WO2022102675A1

WO2022102675A1 - Photosensitive element, method for producing cured product, method for producing cured product pattern, and method for producing wiring board

Info

Publication number: WO2022102675A1
Application number: PCT/JP2021/041406
Authority: WO
Inventors: 壮和粂; 剛黒澤; 陽介賀口; 健一岩下; 真生成田; 哲也加藤
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2020-11-13
Filing date: 2021-11-10
Publication date: 2022-05-19
Also published as: KR20230107474A; JPWO2022102675A1; TW202225837A; CN116830037A; WO2022102101A1

Abstract

A photosensitive element 1 which is provided with a support film 10 and a photosensitive layer 20 that is arranged on the support film 10, wherein: the number of defects within the support film 10, said defects having a maximum diameter of 1 μm or more, is 100 or less per 0.225 mm2; and the photosensitive layer 20 contains a binder polymer, a photopolymerizable compound that has an ethylenically unsaturated bond, and a photopolymerization initiator.

Description

Photosensitive element, method for manufacturing a cured product, method for manufacturing a cured product pattern, and method for manufacturing a wiring board.

This disclosure relates to a photosensitive element, a method for manufacturing a cured product, a method for manufacturing a cured product pattern, a method for manufacturing a wiring board, and the like.

Conventionally, as a resist material used for etching, plating, etc. in the field of manufacturing a wiring board (for example, a printed wiring board), the field of precision processing of a metal, etc., a layer made of a support film and a photosensitive resin composition (hereinafter, "photosensitive layer"). ") And a photosensitive element composed of a protective film is widely used.

The wiring board is manufactured as follows, for example. First, the protective film of the photosensitive element is peeled off from the photosensitive layer, and then the photosensitive layer is laminated on the substrate. Next, after pattern exposure is applied to the photosensitive layer, the unexposed portion is removed with a developing solution to form a resist (resist pattern). Then, a wiring board is formed by performing an etching treatment or a plating treatment via this resist.

As the support film used for the photosensitive element, a support film having a specific haze value, a support film having a specific lubricant particle size, and the like are known (see, for example,

Patent Documents

1 and 2 below).

Japanese Unexamined Patent Publication No. 2001-13681 Japanese Unexamined Patent Publication No. 2014-74764

When manufacturing a wiring board or the like, it is required to suppress the occurrence of resist defects (for example, defects such as resist chips). When such a resist defect occurs, an open defect during etching or a short defect during plating is likely to occur, and the manufacturing yield of wiring boards and the like tends to decrease. On the other hand, it is required to further suppress the occurrence of resist defect by increasing the resolution as the wiring becomes finer.

One aspect of the present disclosure is to provide a photosensitive element capable of suppressing the occurrence of resist defects. Another aspect of the present disclosure is to provide a method for producing a cured product, a method for producing a cured product pattern, and a method for producing a wiring board using such a photosensitive element.

According to the above-mentioned Patent Document 2, particles having a diameter of 5 μm or more and agglomerates having a diameter of 5 μm or more contained in the support film cause resist defect. On the other hand, the present inventor has found that small defects such as a maximum diameter of 1 μm increase the number of resist defects as defects contained inside the support film, and then reduce the number of defects having a maximum diameter of 1 μm or more. By doing so, it was found that the occurrence of resist deficiency can be suppressed.

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

According to the photosensitive element according to one aspect of the present disclosure, the occurrence of resist defect can be suppressed.

Another aspect of the present disclosure comprises an exposure step of irradiating the photosensitive layer with an active ray through the support film in a state where the above-mentioned photosensitive element is laminated on a substrate to obtain a cured product. Regarding the manufacturing method of things.

Another aspect of the present disclosure is a method for producing a cured product pattern, comprising a step of removing at least a part of a portion other than the cured product in the photosensitive layer after the exposure step in the above-mentioned method for producing a cured product. Regarding.

Another aspect of the present disclosure is the manufacture of a wiring board comprising a step of etching or plating a laminate provided on the substrate with the cured product pattern obtained by the above-mentioned method for producing a cured product pattern. Regarding the method.

According to one aspect of the present disclosure, it is possible to provide a photosensitive element capable of suppressing the occurrence of resist defect. Further, according to another aspect of the present disclosure, it is possible to provide a method for producing a cured product, a method for producing a cured product pattern, and a method for producing a wiring board using such a photosensitive element.

It is a schematic cross-sectional view which shows an example of a photosensitive element. It is a figure which shows the observation result of the surface of a support film. It is a figure about the evaluation of the defect in the support film. It is a figure regarding the evaluation of the defect of the resist.

Hereinafter, the mode for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments.

In the present specification, the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. "A or more" in the numerical range means A and a range exceeding A. "A or less" in the numerical range means A and a range less than A. Within the numerical range described stepwise herein, the upper or lower limit of the numerical range at one stage may be optionally combined with the upper or lower limit of the numerical range at another stage. In the numerical range 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. "A or B" may include either A or B, and may include both. Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. The terms "layer" and "film" include not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view. The term "process" is included in this term not only in an independent process but also in the case where the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. By "(meth) acrylate" is meant at least one of the acrylate and the corresponding methacrylate. The same applies to other similar expressions such as "(meth) acrylic acid". "EO" indicates ethylene oxide, and the "EO-modified" compound means a compound having an oxyethylene group. "PO" indicates propylene oxide, and the "PO-modified" compound means a compound having an oxypropylene group.

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

According to the photosensitive element according to the present embodiment, it is possible to suppress the occurrence of resist defect after exposure and development of the photosensitive layer, and even when a high-resolution exposure machine is used, the resist defect is not present. The occurrence can be suppressed. According to the photosensitive element according to the present embodiment, it is possible to suppress the occurrence of resist defects while obtaining good resolution and adhesion (developer resistance). According to one aspect of the photosensitive element according to the present embodiment, as will be described later, it is possible to shorten the minimum development time, reduce the exposure amount (improve the sensitivity), suppress the residue, and the like.

Defects inside the support film can cause resist defects after development by causing light scattering when the photosensitive layer is exposed through the support film. In particular, when a high-resolution exposure machine is used, the influence of light scattering is large, and resist defects are likely to occur after development. When such a resist defect occurs, an open defect during etching or a short defect during plating is likely to occur, and the manufacturing yield of the wiring board tends to decrease. It is conceivable to use a support film having a haze value of 0.01 to 3.0% for the purpose of suppressing the occurrence of resist deficiency, but it is not sufficient to suppress the occurrence of resist deficiency. On the other hand, according to the knowledge of the present inventor, small defects such as a maximum diameter of 1 μm increase the number of resist defects. Therefore, reducing the number of defects having a maximum diameter of 1 μm or more causes resist defects. Can be suppressed.

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 first main surface 10a of the support film 10. The support film 10 has a second main surface 10b on the side opposite to the first main surface 10a.

The number of defects with a maximum diameter of 1 μm or more inside the support film is 80 or less, 50 or less, 30 or less, 20 or less, 18 per 0.225 mm ² from the viewpoint of easily suppressing the occurrence of resist defects. It may be 10 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 zero. The number of defects can be reduced by selectively removing components that can generate defects. For example, the number of defects can be reduced by filtering the film-forming composition of the support film before film formation. The number of defects inside the support film is the number of defects per 0.225 mm ² (0.150 mm × 0.150 mm). The number of defects is the average of multiple measurements. For example, the average value can be obtained as the average value of the measured values of a total of 50 regions obtained by performing the operation of measuring the number of defects in any 10 regions on the support film five times. The unit area of 0.225 mm ² with respect to the number of defects is the area in the plane parallel to the main plane of the support film.

It is presumed that the defect inside the support film is, for example, a light blocking substance and may be caused by a component having a refractive index different from the refractive index of the constituent material which is the main component of the support film. Factors that form the light blocker include polymer gels; raw material monomers; catalysts used during production; inorganic particles (such as lubricants), organic particles, or aggregates of particles used in the production of support films. Things can be mentioned. Examples of the inorganic component of the inorganic particles include simple substances such as calcium, magnesium, and silica; and compounds containing at least one of these. The light blocker blocks the active light beam at the time of exposure without transmitting it.

According to the knowledge of the present inventor, the number of defects inside the support film has a great influence on the occurrence of resist defects. The number of defects inside the support film is the number of defects inside the support film (for example, the number of light blocking objects) measured using a confocal microscope (confocal microscope). Depending on whether or not the photosensitive layer is formed, the conditions under which the inside of the support film can be suitably observed may be adjusted. When the support film has a layer containing particles (such as a lubricant layer) on the surface layer portion, the inner layer portion of the support film is evaluated excluding the surface layer portion in order to evaluate the number of defects inside the support film. For example, when the lubricant layer is formed on the surface layer portions on both sides, the region (inner layer portion) between the portion having a depth of 0.5 μm from one surface and the portion having a depth of 0.5 μm from the other surface can be measured. .. That is, the number of defects inside the support film is the number of defects inside the support film excluding the lubricant layer when the support film has a lubricant layer on the surface. According to the findings of the present inventor, there is a possibility that a defect may occur inside the support film due to the influence of providing the lubricant layer on the surface layer portion.

As the confocal microscope, a hybrid laser microscope OPTELICS HYBRID (Lasertec Co., Ltd., trade name) or the like can be used. Observation with a confocal microscope is a measurement method for detecting reflected light from an object to be observed by a light receiving unit. When the object to be observed is in focus (when it is in focus), the reflected light is strongly obtained, and the intensity of the light is strongly observed (often observed in white). When the object to be observed is out of focus (out of focus), the light intensity is weak (often observed in black).

The numerical aperture (Na) of the objective lens used for observation may be 0.8 from the viewpoint of accurate and efficient observation. When the numerical aperture is 0.8, it is easier to prevent the lens from coming into contact with the observation object and the microscope from being soiled as compared with the case where the numerical aperture exceeds 0.8, and the magnification is excessively high. Therefore, it is easy to suppress the decrease in the amount of light in the visual field and the decrease in the detection level. Further, when the numerical aperture (Na) is 0.8, the decrease in resolution is suppressed and an error is less likely to occur in the size detection of the observation object as compared with the case where the numerical aperture is less than 0.8. Therefore, it is easy to measure with high accuracy.

When observing with 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 amount of light in the visual field is suppressed and the decrease in the detection level is more likely to be suppressed, and the measurement magnification is less than 50 times, as compared with the case where the measurement magnification exceeds 50 times. It is easier to measure the size of the defect more accurately than in the case of. When the digital zoom is 2 times, the decrease in the amount of light in the field of view is suppressed and the decrease in the detection level is likely to be suppressed as compared with the case where the digital zoom is the same magnification (no setting).

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 have a polyester film or a PET film from the viewpoint of easily suppressing the occurrence of resist defects. The support film is a light-transmitting film and may be a transparent resin film.

The support film may be a single layer or a multilayer. The support film may have a lubricant layer disposed on at least one surface of an inner layer portion (eg, a film of the above-mentioned 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 surface of the polyester film. The lubricant layer can be formed by using a known method such as a roll coater, a flow coater, a spray coater, a curtain flow coater, a dip coater, and a slit die coater.

The haze value of the support film is 0.01% or more, 0.05 from the viewpoint of easily improving the operability when laminating the photosensitive element on the substrate, the operability when forming the photosensitive layer on the support film, and the like. % Or more, 0.1% or more, 0.3% or more, 0.5% or more, or 0.7% or more. 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 easily obtaining good sensitivity and resolution. From these viewpoints, the haze value of the support film is 0.01 to 3.0%, 0.01 to 1.5%, 0.01 to 0.8%, or 0.01 to 0.7%. It may be there. "Haze value" means cloudiness. For the haze value of the support film, a commercially available turbidity meter (turbidity meter, for example, trade name "NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.) is used in accordance with the method specified in JIS K7105. Can be measured.

The light transmittance of the support film (for example, the light transmittance in the entire range of wavelengths of 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 cloudiness meter (for example, trade name "NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.).

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 not easily torn 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 ensuring the focal margin at the time of exposure. From these viewpoints, the thickness may be 5 to 200 μm, 11 to 100 μm, 12 to 50 μm, or 15 to 40 μm.

The photosensitive layer is a layer made of a photosensitive resin composition. The photosensitive layer and the photosensitive resin composition constituting the photosensitive layer are composed of (A) a binder polymer ((A) component), (B) a photopolymerizable compound having an ethylenically unsaturated bond ((B) component), and the like. It also contains (C) a photopolymerization initiator (component (C)). 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 may have negative photosensitive properties.

Examples of the constituent material of the binder polymer as the component (A) include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, and phenol resin. The component (A) may contain an acrylic resin from the viewpoint of easily obtaining good alkaline developability. As the component (A), a binder polymer used in a conventional photosensitive resin composition can be used.

The component (A) 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) acrylate ((meth) methyl acrylate, etc.), benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and (meth) acrylic. Examples thereof include glycidyl acid acid, styrene compounds (styrene and styrene derivatives (vinyltoluene, α-methylstyrene, etc.)), and maleic acid. A substituent 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 easily obtaining 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. The component (A) may have a polymerizable monomer having a carboxyl group as a monomer unit and (meth) acrylic acid as a monomer unit from the viewpoint of easily obtaining good alkaline developability. It's okay.

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 is good resist peeling. From the viewpoint of characteristics (easiness of peeling of the cured product of the photosensitive layer from the substrate) and developability, the range may be as follows based on the total amount of the monomer units constituting the component (A). The content of the monomer unit of (meth) acrylic acid may be 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more. The content of the monomer unit of (meth) acrylic acid may be 40% by mass or less, 35% by mass or less, or 30% by mass or less. From these viewpoints, the content of the monomer unit of (meth) acrylic acid may be 10 to 40% by mass, 15 to 35% by mass, 20 to 35% by mass, or 20 to 30% by mass.

The component (A) may have an alkyl (meth) acrylate as a monomer unit (a structural unit derived from an alkyl (meth) acrylate) from the viewpoint of easily obtaining good alkali developability and resist peeling properties. , (Meta) acrylic acid and (meth) alkyl acrylate may be contained as a monomer unit. The alkyl (meth) acrylate may contain methyl (meth) acrylate from the viewpoint of easily obtaining good alkali developability and resist peeling properties.

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

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

The component (A) may have a styrene compound as a monomer unit (structural unit derived from the styrene compound) from the viewpoint of easily obtaining good resolution and adhesion. In this case, the content of the monomer unit 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 is 10% by mass or more, 20% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass from the viewpoint of easily obtaining good resolution. It may be% or more. The content of the monomer unit of the styrene compound may be 60% by mass or less, 50% by mass or less, or 45% by mass or less from the viewpoint of easily obtaining good resist peeling characteristics. From these viewpoints, the content of the monomer unit of the styrene compound is 10 to 60% by mass, 10 to 50% by mass, 20 to 45% by mass, 30 to 45% by mass, or 40 to 45% by mass. It's okay.

The weight average molecular weight (Mw) of the component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, 35,000 or more, 40,000 or more, or 45,000 or more from the viewpoint of easily obtaining good adhesion. The weight average molecular weight of the component (A) may be 80,000 or less, 50,000 or less, or 45,000 or less from the viewpoint of easily obtaining good developability. From these viewpoints, the weight average molecular weight of the component (A) may be 10,000 to 80,000, 20,000 to 50,000, or 25,000 to 45,000.

The dispersity (Mw / Mn) of the component (A) 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 easily obtaining good adhesion and resolution.

The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) can be obtained, for example, by measuring by gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. More specifically, it can be measured by the method described in Examples. When it is difficult to measure a compound having a low molecular weight by such a measuring method, the molecular weight can be measured by another method and the average value can be calculated.

The acid value of the component (A) is 60 mgKOH / g or more, 65 mgKOH / g or more, 70 mgKOH / g or more, 75 mgKOH / g or more, 80 mgKOH / g or more, 85 mgKOH / g or more, 90 mgKOH from the viewpoint of easily obtaining good developability. It may be / g or more, 95 mgKOH / g or more, 100 mgKOH / g or more, or 105 mgKOH / g or more. The acid value of the component (A) is 250 mgKOH / g or less, 240 mgKOH / g or less, 230 mgKOH / g or less, 200 mgKOH / g or less, 150 mgKOH / g or less, or 120 mgKOH / g or less from the viewpoint of easily obtaining good adhesion. May be. From these viewpoints, it may be 60 to 250 mgKOH / g, 65 to 250 mgKOH / g, 70 to 240 mgKOH / g, or 75 to 230 mgKOH / g. 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).

The content of the component (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. The content of the component (A) is 20% by mass or more, 25% by mass or more, 30% by mass or more, from the viewpoint that good formability of the film can be easily obtained and that the cured product is easily suppressed from becoming brittle. It may be 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, or 55% by mass or more. The content of the component (A) is 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, from the viewpoint of easily obtaining good sensitivity and resolution. Alternatively, it may be 60% by mass or less. From these viewpoints, the content of the component (A) may be 20 to 90% by mass, 30 to 80% by mass, or 40 to 65% by mass.

The content of the component (A) 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). The content of the component (A) is 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, from the viewpoint that good formability of the film can be easily obtained and that the cured product is easily suppressed from becoming brittle. It may be 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more. The content of the component (A) is 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, from the viewpoint of easily obtaining good sensitivity and resolution. It may be 65 parts by mass or less, or 60 parts by mass or less. From these viewpoints, the content of the component (A) is 30 to 95 parts by mass, 30 to 70 parts by mass, 35 to 70 parts by mass, 40 to 70 parts by mass, 40 to 65 parts by mass, or 50 to 60 parts by mass. It may be a department.

The component (B) (photopolymerizable compound having an ethylenically unsaturated bond) may be a compound having an ethylenically unsaturated bond and polymerizing by light.

The component (B) may contain a bisphenol A type di (meth) acrylate compound from the viewpoint of easily obtaining good alkali developability, resolution, adhesion and resist peeling characteristics. The bisphenol A type di (meth) acrylate compound may be alkylene oxide-modified and may have a 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, etc.), 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2, 2-Bis (4-((meth) acryloxipolyethoxypolypropoxy) phenyl) propane and the like can be mentioned.

The component (B) may contain 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane from the viewpoint of obtaining good resolution, adhesion and resist peeling characteristics, and may contain 2,2. -Contains at least one selected from the group consisting of 4-((meth) acryloxipentethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxidiethoxy) phenyl) propane. In combination with 2,2-bis (4-((meth) acryloxipentaethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxidiethoxy) phenyl) propane. May be good.

The component (B) is a bisphenol A type didi having a polyoxyalkylene group from the viewpoint of easily suppressing the occurrence of resist defects, easily shortening the minimum development time, and easily obtaining good resolution and adhesion. The (meth) acrylate compound may include a bisphenol A type di (meth) acrylate compound in which the number of oxyalkylene groups in the polyoxyalkylene chain (the number of oxyalkylene groups in one molecule) is in the following range. Further, in the component (B) contained in the photosensitive layer or the photosensitive resin composition, the number of oxyalkylene groups in the polyoxyalkylene chain of the bisphenol A type di (meth) acrylate compound having a polyoxyalkylene group (photosensitive layer or The average value of the (B) component contained in the photosensitive resin composition) is easy to suppress the occurrence of resist defects, easy to shorten the minimum development time, and easy to obtain good resolution and adhesion. From the viewpoint, it may be in the following range. 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 is 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. good. From these viewpoints, the number of oxyalkylene groups may be 1 to 20.

The content of the bisphenol A type di (meth) acrylate compound is based on the total amount of the photosensitive layer or the total solid content of the photosensitive resin composition from the viewpoint of easily obtaining good resolution and easily suppressing the residue. It may be in the following range. The content of the bisphenol A type di (meth) acrylate compound is 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 36% by mass or more, or. , 38% by mass or more. The content of the bisphenol A type di (meth) acrylate compound is 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45. It may be 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% by mass.

The content of the bisphenol A type di (meth) acrylate compound may be in the following range based on the total amount of the component (B) from the viewpoint of easily obtaining a good resolution and easily suppressing the residue. The content of bisphenol A type di (meth) acrylate compound is 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85. It may be mass% or more, or 90 mass% or more. The content of the bisphenol A type di (meth) acrylate compound may be 99% by mass or less, 95% by mass or less, or 90% by mass or less. From these viewpoints, the content of the bisphenol A type di (meth) acrylate compound may be 50 to 99% by mass or 60 to 99% by mass.

The content of the bisphenol A type di (meth) acrylate compound is as follows with respect to 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of easily obtaining a good resolution and easily suppressing the residue. It may be in the range of. The content of the bisphenol A type di (meth) acrylate compound is 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. May be. The content of the bisphenol A type di (meth) acrylate compound is 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. It may be 10 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.

The component (B) may contain a (meth) acrylate compound having a skeleton derived from dipentaerythritol (hereinafter referred to as “(meth) acrylate compound A”), and the (meth) acrylate compound A and the bisphenol A type di (meth). ) May contain an 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 inventor can suppress the formation of a residue when the photosensitive layer is exposed and developed by adjusting the content of the (meth) acrylate compound A (in particular, even if the development time is shortened). It is possible to suppress the formation of residues).

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 solid content of the photosensitive resin composition. The content of the (meth) acrylate compound A is 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, 5% by mass or less, and 4 from the viewpoint of easily suppressing the residue. It may be 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.1% by mass or less. The content of the (meth) acrylate compound A is 0% by mass or more, more than 0% by mass, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, or 4% by mass or more. It may be there. From these viewpoints, the content of the (meth) acrylate compound A is 0 to 20% by mass, more than 0% by mass and 20% by mass or less, 0 to 3% by mass, or more than 0% by mass and 3% by mass or less. It may be there.

The content of the (meth) acrylate compound A may be in the following range based on the total amount of the component (B). The content of the (meth) acrylate compound A is 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 6 from the viewpoint of easily suppressing the residue. It may be mass% or less, 5 mass% or less, 3 mass% or less, 1 mass% or less, or 0.1 mass% or less. The content of (meth) acrylate compound A is 0% by mass or more, more than 0% by mass, 0.1% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, 6% by mass or more, and 8% by mass. % Or more, or 10% by mass or more. From these viewpoints, the content of the (meth) acrylate compound A is 0 to 30% by mass, more than 0% by mass and 30% by mass or less, 0 to 8% by mass, or more than 0% by mass and 8% by mass or less. It may be there.

The content of the (meth) acrylate compound A 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). The content of the (meth) acrylate compound A is 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, and 4 from the viewpoint of easily suppressing the residue. It may be 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 is 0 parts by mass or more, more than 0 parts by mass, 0.1 parts 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. It may be 5 parts by mass or more. From these viewpoints, the content of the (meth) acrylate compound A is 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. It may be there.

The component (B) is represented by the following general formula (b1) from the viewpoint of easily suppressing the occurrence of resist defects, the viewpoint of easily shortening the minimum development time, and the viewpoint of easily obtaining good resolution and adhesion. It may contain a compound. N in the general formula (b1) may be 1 to 40, 1 to 30, 1 to 20, 5 to 20, or 10 to 20 from the viewpoint of easily obtaining good resolution and adhesion.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, AO represents an oxyalkylene group (oxyethylene group, oxypropylene group, oxybutylene group, etc.), and n is an oxyalkylene group. Indicates the number of groups and indicates an integer from 1 to 50.)

The content of the compound represented by the general formula (b1) is in the following range based on the total amount of the photosensitive layer or the total solid content of the photosensitive resin composition from the viewpoint of easily obtaining good resolution and adhesion. It may be there. The content of the compound represented by the general formula (b1) is 0% by mass or more, more than 0% by mass, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, or 4 It may be mass% or more. The content of the compound represented by the general formula (b1) is 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, It may be 2% by mass or less, 1% by mass or less, or 0.1% by mass or less. From these viewpoints, the content of the compound represented by the general formula (b1) 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 in the following range based on the total amount of the component (B) from the viewpoint of easily obtaining good resolution and adhesion. The content of the compound represented by the general formula (b1) is 0% by mass or more, more than 0% by mass, 0.1% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, and 8% by mass. As mentioned above, it may be 10% by mass or more, or 11% by mass or more. The content of the compound represented by the general formula (b1) is 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 12% by mass or less, It may be 11% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.1% by mass or less. From these viewpoints, the content of the compound represented by the general formula (b1) may be 0 to 40% by mass, or more than 0% by mass and 40% by mass or less.

The content of the compound represented by the general formula (b1) is 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 easily obtaining good resolution and adhesion. good. The content of the compound represented by the general formula (b1) is 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. It may be 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, or 0.1 parts by mass or less. The content of the compound represented by the general formula (b1) is 0 parts by mass or more, more than 0 parts by mass, 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, and 10 parts by mass. As mentioned above, it may be 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 (b1) 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) is a trimethylolpropane tri (from the viewpoint of easily suppressing the occurrence of resist defects, the viewpoint of easily shortening the minimum development time, and the viewpoint of easily obtaining good resist peeling characteristics, adhesion and flexibility. It may contain at least one compound X selected from the group consisting of meth) acrylates, tetramethylolmethanetri (meth) acrylates, and modified alkylene oxides thereof. Examples of the alkylene oxide-modified product of trimethylolpropane tri (meth) acrylate and tetramethylolmethanetri (meth) acrylate include EO-modified product, PO-modified product, and EO / PO-modified product.

The content of compound X or the content of the alkylene oxide modified product of trimethylolpropane tri (meth) acrylate may be in the following range based on the total amount of the component (B). The above-mentioned content is 1% by mass or more, 3% by mass or more, 5% by mass or more, 8% by mass or more, or 10% by mass or more from the viewpoint of easy to obtain good developability, adhesion and pattern shape. It's okay. The above-mentioned content is 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, and 3% by mass from the viewpoint of easily obtaining good resist peeling characteristics. Hereinafter, it may be 1% by mass or less, or 0.1% by mass or less. From these viewpoints, the content of the compound X may be 0 to 30% by mass, more than 0% by mass and 30% by mass or less, and 1 to 30% by mass.

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

The content of the component (B) 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). The content of the component (B) is 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, from the viewpoint of easily obtaining good sensitivity and resolution. It may be 35 parts by mass or more, or 40 parts by mass or more. The content of the component (B) is 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, from the viewpoint that good formability of the film can be easily obtained and that the cured product is easily suppressed from becoming brittle. It may be 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these viewpoints, the content of the component (B) is 5 to 70 parts by mass, 30 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. It may be a department.

Examples of the photopolymerization initiator as the component (C) include imidazole compounds, aromatic ketones (excluding compounds corresponding to benzophenone compounds), quinone compounds, benzoin compounds, aclysine compounds, N-phenylglycine compounds, benzyl derivatives and the like. Be done. Examples of the imidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, and 2- (o-). Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Examples thereof include 2,4,5-triarylimidazole dimers such as the body. As aromatic ketones, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 And so on. Examples of the quinone compound include alkyl anthraquinone and the like. Examples of the benzoin compound include benzoin, alkylbenzoin, and benzoin ether compounds (benzoin alkyl ether and the like). Examples of the acridine compound include 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 easily obtaining good adhesion and sensitivity.

The content of the component (C) may be in the following range based on the total amount of the photosensitive layer or the total solid content of the photosensitive resin composition. The content of the component (C) is 0.1% by mass or more, 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, or from the viewpoint of easily obtaining good sensitivity. , 2.5% by mass or more. The content of the component (C) is 20% by mass or less and 10% by mass from the viewpoint that the light absorption on the surface of the photosensitive layer is suppressed from being excessively increased during exposure and the inside of the photosensitive layer is easily sufficiently cured. % Or less, 5% by mass or less, or 3% by mass or less. 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. By adjusting the content of the component (C), the occurrence of resist deficiency may be suppressed.

The content of the component (C) 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). The content of the component (C) is 0.1 parts 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 from the viewpoint of easily obtaining good sensitivity. , 2.5 parts by mass or more. The content of the component (C) is 20 parts by mass or less and 10 parts by mass from the viewpoint that the light absorption on the surface of the photosensitive layer is suppressed from being excessively increased during exposure and the inside of the photosensitive layer is easily sufficiently cured. It may be 5 parts by mass or less, or 3 parts by mass or less. From these viewpoints, the content of the component (C) may be 0.1 to 20 parts by mass, 0.2 to 10 parts by mass, or 0.5 to 5 parts by mass. By adjusting the content of the component (C), the occurrence of resist deficiency may be suppressed.

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, stylben compounds, triazine compounds, and thiophene compounds. Examples thereof include naphthalimide compounds and triarylamine compounds. The sensitizer is a pyrazoline compound, a benzophenone compound, an anthracene compound, from the viewpoint of easily suppressing the occurrence of resist defects, the viewpoint of easily shortening the minimum development time, and the viewpoint of easily obtaining good sensitivity, resolution and adhesion. And at least one selected from the group consisting of coumarin compounds may be included. That is, the sensitizer may be an embodiment containing a pyrazoline compound, an embodiment containing a benzophenone compound, an embodiment containing an anthracene compound, or an embodiment containing a coumarin compound.

Examples of the pyrazoline compound include 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline and 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-Dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxy) Styryl) -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-dimethoxyphenyl) -pyrazoline, 4-[[3- (4-Chlorophenyl) -4,5-dihydro-1H-pyrazol] -1-yl] benzenesulfonamide and the like can be mentioned. The sensitizer may contain 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline from the viewpoint of easily obtaining good resolution and adhesion.

Benzophenone compounds are benzophenones; N, N, N', N'-tetramethyl-4,4'-diaminobenzophenone (also known as Michlerketone), N, N, N', N'-tetraethyl-4,4'-diamino. Examples thereof include N, N, N', N'-tetraalkyl-4,4'-diaminobenzophenone such as benzophenone; and dialkylaminobenzophenone such as 4-methoxy-4'-dimethylaminobenzophenone. The sensitizer may contain N, N, N', N'-tetraalkyl-4,4'-diaminobenzophenone from the viewpoint of facilitating good resolution and adhesion.

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene. Dialkoxy anthracene and the like can be mentioned. The sensitizer may contain 9,10-dialkoxyanthracene from the viewpoint of easily obtaining good sensitivity.

Examples of the coumarin compound include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethylamino-4-. Methylcoumarin, 7-aminocyclopenta [c] coumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6- Dimethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-diethyl-7 -Dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1 ] Benzopyrano [6,7,8-ij] quinolidine-11-one and the like. The sensitizer is 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11 from the viewpoint of easily obtaining good sensitivity. -May include on.

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 is the total amount of the photosensitive layer or the total solid content of the photosensitive resin composition. It may be in the following range with reference to. The above-mentioned contents are 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.015% by mass or more, 0. 018% by mass or more, 0.019% by mass or more, 0.02% by mass or more, 0.05% by mass or more, more than 0.05% by mass, 0.1% by mass or more, 0.15% by mass or more, 0.18 Mass% or more, 0.19% by mass or more, 0.2% by mass or more, 0.25% by mass or more, 0.3% by mass or more, 0.35% by mass or more, 0.4% by mass or more, or 0. It may be 45% by mass or more. The above-mentioned content is 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.5% by mass or less, 0 from the viewpoint of easily obtaining good sensitivity, resolution and adhesion. .45% by mass or less, 0.4% by mass or less, 0.35% by mass or less, 0.3% by mass or less, 0.25% by mass or less, 0.2% by mass or less, 0.19% by mass or less, 0. 18% by mass or less, 0.15% by mass or less, 0.1% by mass or less, 0.05% by mass or less, less than 0.05% by mass, 0.02% by mass or less, or 0.019% by mass or less. It's okay. From these viewpoints, the above-mentioned 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 is based on 100 parts by mass of the total amount of the component (A) and the component (B). It may be in the following range. The above-mentioned contents are 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 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, more than 0.1 parts by mass, 0.15 parts by mass or more, 0.2 parts by mass or more, 0.25 parts It may be 0 parts by mass or more, 0.3 parts by mass or more, 0.35 parts by mass or more, 0.4 parts by mass or more, or 0.45 parts by mass or more. The above-mentioned content is 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 from the viewpoint of easily obtaining good sensitivity, resolution and adhesion. .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. It may be 1 part by mass or less, less than 0.1 part by mass, 0.05 part by mass or less, 0.03 part by mass or less, or 0.02 part by mass or less. From these viewpoints, the above-mentioned content may be 0.001 to 5 parts by mass.

The photosensitive layer and the photosensitive resin composition constituting the photosensitive layer are, if necessary, at least in the molecule as a component different from the component (A), the component (B), the component (C) and the sensitizer. Photopolymerizable compound (oxetane compound, etc.) having one cationically polymerizable cyclic ether group, cationic polymerization initiator, dye (malakite green, etc.), photocoloring agent (tribromophenylsulfone, leucocrystal violet, etc.), thermal coloring Inhibitors, plasticizers (p-toluene sulfonamide, etc.), polymerization inhibitors (4-t-butylcatechol, etc.), pigments, fillers, defoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, etc. It may contain additives such as a peeling accelerator, an antioxidant (dibutylhydroxytoluene (also known as 2,6-di-tert-butyl-p-cresol), etc.), a fragrance, an imaging agent, and a thermal cross-linking agent. The content of these additives may be 0.01 to 20 parts by mass, respectively, with respect 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 contain an antioxidant (dibutylhydroxytoluene) from the viewpoint of easily suppressing the occurrence of resist defects and easily shortening the minimum development time. You can do it.

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

The photosensitive layer can be formed by applying the photosensitive resin composition on the support film and then removing the solvent. As the coating method, for example, a known method such as a roll coat, a comma coat, a gravure coat, an air knife coat, a die coat, and a bar coat can be adopted. The solvent can be removed by, for example, treating at 70 to 150 ° C. for about 5 to 30 minutes. The amount of the residual organic solvent in the photosensitive layer may be 2% by mass or less from the viewpoint of easily preventing the diffusion of the organic solvent in a later step.

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 easily obtaining good resolution and adhesion. The thickness of the photosensitive layer is 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 these viewpoints, the thickness of the photosensitive layer may be 1 to 300 μm.

The photosensitive element according to the present embodiment may be provided with a protective film on the side opposite to the support film of the photosensitive layer. As the protective film, a film can be used in which the adhesive force between the photosensitive layer and the protective film is smaller than the adhesive force between the support film and the photosensitive layer. As the protective film, a low fisheye film 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 easily obtaining good peeling characteristics from the photosensitive layer. The thickness of the protective film varies depending on the application, but may be about 1 to 100 μm.

The photosensitive element according to the present embodiment may include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer or a protective 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 as it is, for example, or may be stored in a state where a protective film is laminated on the photosensitive layer and wound around a cylindrical core. At this time, the support film may be wound into a roll so as to be the outermost layer.

<Manufacturing method of cured product and manufacturing method of cured product pattern>
The method for producing a cured product according to the present embodiment includes a curing step of curing the photosensitive layer of the photosensitive element to obtain a cured product (photo-cured product). In the method for producing a cured product according to the present embodiment, as a curing step, a cured product (photo-cured product) is obtained by irradiating a photosensitive layer with active light via a support film in a state where photosensitive elements are laminated on a substrate. It may be provided with an exposure process for obtaining the above. In the curing step, for example, a predetermined portion of the photosensitive layer is irradiated with active light rays. In the curing step, the photosensitive element may be laminated on the substrate so that the photosensitive layer is located closer to the substrate than the support film.

In the curing step, for example, a photomask having a negative or positive mask pattern is in close contact with the support film, and the photosensitive layer is irradiated with active light through the support film (for example, irradiated in an image) to cure. You may get things. Examples of the light source of the active light include a light source that emits ultraviolet rays, visible light, and the like (carbon arc lamp, mercury vapor arc lamp, high-pressure mercury lamp, xenon lamp, etc.). In the curing step, a laser direct drawing exposure method can also be used.

The method for producing a cured product according to the present embodiment may include a laminating step of laminating a photosensitive element on a substrate before the curing step. In the laminating step, the photosensitive element can be laminated on the substrate so that the photosensitive layer is located 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 layer on the substrate by pressure bonding at a pressure of about 0.1 to 1 MPa while heating to about 70 to 130 ° C. If 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 laminating step, the photosensitive elements can also be laminated under reduced pressure. From the viewpoint of improving the stackability, the substrate may be preheat-treated. The constituent material of the surface of the substrate on which the photosensitive elements are laminated may be a metal or a resin material.

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

In the developing process, the photomask is peeled off from the support film, and the support film is peeled off from the photosensitive layer. In the developing process, wet development with a developing solution (alkaline aqueous solution, aqueous developer, organic solvent, etc.); development is performed by removing the unexposed part (unlightened part) of the photosensitive layer by dry development or the like to form a cured product pattern. Obtainable.

Examples of the alkaline aqueous solution include 0.1 to 5% by mass sodium carbonate solution, 0.1 to 5% by mass potassium carbonate solution, 0.1 to 5% by mass sodium hydroxide solution and the like. The pH of the alkaline aqueous solution may be 9-11. The temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive layer. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, an organic solvent and the like. Examples of the developing method include a dip method, a spray method, brushing, and slapping.

In the method for producing a cured product pattern according to the present embodiment, from the viewpoint of improving solder heat resistance, chemical resistance, etc., the cured product pattern is further heated and / or exposed as necessary after the developing step. It may be provided with a curing step. Heating may be performed, for example, at 60 to 250 ° C. or 100 to 170 ° C. for 15 to 90 minutes. The exposure can be performed by irradiating ultraviolet rays with a high-pressure mercury lamp. The exposure amount may be, for example, 0.2 to 10 J / cm ² . Heating and exposure (for example, ultraviolet irradiation) may be performed simultaneously, and one of heating and exposure may be performed and then the other. When heating and exposure are performed at the same time, it can be heated at 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like.

By the method for manufacturing 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 to prevent solder from adhering to unnecessary portions of the conductor layer when joining the mounted components. 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 has physical properties (tensile strength, elongation, etc.) and heat resistance. Since it has excellent impact resistance, it is effective as a permanent mask for semiconductor packages. After mounting a semiconductor element or the like (wire bonding, solder connection, etc.) on a package substrate having such a cured product pattern (resist pattern), it can be 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 has excellent physical characteristics (tensile strength, elongation, etc.), and a cured resin satisfying electrolytic corrosion resistance is formed on a rigid substrate. It may be used as a solder resist (permanent mask) formed on a rigid substrate. Specifically, it can be used as a solder resist for a printed wiring board including a rigid substrate, a solder resist for a package substrate including a rigid substrate, and the like.

<Manufacturing method of wiring board>
The method for manufacturing a wiring board (for example, a printed wiring board) according to the present embodiment is such that a laminate having a cured product pattern obtained by the method for manufacturing a cured product pattern according to the present embodiment is etched or plated on a laminate. It is provided with a process for performing processing. In this case, the cured product pattern can be used as a mask to perform an etching treatment or a plating treatment on the laminated body by a known method. The wiring board may be a multilayer printed wiring board and may have a small diameter through hole.

Examples of the etching solution used for the etching process include a cupric chloride solution, a ferric chloride solution, and an alkaline etching solution. Examples of the plating treatment include copper plating, solder plating, nickel plating, gold plating and the like.

After performing the etching treatment or the plating treatment, for example, the cured product pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of this strongly alkaline aqueous solution include a 1 to 10% by mass sodium hydroxide aqueous solution and a 1 to 10% by mass potassium hydroxide aqueous solution. Examples of the method for peeling the cured product pattern include a dipping method and a spraying method.

When the substrate including the insulating layer and the conductor layer arranged on the insulating layer is plated, the conductor layer other than the pattern portion can be removed. As a method of removing the conductor layer, a method of lightly etching after peeling the cured product pattern; a method of masking the wiring portion with solder by peeling off the cured product pattern after performing solder plating or the like after the plating process, and then Examples thereof include a method of treating only the conductor layer with an etching solution capable of etching.

Hereinafter, the contents of the present disclosure will be described in more detail using Examples and Comparative Examples, but the present disclosure is not limited to the following Examples.

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

420 g 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 introduction tube. Then, the mixture b was heated to 80 ° C. while stirring while blowing nitrogen gas. Subsequently, the above solution a was added dropwise to the mixture b using a dropping funnel over 4 hours. Then, the inside of the dropping funnel was washed with 40 g of a mixture of toluene and methyl cellosolve (mass ratio = 6: 4) as a washing liquid, and then this washing liquid was added to a flask to obtain a mixture c.

Next, the mixture c was kept warm at 80 ° C. for 2 hours with stirring. Subsequently, using a dropping funnel, solution d obtained by dissolving 1.0 g of azobisisobutyronitrile in 40 g of a mixture of methyl cellosolve and toluene (mass ratio = 6: 4) was placed in a flask over 30 minutes. Dropped into. Subsequently, the inside of the dropping funnel was washed with 120 g of a mixture of toluene and methyl cellosolve (mass ratio = 6: 4) as a washing liquid, and then this washing liquid was added to a flask to obtain a mixture e.

Next, the mixture e was kept warm at 80 ° C. for 3 hours with stirring. Subsequently, it was heated to 90 ° C. over 30 minutes. A binder polymer solution was obtained by incubating at 90 ° C. for 2 hours and then cooling. Toluene was added to this binder polymer solution to adjust the non-volatile component concentration (solid content concentration) to 40% by mass.

The weight average molecular weight of the binder polymer was 45,000. The weight average molecular weight was calculated by measuring by gel permeation chromatography (GPC) under the following conditions and converting using a calibration curve of standard polystyrene.

Pump: L-2130 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-2490 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-2350 [manufactured by Hitachi High-Technologies Corporation]
Column: Gelpack GL-R440 + Gelpack GL-R450 + Gelpack GL-R400M (3 in total) [Showa Denko Materials Co., Ltd., product name]
Column size: 10.7 mm I. D x 300 mm
Eluent: Tetrahydrofuran Sample concentration: 10 mg / 2 mL
Injection volume: 200 μL
Flow rate: 2.05 mL / min Measurement temperature: 25 ° C

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

<Preparation of photosensitive resin composition>
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, and TBC (4-t-butylcatechol) or BHT (dibutylhydroxytoluene). ), Leuco Crystal Violet 0.5 parts by mass, Malakite Green 0.03 parts by mass, 5 parts by mass of methanol, 9 parts by mass of acetone, and 5 parts by mass of toluene to obtain a photosensitive resin composition. Got Table 1 shows the photopolymerizable compounds, photopolymerization initiators, sensitizers, TBC and BHT used in Examples and Comparative Examples. The numerical values in Table 1 indicate the content (unit: parts by mass) of each component. The following components were used as the photopolymerizable compound, the photopolymerization initiator and the sensitizer.

(Photopolymerizable compound)
FA-321M: EO-modified bisphenol A dimethacrylate, EO10 mol, manufactured by Showa Denko Materials Co., Ltd., trade name BPE-200: EO-modified bisphenol A dimethacrylate, EO4.0 mol, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name BPE- 100: EO-modified bisphenol A dimethacrylate, EO2.6 mol, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name DPEA-12: dipentaerythritol EO-modified acrylate, manufactured by Nippon Kayaku Co., Ltd., trade name FA-024M: EO / PO Modified Dimethacrylate, Showa Denko Materials Co., Ltd., Product Name TMPT-211: Trimethylol Propane EO Modified Triacrylate, EO21mol, Showa Denko Materials Co., Ltd., Product Name

(Photopolymerization initiator)
BCIM: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, manufactured by Hodogaya Chemical Industry Co., Ltd., trade name

(Sensitizer)
PZ-501D: 1-Phenyl-3- (4-Methoxystylyl) -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] benzopyrano [6,7,8-ij] quinolidine-11-one, Tokyo Made by Kasei Kogyo Co., Ltd., product name

<Preparation of support film>
The following PET film was prepared as a support film.
Films A1 to A7: Biaxially oriented films having a three-layer structure having lubricant layers containing particles on the front and back of the PET film. The time of the filtration treatment applied to the film-forming composition (the same film-forming composition as the FB40 PET film manufactured by Toray Industries, Inc.) before the formation of the PET film was adjusted. The filtration time of the films A1 to A3 was 24 hours or more, the filtration time of the films A4 to A6 was 12 to 18 hours, and the filtration time of the films A7 was 6 hours or less.
Film B: A biaxially oriented film having a two-layer structure having a lubricant layer containing particles on one side of a PET film. Made by Mitsubishi Chemical Corporation, Product name: R-705G
Film C: Single-layer structure biaxially oriented PET film containing particles, manufactured by Teijin DuPont Film Co., Ltd., trade name: G2

By applying the above-mentioned photosensitive resin composition on the above-mentioned support film (PET film) so as to have a uniform thickness, and then drying with a hot air convection dryer at 100 ° C. for 2 minutes to remove the solvent. , An evaluation laminate having a photosensitive layer (thickness: 25 μm) on the support film was obtained. When the above-mentioned film B is used as the support film, a photosensitive layer is formed on the surface opposite to the lubricant layer. Ten areas of 0.225 mm ² (0.150 mm × 0.150 mm) of the support film of the evaluation laminate were selected, and the number of defects (light blockers) having a maximum diameter of 1 μm or more contained in each area was measured. .. In order to evaluate the defects contained inside the support film, the region (inner layer) between the surface layer portion having a depth of 0.5 μm from one side of the support film and the surface layer portion having a depth of 0.5 μm from the other surface of the support film. Department) was evaluated. Using a confocal microscope (manufactured by Laser Tech Co., Ltd., trade name: hybrid laser microscope OPTELICS HYBRID), the image has a numerical aperture (Na) of 0.8, a magnification of 50 times, a digital zoom of 2 times, and the conditions shown in Table 2 below. Was obtained, and the size and number of defects were measured from the pixels in the image. As for the measurement conditions that need to be adjusted each time, the conditions that make it easy to recognize defects were adopted as appropriate. Focusing was sequentially applied from one surface to the other, and the entire inner layer was observed. The number of measurements (n number) was 5 times (50 areas in total), and the average value of the number of defects was obtained. The measurement results are shown in Tables 3-6.

FIG. 2A shows the results (magnification: 600 times) of observing the surface of the support film (film A1) of Example 1 using a confocal microscope (manufactured by Lasertec Co., Ltd., trade name: hybrid laser microscope OPTELICS HYBRID). 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 FIGS. 2 (a) and 2 (b) are the same as each other. The image of the support film of Example 1 observed by the above-mentioned confocal microscope is shown in FIG. 3 (a), and the image of the support film of Comparative Example 1 is shown in FIG. 3 (b). The scales in the images of FIGS. 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 (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: NDH-5000). The thickness (total thickness) of the support film was measured using MH-15M (trade name) manufactured by Nikon Corporation. The results are shown in Tables 3-6.

<Manufacturing of photosensitive element>
After applying the above-mentioned photosensitive resin composition on the above-mentioned support film (PET film, support film of Tables 3 to 6) so as to have a uniform thickness, it is dried in a hot air convection dryer at 100 ° C. for 2 minutes. By removing the solvent, a photosensitive layer (thickness: 25 μm) was formed. When the above-mentioned film B is used as the support film, a photosensitive layer is formed on the surface opposite to the lubricant layer. Then, a photosensitive element was obtained by coating the photosensitive layer with a protective film made of polyethylene (manufactured by Tamapoli Co., Ltd., trade name: NF-15, thickness: 18 μm).

<Evaluation>
(Preparation of laminated body)
After forming a copper layer (electroless copper, thickness: 500 nm) by electroless plating on both sides of an interlayer insulating material (manufactured by Ajinomoto Fine-Techno Co., Ltd., trade name: GX-T31), the surface of the copper layer is acidified. The substrate a was obtained by washing, washing with water and drying (air flow). After heating this substrate a to 80 ° C., the photosensitive element was laminated so that the photosensitive layer was in contact with the copper layer while peeling off the protective film of the photosensitive element described above. As a result, a laminated body having the substrate a, the photosensitive layer, and the support film in this order was obtained in the laminated direction. Lamination was performed using a heat roll at 110 ° C. at a crimping pressure of 0.4 MPa and a roll speed of 1.5 m / min.

(Minimum development time)
After peeling off the support film, the photosensitive layer was spray-developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C., and the time for completely removing the unexposed portion was obtained as the minimum development time. The measurement results are shown in Tables 3-6.

(Light sensitivity)
A 41-step step tablet was placed as a negative on the support film of the above-mentioned laminate. Then, using a high-resolution projection exposure machine (manufactured by Ushio, Inc., trade name: UX-2240) equipped with a high-pressure mercury lamp, the irradiation amount is determined in order to obtain the irradiation energy amount at which the number of resist curing stages after development is 11. The photosensitive layer was exposed while adjusting.

Next, after peeling off the support film, the photosensitive layer was spray-developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. for twice the minimum development time to remove the unexposed portion. Then, it was confirmed that the number of steps of the step tablet of the photocurable film formed on the above-mentioned substrate was 11, and the irradiation energy amount (exposure amount, mJ / cm ² ) in the above-mentioned exposure was obtained. The results are shown in Tables 3-6.

(Adhesion and resolution)
A photo tool with a 41-step step tablet to check adhesion and resolution, and a glass chrome type with a wiring pattern with a line width / space width of 2/6 to 20/90 (unit: μm) as a negative for adhesion evaluation. Photo tool, a glass chrome type photo tool with a line width / space width of 2/2 to 20/20 (unit: μm) as a negative for resolution evaluation, and high-resolution projection exposure with a high-pressure mercury lamp. Using a machine (UX-2240 manufactured by Ushio Denki Co., Ltd.), the photosensitive layer of the laminated body was exposed with an irradiation energy amount such that the number of remaining steps after development of the 41-step step tablet was 11. Next, the support film was peeled off, and a 1% by mass sodium carbonate aqueous solution was spray-developed at 30 ° C. for twice the minimum development time to remove the unexposed portion. Here, the adhesion was evaluated by the smallest value (unit: μm) of the line width that could be formed neatly by the developing process. The resolution was evaluated by the smallest value (unit: μm) of the space width between the line portions where the unexposed portion could be removed cleanly by the development process. The results are shown in Tables 3-6. The smaller the numerical value, the better the evaluation of adhesion and resolution.

(Number of resist defects)
Using a scanning electron microscope (manufactured by Hitachi, Ltd., trade name: SU-1500), randomly observe 10 resist lines (L / S = 10/10 μm) of the laminate used in the above resolution evaluation. (Magnification: 500 times) was performed, and the number of defects (deficiencies of 0.5 μm or more) as shown in FIG. 4 was evaluated. Tables 3 to 6 show the converted values obtained by converting the average value of the number of defects into the number per 0.225 mm ² .

(Residue)
The photosensitive layer of the laminated body was exposed in the same manner as in the evaluation of the light sensitivity described above. Next, after peeling off the support film, the photosensitive layer was spray-developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. for 2 times and 6 times the minimum development time to remove the unexposed portion. Then, the surfaces of the substrate b1 developed at twice the minimum development time and the substrate b2 developed at six times the minimum development time were visually observed, and the area of the discolored portion was calculated. The ratio of the area of the substrate b1 to the area of the substrate b2 (= [b1 / b2] × 100) was calculated. When the ratio was less than 10%, it was evaluated as "A", and when the ratio was 10% or more, it was evaluated as "B". The results are shown in Tables 3-6.

As shown in Tables 3 to 6, when the high-resolution projection exposure machine was used, the number of resist defects was 100 or less in the examples, whereas the number of resists in the comparative example was very large. Deficiency was confirmed. In Example 1, although the number of defects inside the support film was 0, it is presumed that the resist was defective due to an external factor that was difficult to avoid in the evaluation process.

When the number of particles in the surface layer portion of the films A1 to A7 (the surface layer portion excluded in the evaluation of the number of defects described above) was confirmed, the number of particles (lubricant, agglomerates thereof, etc.) having a maximum diameter of 1 μm or more and less than 2 μm was 0. The number of particles (lubricant, agglomerates thereof, etc.) having a maximum diameter of ² μm or more and less than 5 μm was 100,000 or more per 225 mm ² . This confirms that the particles in the surface layer portion do not significantly contribute to the defect of the resist.

1 ... Photosensitive element, 10 ... Support film, 10a ... First main surface, 10b ... Second main surface, 20 ... Photosensitive layer.

Claims

A support film and a photosensitive layer arranged on the support film are provided.
The number of defects having a maximum diameter of 1 μm or more inside the support film is 100 or less per 0.225 mm 2 .
A photosensitive element in which the photosensitive layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.
The photosensitive element according to claim 1, wherein the number of defects having a maximum diameter of 1 μm or more inside the support film is 5 or less per 0.225 mm 2 .
The photosensitive element according to claim 1 or 2, wherein the support film has a polyester film and a lubricant layer arranged on at least one surface of the polyester film.
The photosensitive element according to any one of claims 1 to 3, wherein the support film has a haze value of 0.01 to 3.0%.
The photosensitive element according to any one of claims 1 to 4, wherein the photosensitive layer does not contain a (meth) acrylate compound having a skeleton derived from dipentaerythritol.
The photopolymerizable compound contains a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and the content of the (meth) acrylate compound is 100 parts by mass based on the total amount of the binder polymer and the photopolymerizable compound. The photosensitive element according to any one of claims 1 to 4, which is more than 0 parts by mass and 3 parts by mass or less.
The photosensitive element according to claim 6, wherein the photopolymerizable compound further contains a bisphenol A type di (meth) acrylate compound.
The photosensitive element according to claim 7, wherein the content of the bisphenol A type di (meth) acrylate compound is 30 to 50 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.
The photosensitive element according to any one of claims 1 to 8, further containing a sensitizer.
The photosensitive element according to claim 9, wherein the sensitizer contains a pyrazoline compound.
The photosensitive element according to claim 9 or 10, wherein the sensitizer contains N, N, N', N'-tetraalkyl-4,4'-diaminobenzophenone.
The photosensitive element according to any one of claims 9 to 11, wherein the sensitizer contains 9,10-dialkoxyanthracene.
The photosensitive element according to any one of claims 9 to 12, wherein the sensitizer contains a coumarin compound.
The photosensitive element according to any one of claims 9 to 13, wherein the content of the sensitizer is less than 0.1 part by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. ..
The present invention comprises an exposure step of irradiating the photosensitive layer with an active ray through the support film in a state where the photosensitive element according to any one of claims 1 to 14 is laminated on a substrate to obtain a cured product. , How to make a cured product.
A method for producing a cured product pattern, comprising a step of removing at least a part of a portion other than the cured product in the photosensitive layer after the exposure step in the method for producing a cured product according to claim 15.
A method for manufacturing a wiring board, comprising a step of performing an etching treatment or a plating treatment on a laminate provided on the substrate with the cured product pattern obtained by the cured product pattern manufacturing method according to claim 16.