of irradiating the photosensitive layer with an active light beam through the support film in a state where the photosensitive element is laminated on the substrate to obtain a cured product (photo-cured product). In the curing step, for example, an active light is irradiated to a predetermined portion of the photosensitive layer. In the curing step, the photosensitive element may be laminated on the substrate so that the photosensitive layer is positioned closer to the substrate than the support film.

In the curing step, for example, a photomask having a negative or positive mask pattern is brought into close contact with the support film, and an active light is irradiated onto the photosensitive layer (for example, irradiated in an image) through the support film to obtain a cured product. Examples of the light source of the active light include a light source (such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, and a xenon lamp) that emits ultraviolet light, visible light, and the like. In the curing step, a laser direct writing exposure method may be used.

The method for producing a cured product according to the present embodiment may include a lamination step of laminating the photosensitive element on the substrate before the curing step. In the lamination step, the photosensitive element can be laminated on the substrate so that the photosensitive layer is positioned closer to the substrate than the support film.

Examples of the method of laminating the photosensitive element on the substrate include a method of laminating the photosensitive element by heating to about 70 to 130 ℃ and pressing the photosensitive layer against the substrate under a pressure of about 0.1 to 1 MPa. When the protective film is present on the photosensitive layer, the photosensitive layer may be pressure-bonded to the substrate after the protective film is removed. In the lamination step, the photosensitive elements may be laminated under reduced pressure. From the viewpoint of improving the lamination property, the substrate may be subjected to a preheating treatment. The constituent material of the surface of the laminated photosensitive element in the substrate may be metal or resin material.

The method for producing a cured product pattern (method for forming a resist pattern) according to the present embodiment includes a developing step of removing at least a part of a portion (unexposed portion) of the photosensitive layer other than the cured product after the exposure step in the method for producing a cured product according to the present embodiment, to obtain a cured product pattern (resist pattern).

In the developing process, the photomask is peeled from the support film, and the support film is peeled from the photosensitive layer. In the development step, wet development using a developer (an alkaline aqueous solution, an aqueous developer, an organic solvent, or the like) can be used; the unexposed portion (uncured portion) of the photosensitive layer is removed by dry development or the like, and the cured product pattern is obtained by development.

Examples of the alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate solution, 0.1 to 5% by mass of potassium carbonate solution, and 0.1 to 5% by mass of sodium hydroxide solution. The pH of the aqueous alkaline solution may be 9 to 11. The temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive layer. The aqueous alkaline solution may contain surfactants, defoamers, organic solvents, and the like. Examples of the development method include dipping, spraying, brushing, and beating.

The method for producing a cured product pattern according to the present embodiment may include a step of further curing the cured product pattern by heating and/or exposing the cured product pattern after the developing step, if necessary, from the viewpoint of improving the solder heat resistance, chemical resistance, and the like. The heating may be carried out, for example, at 60 to 250℃or 100 to 170℃for 15 to 90 minutes. The exposure can be performed by irradiating ultraviolet rays by a high-pressure mercury lamp. The exposure amount may be, for example, 0.2 to 10J/cm ² . The heating and the exposure (for example, ultraviolet irradiation) may be performed simultaneously, or one of the heating and the exposure may be performed after the other. When the heating and the exposure are performed simultaneously, the heating can be performed at 60 to 150 ℃ from the viewpoint of effectively imparting heat resistance, chemical resistance, and the like to the solder.

With the method for producing a cured product pattern according to the present embodiment, a cured product pattern (resist pattern) can be formed on a patterned conductor layer (wiring). The cured product pattern can be used as a solder resist for preventing solder from adhering to an unnecessary portion of the conductor layer when the mounting member is bonded. The cured product pattern obtained by the method for producing a cured product pattern according to the present embodiment can be used as a protective film for a conductor layer after soldering, and is excellent in physical properties (tensile strength, elongation, etc.) and thermal shock resistance, and therefore is effective as a permanent mask for semiconductor packaging. The semiconductor device and the like can be mounted (wire bonded, solder bonded, or the like) on a package substrate having such a cured pattern (resist pattern), and then mounted on an electronic device (personal computer or the like).

The cured product pattern obtained by the method for producing a cured product pattern according to the present embodiment can be used for forming a cured resin that has excellent physical properties (tensile strength, elongation, etc.) and satisfies corrosion resistance on a rigid substrate, and can also be used as a solder resist (permanent mask) formed on a rigid substrate. Specifically, the solder resist composition can be used as a solder resist for a printed wiring board having a rigid substrate, a solder resist for a package substrate having a rigid substrate, or the like.

Method for manufacturing circuit board

The method for manufacturing a wiring board (for example, a printed wiring board) according to the present embodiment includes a step of performing an etching process or a plating process on a laminate having a cured product pattern obtained by the method for manufacturing a cured product pattern according to the present embodiment on a substrate. In this case, the laminate can be subjected to etching treatment or plating treatment by a known method using the cured product pattern as a mask. The circuit board may be a multilayer printed circuit board or may have small-diameter through holes.

Examples of the etching liquid used for the etching treatment include a copper chloride solution, an iron chloride solution, and an alkali etching solution. Examples of the plating treatment include copper plating, solder plating, nickel plating, and gold plating.

After the etching treatment or the plating treatment is performed, for example, the cured product pattern can be peeled off with an aqueous alkali solution stronger than the aqueous alkali solution used for development. Examples of the strongly alkaline aqueous solution include 1 to 10 mass% aqueous sodium hydroxide solution and 1 to 10 mass% aqueous potassium hydroxide solution. Examples of the method for peeling off the cured product pattern include an immersion method and a spray method.

When a substrate having an insulating layer and a conductor layer disposed on the insulating layer is subjected to a plating process, the conductor layer other than the pattern portion can be removed. As a method for removing the conductor layer, a method of slightly etching after peeling off the cured product pattern; after the plating process is continued, the cured product pattern is peeled off after the solder plating or the like, so that the line portion is masked with the solder, and then, a method of performing a process using an etching solution capable of etching only the conductor layer is used.

Examples

Hereinafter, the present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited to the examples.

< preparation of adhesive Polymer >

Solution a (mass ratio of monomers=methacrylic acid/methyl methacrylate/styrene/benzyl methacrylate=27/5/45/23) was obtained by mixing 162g of methacrylic acid, 30g of methyl methacrylate, 270g of styrene, 138g of benzyl methacrylate and 5.4g of azobisisobutyronitrile.

420g of a mixture b of toluene and methyl cellosolve (mass ratio=6:4 (toluene: methyl cellosolve)) was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas inlet tube. Then, nitrogen was blown in and stirring was performed, and the mixture b was heated to 80 ℃. Next, the solution a was added dropwise to the mixture b over 4 hours using a dropping funnel. Then, after 40g of a mixture of toluene and methyl cellosolve (mass ratio=6:4) was used as a cleaning liquid to clean the inside of the dropping funnel, the cleaning liquid was added to the flask to obtain a mixture c.

Subsequently, stirring was carried out and the mixture c was incubated at 80℃for 2 hours. Next, a solution d obtained by dissolving 1.0g of azobisisobutyronitrile in 40g of a mixture of methyl cellosolve and toluene (mass ratio=6:4) was added dropwise to the flask over 30 minutes using a dropping funnel. Next, 120g of a mixture of toluene and methyl cellosolve (mass ratio=6:4) was used as a cleaning liquid, and then the cleaning liquid was added to a flask to obtain a mixture e.

Subsequently, stirring was carried out and the mixture e was incubated at 80℃for 3 hours. Then, the mixture was heated to 90℃over 30 minutes. After 2 hours of incubation at 90 ℃, cooling was performed, thereby obtaining an adhesive polymer solution. Toluene was added to the binder polymer solution to adjust the nonvolatile content concentration (solid content concentration) to 40 mass%.

The weight average molecular weight of the binder polymer was 45000. The weight average molecular weight was calculated by measurement by Gel Permeation Chromatography (GPC) under the following conditions and conversion using a calibration curve of standard polystyrene.

And (3) a pump: type L-2130 (Hitachi High-Tech Corporation)

A detector: l-2490 RI (Hitachi High-Tech Corporation)

Tubular column oven: L-2350[Hitachi High-Tech Corporation ]

And (3) pipe column: gelpack GL-R440+Gelpack GL-R450+Gelpack GL-R400M (3 pieces by weight) [ Showa Denko Materials Co., ltd., product name ]

Column size: 10.7 mmI.DX100 mm

Eluent: tetrahydrofuran (THF)

Sample concentration: 10mg/2mL

Injection amount: 200 mu L

Flow rate: 2.05 mL/min

Measuring temperature: 25 DEG C

The acid value of the binder polymer was 107mgKOH/g. The acid value was measured by the following procedure. First, the binder polymer was weighed in an Erlenmeyer flask. Next, a mixed solvent (mass ratio: toluene/methanol=70/30) was added and the binder polymer was dissolved, and then a phenolphthalein solution was added as an indicator. Then, titration was performed using 0.1mol/L (N/10) potassium hydroxide solution (ethanol solution) to obtain an acid value.

Preparation of photosensitive resin composition

The photosensitive resin composition was obtained by mixing 145 parts by mass (solid content: 58 parts by mass) of the above-mentioned binder polymer solution, a photopolymerizable compound, a photopolymerization initiator, a sensitizer, TBC (4-t-butylcatechol) or BHT (dibutylhydroxytoluene), 0.5 part by mass of leuco crystal violet, 0.03 part by mass of malachite green, 5 parts by mass of methanol, 9 parts by mass of acetone, and 5 parts by mass of toluene. Table 1 shows the photopolymerizable compounds, photopolymerization initiators, sensitizers, TBCs, and BHTs used in examples and comparative examples. The values in Table 1 show the contents (unit: parts by mass) of the respective components. The following components were used as the photopolymerizable compound, photopolymerization initiator and sensitizer.

(photopolymerizable Compound)

FA-321M: EO-modified bisphenol A dimethacrylate, EO10mol, showa Denko Materials Co., ltd., product name

BPE-200: EO-modified bisphenol A dimethacrylate, EO4.0mol, SHIN-NAKAMURA CHEMICAL CO, LTD. Product name

BPE-100: EO-modified bisphenol A dimethacrylate, EO2.6mol, SHIN-NAKAMURA CHEMICAL CO, LTD. Product name

DPEA-12: dipentaerythritol EO-modified acrylate, nippon Kayaku Co., ltd., product name

FA-024M: EO-PO modified dimethacrylate, showa Denko Materials Co., ltd., product name

TMPT-21: trimethylolpropane EO-modified triacrylate, EO21mol, showa Denko Materials Co., ltd., product name

(photopolymerization initiator)

BCIM:2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, HODOGAYA CHEMICA L CO., LTD, product name

(sensitizer)

PZ-501D: 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline

EAB: n, N, N ', N ' -tetraethyl-4, 4' -diaminobenzophenone

DBA:9, 10-dibutoxyanthracene

Coumarin 102:2,3,6, 7-tetrahydro-9-methyl-1H, 5H,11H- [1] benzopyran [6,7,8-ij ] quinolizin-11-one, tokyo Chemical Industry Co., ltd., product name

TABLE 1

Preparation of support film

The following PET film was prepared as a support film.

Films A1 to A7: a biaxially oriented film having a 3-layer structure comprising a lubricant layer containing particles on the front and back surfaces of a PET film. The time of the filtration treatment performed on the composition for film formation (the same composition for film formation as the PET film of FB40 manufactured by Toray Industries, inc.) before the film formation of the PET film was adjusted. The filtration time of the membranes A1 to A3 is 24 hours or more, the filtration time of the membranes A4 to A6 is 12 to 18 hours, and the filtration time of the membrane A7 is 6 hours or less.

Film B: a biaxially oriented film having a 2-layer structure comprising a lubricant layer containing particles on one side of a PET film. Mitsubishi Chemical Corporation, product name: R-705G

Film C: particle-containing biaxially oriented PET film having a monolayer structure, manufactured by Teijin DuPont Films Limited, product name: G2G 2

The photosensitive resin composition was applied to the support film (PET film) so that the thickness was uniform, and then dried by a hot air convection dryer at 100 ℃ for 2 minutes to remove the solvent, whereby a laminate for evaluation having a photosensitive layer (thickness: 25 μm) on the support film was obtained. When the film B is used as a support film, a photosensitive layer is formed on the surface opposite to the lubricant layer. Select 0.225mm of the support film of the laminate for evaluation at 10 ² The number of defects (light-shielding material) having a maximum diameter of 1 μm or more in each region was measured in the region (0.150 mm. Times.0.150 mm). In order to evaluate defects contained in the inside of the support film, a region (inner layer portion) between a surface layer portion from one surface of the support film to a depth of 0.5 μm and a surface layer portion from the other surface of the support film to a depth of 0.5 μm was evaluated. Using a confocal microscope (manufactured by Lasertec Corporation, product name: HYBRID laser microscope) and obtaining an image under the conditions of a lens aperture number (Na) of 0.8, a magnification of 50 times, a digital zoom of 2 times, and table 2 below, the size and number of defects were measured from pixels in the image. For the measurement conditions to be adjusted each time, conditions for easily identifying defects are suitably used. Focusing is performed sequentially from one surface to the other surface, and the whole of the inner layer portion is observed. The number of measurements (n number) was 5 times (total 50 areas), and an average value of the number of defects was obtained. The measurement results are shown in tables 3 to 6.

TABLE 2

The result (magnification: 600 times) of observing the surface of the support film (film A1) of example 1 using a confocal microscope (manufactured by Lasertec Corporation, product name: HYBRID laser microscope) is shown in FIG. 2 (a), and the result (magnification: 600 times) of observing the surface of the support film (film C) of comparative example 1 is shown in FIG. 2 (b). The scales in the images of fig. 2 (a) and 2 (b) are the same as each other. An image of the support film of example 1 observed by the above-described confocal microscope is shown in fig. 3 (a), and an image of the support film of comparative example 1 is shown in fig. 3 (b). The scales in the images of fig. 3 (a) and 3 (b) are the same as each other.

The light transmittance (wavelength: 380 to 780 nm) and haze value of the support film were measured using a haze meter (NIPPON DENSHOKU INDUSTRIES Co., ltd., product name: NDH-5000). The thickness (total thickness) of the support film was measured using MH-15M (product name) manufactured by Nikon Corporation. The results are shown in tables 3 to 6.

< production of photosensitive element >)

The photosensitive resin composition was applied to the support film (PET film, support films of tables 3 to 6) so that the thickness became uniform, and then dried with a hot air convection dryer at 100 ℃ for 2 minutes to remove the solvent, thereby forming a photosensitive layer (thickness: 25 μm). When the film B is used as a support film, a photosensitive layer is formed on the surface opposite to the lubricant layer. Thereafter, the photosensitive layer was covered with a protective film (TAMAPOLY CO., LTD., product name: NF-15, thickness: 18 μm) made of polyethylene, thereby obtaining a photosensitive element.

< evaluation >

(production of laminate)

The substrate a was obtained by forming a copper layer (electroless copper, thickness: 500 nm) by electroless plating on both sides of an interlayer insulating material (Ajinomoto Fine-Techno co., inc. Manufactured by inc. Under the product name: GX-T31), and then subjecting the surface of the copper layer to acid washing, water washing and drying (air flow). After the substrate a was heated to 80 ℃, the protective film of the photosensitive element was peeled off and the photosensitive element was laminated so that the photosensitive layer and the copper layer were in contact. Thus, a laminate having the substrate a, the photosensitive layer, and the support film in this order in the lamination direction was obtained. Lamination was performed using a 110℃heated roll and with a crimping pressure of 0.4MPa and a roll speed of 1.5 m/min.

(minimum development time)

After peeling the support film, the photosensitive layer was subjected to spray development using a 1 mass% sodium carbonate aqueous solution at 30 ℃, and the time for completely removing the unexposed portion was obtained as the minimum development time. The measurement results are shown in tables 3 to 6.

(light sensitivity)

A 41-stage step table was placed as a negative film on the support film of the laminate. Then, using a high-resolution projection exposure machine (manufactured by USHIO INC. Under the product name: UX-2240) having a high-pressure mercury lamp, the irradiation amount was adjusted to obtain irradiation energy at which the number of curing stages of the developed resist became 11, and the photosensitive layer was exposed.

Next, after peeling the support film, the photosensitive layer was subjected to spray development using a 1 mass% sodium carbonate aqueous solution at 30 ℃ for 2 times the minimum development time, removing the unexposed portions. Then, it was confirmed that the number of steps of the step surface of the photocurable film formed on the substrate was 11, and the irradiation energy (exposure amount, mJ/cm) during the exposure was obtained ² ). The results are shown in tables 3 to 6.

(adhesion and resolution)

In order to examine the adhesion and resolution, a photo tool (photo tool) having a 41-step table, a glass chrome type tool having a line pattern with a line width/space width of 2/6 to 20/90 (unit: μm) as a negative film for adhesion evaluation, a glass chrome type tool having a line pattern with a line width/space width of 2/2 to 20/20 (unit: μm) as a negative film for resolution evaluation, and a high-resolution projection exposure machine (USHIO inc. Manufactured by UX-2240) having a high-pressure mercury lamp were used, and exposure of the photosensitive layer of the laminate was performed with irradiation energy at 11 steps of the number of steps remaining after development of the 41-step table. Then, the support film was peeled off, and a 1 mass% aqueous sodium carbonate solution was subjected to spray development at 30 ℃ for 2 times the minimum development time, to remove the unexposed portion. Here, the adhesion was evaluated based on the minimum value (unit: μm) of the line width that can be formed neatly by the development treatment. The resolution was evaluated from the minimum value (unit: μm) of the space width between the line portions where the unexposed portions can be removed neatly by the development process. The results are shown in tables 3 to 6. The smaller the number of the evaluation of the adhesion and resolution, the better.

(number of defects of resist)

The number of defects (defects of 0.5 μm or more) as shown in fig. 4 was evaluated using a scanning electron microscope (Hitachi, ltd. Manufactured by ltd. Product name: SU-1500), and resist lines (L/s=10/10 μm) of the laminate used in the above-described evaluation of the resolution at 10 were randomly observed (magnification: 500 times). The average value of the number of defects was converted to 0.225mm each ² The conversion values of the number of (a) are shown in tables 3 to 6.

(residue)

The photosensitive layer of the laminate was exposed in the same manner as in the evaluation of the above-described photosensitivity. Next, after peeling the support film, the photosensitive layer was subjected to spray development using a 1 mass% sodium carbonate aqueous solution at 30 ℃ for 2 times and 6 times the minimum development time, removing the unexposed portions. Then, the surface of each of the substrate b1 after 2 times of the minimum development time and the substrate b2 after 6 times of the minimum development time was visually observed, and the area of the color change portion was calculated. The ratio of the area of the substrate b1 to the area of the substrate b2 (= [ b1/b2] ×100) was calculated. A case where the ratio was less than 10% was evaluated as "A", and a case where the ratio was 10% or more was evaluated as "B". The results are shown in tables 3 to 6.

TABLE 3

TABLE 4

TABLE 5

TABLE 6

As shown in tables 3 to 6, when the high-resolution projection exposure machine was used, the number of defects of the resist was 100 or less in the examples, and a very large number of defects of the resist was confirmed in the comparative examples. In example 1, although the number of defects in the support film was 0, it was assumed that defects in the resist were generated due to external factors that were difficult to avoid in the evaluation step.

As a result of confirming the number of particles in the surface layer portions (surface layer portions other than the above-mentioned evaluation of the defect number) of the films A1 to A7, the number of particles (lubricant, agglomerate thereof, etc.) having a maximum diameter of 1 μm or more and less than 2 μm was 0.225mm per ² 10000 or more particles (lubricant, agglomerate thereof, etc.) having a maximum diameter of 2 μm or more and less than 5 μm are present in an amount of 0.225mm ² More than 100. Thus, it was confirmed that particles in the surface layer portion did not greatly contribute to the defect of the resist.

Symbol description

1-photosensitive element, 10-support film, 10 a-1 st main surface, 10 b-2 nd main surface, 20-photosensitive layer.

Claims

1. A photosensitive element includes a support film and a photosensitive layer disposed on the support film,

the number of defects of 1 μm or more in maximum diameter in the inside of the support film is 0.225mm each ² Is less than or equal to 100 of the total number,

the photosensitive layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.

2. The photosensitive element according to claim 1, wherein,

the number of defects of 1 μm or more in maximum diameter in the inside of the support film is 0.225mm each ² Less than 5.

3. The photosensitive element according to claim 1 or 2, wherein,

the support film has a polyester film and a lubricant layer disposed on at least one surface of the polyester film.

4. The photosensitive element according to any one of claim 1 to 3, wherein,

the haze value of the support film is 0.01 to 3.0%.

5. The photosensitive element according to any one of claims 1 to 4, wherein,

the photosensitive layer is free of a (meth) acrylate compound having a skeleton derived from dipentaerythritol.

6. The photosensitive element according to any one of claims 1 to 4, wherein,

the photopolymerizable compound includes a (meth) acrylate compound having a dipentaerythritol-derived skeleton, and the content of the (meth) acrylate compound is greater than 0 parts by mass and 3 parts by mass or less relative to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

7. The photosensitive element according to claim 6, wherein,

the photopolymerizable compound further comprises a bisphenol a type di (meth) acrylate compound.

8. The photosensitive element of claim 7, wherein,

the content of the bisphenol A type di (meth) acrylate compound is 30 to 50 parts by mass relative to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

9. The photosensitive element according to any one of claims 1 to 8, further comprising a sensitizer.

10. The photosensitive element according to claim 9, wherein,

the sensitizer comprises a pyrazoline compound.

11. The photosensitive element according to claim 9 or 10, wherein,

the sensitizer comprises N, N '-tetraalkyl-4, 4' -diaminobenzophenone.

12. The photosensitive element according to any one of claims 9 to 11, wherein,

the sensitizer comprises 9, 10-dialkoxyanthracene.

13. The photosensitive element according to any one of claims 9 to 12, wherein,

the sensitizer comprises a coumarin compound.

14. The photosensitive element according to any one of claims 9 to 13, wherein,

the sensitizer is contained in an amount of less than 0.1 parts by mass per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

15. A method for producing a cured product, comprising:

an exposure step of irradiating the photosensitive layer with active light through the support film in a state in which the photosensitive element according to any one of claims 1 to 14 is laminated on a substrate, to obtain a cured product.

16. A method for producing a cured product pattern, comprising:

the method of producing a cured product according to claim 15, wherein at least a part of the photosensitive layer other than the cured product is removed after the exposure step.

17. A method for manufacturing a circuit board includes:

a step of performing etching treatment or plating treatment on a laminate having a cured product pattern obtained by the method for producing a cured product pattern according to claim 16 on the substrate.