WO2021221025A1

WO2021221025A1 - Method for manufacturing structure, and structure

Info

Publication number: WO2021221025A1
Application number: PCT/JP2021/016684
Authority: WO
Inventors: 慎一漢那
Original assignee: 富士フイルム株式会社
Priority date: 2020-04-30
Filing date: 2021-04-26
Publication date: 2021-11-04
Also published as: CN115486211A; KR20220162158A; TW202208988A; JPWO2021221025A1

Abstract

Provided are a method for manufacturing a structure, and a structure, the method comprising: a step for preparing a laminate that has a transparent base material, a light-shielding pattern 1 disposed on the transparent base material, and a negative photosensitive resin layer N that is disposed on the transparent substrate and the light-shielding pattern and is in contact with the transparent base material; a step for irradiating a portion of the negative photosensitive resin layer N with light from a surface of the transparent substrate on a side opposite from a surface on which the light-shielding pattern 1 is provided; a step for forming a resin pattern 2 on the transparent base material by developing the negative photosensitive resin layer N irradiated with light; and a step for forming a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2, wherein the obtained structure has the resin pattern 2 as a permanent film.

Description

Structure manufacturing method and structure

This disclosure relates to a method for manufacturing a structure and the structure.

Conductive patterns such as thin metal wires are used for various purposes. Applications of the conductive pattern include, for example, a touch sensor of a touch panel, an antenna, a fingerprint authentication unit, a foldable device, and a transparent FPC (Flexible Printed Circuits). For example, in the manufacture of a semiconductor package, a printed wiring board, and a rewiring layer of an interposer, a fine conductive pattern is formed on the base material. As the base material, for example, a film, a sheet, a metal substrate, a ceramic substrate, or glass is used.

As a general method for forming a conductive pattern, for example, a subtractive method and a semi-additive method are known (for example, Patent Document 1 and Patent Document 2). In the subtractive method, for example, a conductive pattern can be formed by protecting the conductive layer on the base material with a resist pattern and then removing the conductive layer not protected by the resist pattern by etching. On the other hand, in the semi-additive method, for example, an electroless copper plating layer called a seed layer is provided on the base material, and then a resist pattern is further provided on the electroless copper plating layer. Next, after forming a conductive pattern by plating on the electroless copper plating layer on which the resist pattern is not provided, the unnecessary resist pattern and the electroless copper plating layer (seed layer) are removed.

Patent Document 1: Japanese Patent Application Laid-Open No. 2015-225650 Patent Document 2: Japanese Patent Application Laid-Open No. 2015-065376

For example, in order to reduce the electrical resistance of the conductive pattern, a thick conductive pattern may be formed. However, in the subtractive method, the resist pattern is protected by a phenomenon in which etching proceeds isotropically in the in-plane direction of the base material on which the conductive layer is arranged (for example, referred to as "side etching"). The conductive layer may also be eroded by the chemical solution. Since the occurrence of side etching affects the morphology (eg, shape and dimensions) of the conductive pattern formed through etching, it may be difficult to form, for example, a rectangular conductive pattern. .. In the semi-additive method, it is a problem that the formation of the conductive pattern becomes unstable due to the adhesion between the seed layer and the resist pattern. Further, since a part of the conductive pattern may be removed when the unnecessary seed layer is removed, the semi-additive method has the same problems as the subtractive method.

This disclosure has been made in view of the above circumstances.
The problem to be solved by one embodiment of the present disclosure is the occurrence of morphological abnormalities (generation of tapered shape due to cracking, peeling, chipping or side etching, or dimensional fluctuation due to etching variation. The same shall apply hereinafter. ) Is to provide a method of manufacturing a structure having a reduced pattern.
Another problem to be solved by other embodiments of the present disclosure is to provide a structure having a pattern in which the occurrence of morphological abnormalities is reduced.

Means for solving the above problems include the following aspects.
<1> A negative type that is arranged on the transparent base material, the light-shielding pattern 1 arranged on the transparent base material, the transparent base material, and the light-shielding pattern 1 and is in contact with the transparent base material. A part of the negative type photosensitive resin layer N from a surface opposite to the surface of the transparent base material provided with the light-shielding pattern 1 in the step of preparing a laminate having the photosensitive resin layer N. The step of irradiating the transparent substrate with light, the step of forming the resin pattern 2 on the transparent substrate by developing the negative type photosensitive resin layer N irradiated with light, and the light-shielding pattern 1 and the resin. A method for producing a structure comprising the step of forming a pattern 3 in a region defined by the pattern 2 and the obtained structure having the resin pattern 2 as a permanent film.
<2> The method for producing a structure according to <1>, wherein the light-shielding pattern 1 contains a metal.
<3> The method for producing a structure according to <1> or <2>, wherein the pattern 3 has conductivity.
<4> The method for manufacturing a structure according to any one of <1> to <3>, wherein the pattern 3 is a pattern formed by a plating method.
<5> The method for producing a structure according to any one of <1> to <4>, wherein the light-shielding pattern 1 and the pattern 3 contain the same kind of material.
<6> The structure according to any one of <1> to <5>, wherein the negative photosensitive resin layer N contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator. Production method.
<7> The method for producing a structure according to <6>, wherein the ethylenically unsaturated compound contains a trifunctional or higher functional ethylenically unsaturated compound.
<8> The method for producing a structure according to <6> or <7>, wherein the ethylenically unsaturated compound contains a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
<9> The structure according to any one of <1> to <5>, wherein the negative photosensitive resin layer N contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocationic polymerization initiator. Production method.
<10> The method for producing a structure according to any one of <1> to <9>, wherein the negative photosensitive resin layer N contains a metal oxidation inhibitor.
<11> A step of forming a light-shielding layer on one surface of a transparent substrate, a step of forming a photoresist layer on the light-shielding layer, a step of exposing and developing the photoresist layer to form a resist pattern, and a step of forming a resist pattern. The method for producing a structure according to any one of <1> to <10>, further comprising a step of etching the light-shielding layer to form the light-shielding pattern 1.
<12> The method for producing a structure according to any one of <1> to <11>, wherein the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
<13> The method for producing a structure according to any one of <1> to <12>, wherein the transparent base material is a transparent film base material.
<14> The method for producing a structure according to any one of <1> to <13>, further comprising a step of performing at least one of post-exposure and post-heating on the resin pattern 2.
<15> The method for producing a structure according to any one of <1> to <14>, wherein the negative photosensitive resin layer N is a layer formed of a photosensitive transfer material.
<16> The obtained structure is one type of structure selected from the group consisting of a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film <1> to <15. > The method for manufacturing a structure according to any one of.
<17> The transparent base material, the light-shielding pattern 1 arranged on the transparent base material, and the transparent base material arranged adjacent to the light-shielding pattern 1 on the transparent base material and on the transparent base material. The resin pattern 2 in contact with the light-shielding pattern 1 and the pattern 3 in the region defined by the light-shielding pattern 1 and the resin pattern 2 are provided, and the average thickness of the light-shielding pattern 1 is 2 μm or less, and the resin pattern 2 The average thickness of the pattern 3 exceeds 2 μm, the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1, and the structure has the resin pattern 2 as a permanent film.

According to one embodiment of the present disclosure, it is possible to provide a method for manufacturing a structure having a pattern in which the occurrence of morphological abnormalities is reduced.
Further, according to another embodiment of the present disclosure, it is possible to provide a structure having a pattern in which the occurrence of morphological abnormalities is reduced.

It is a schematic cross-sectional view which shows an example of the manufacturing method of the structure which concerns on this disclosure. It is a schematic cross-sectional view which shows an example of the structure which concerns on this disclosure.

The contents of the present disclosure will be described below. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
In addition, the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam. In addition, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams (active energy rays) are used. Can be mentioned.
Further, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
In the present disclosure, "alkali-soluble" means the property that the solubility of sodium carbonate in an aqueous solution (100 g, sodium carbonate concentration: 1% by mass) is 0.1 g or more at a liquid temperature of 22 ° C.
In the present disclosure, "conductive" means a property in which an electric current easily flows. The required current flowability is not limited and may be as long as it is necessary for the purpose and application. When the conductivity is expressed by the volume resistivity, the volume resistivity is preferably less than ^{1 × 10 6} Ωcm, and more preferably less than ^{1 × 10 4 Ωcm.}
In the present disclosure, "light" means electromagnetic waves including ultraviolet rays, visible rays, and infrared rays. The light is preferably light having a wavelength in the range of 200 nm to 1,500 nm, more preferably light having a wavelength in the range of 250 nm to 450 nm, and particularly preferably light having a wavelength in the range of 300 nm to 410 nm. preferable.
In the present disclosure, the "solid content" means a component obtained by removing a solvent from all the components of an object.

(Manufacturing method of structure)
The method for producing a structure according to the present disclosure includes a transparent base material, a light-shielding pattern 1 arranged on the transparent base material, a transparent base material, and a light-shielding pattern 1 arranged on the transparent base material and the light-shielding pattern 1. A step of preparing a laminate having a negative type photosensitive resin layer N in contact with the transparent base material (hereinafter, also referred to as a “preparation step”) and the light-shielding pattern 1 of the transparent base material are provided. A step of irradiating a part of the negative type photosensitive resin layer N with light from a surface opposite to the surface (hereinafter, also referred to as “exposure step”), the negative type photosensitive resin layer N irradiated with light. By developing the above, a step of forming the resin pattern 2 on the transparent substrate (hereinafter, also referred to as “development step”), and a region defined by the light-shielding pattern 1 and the resin pattern 2 The structure including the step of forming the pattern 3 (hereinafter, also referred to as “pattern 3 forming step”) has the resin pattern 2 as a permanent film.

The reason why the method for producing the structure according to the present disclosure exerts the above effect is presumed as follows.
As described above, the present inventor has found that the controllability of the shape and dimensions of the pattern may not be sufficient in the conventional method for manufacturing a structure (for example, the subtractive method and the semi-additive method).
On the other hand, in the method for producing a structure according to the present disclosure, by including each of the above steps, it is possible to reduce the occurrence of pattern morphological abnormality due to, for example, side etching or removal of the seed layer.
Here, a method for manufacturing the structure according to the present disclosure will be described with reference to FIG.
FIG. 1 is a schematic cross-sectional view showing an example of a method for manufacturing a structure according to the present disclosure. FIG. 1A shows an example of the preparation step. FIG. 1B shows an example of the exposure process. FIG. 1C shows an example of the developing process. FIG. 1D shows an example of the pattern 3 forming step.
The laminate 100 shown in FIG. 1A has a transparent base material 10, a light-shielding pattern 20 (light-shielding pattern 1), and a negative-type photosensitive resin layer 30 (negative-type photosensitive resin layer N). Have. As shown in FIG. 1 (b), the surface of the transparent base material 10 opposite to the surface facing the light-shielding pattern 20 (that is, the surface to be exposed 10a) is irradiated with light. Since the proportion of light passing through the light-shielding pattern 20 is small, the light incident on the exposed surface 10a of the transparent base material 10 passes through the exposed portion 30a of the negative photosensitive resin layer 30 via the transparent base material 10. As a result, the exposed portion 30a of the negative type photosensitive resin layer 30 is selectively exposed. As shown in FIG. 1 (c), the negative type photosensitive resin layer 30 is developed to remove the portion of the negative type photosensitive resin layer 30 other than the exposed portion 30a, and the transparent base material 10 and the light-shielding pattern 20 are removed. The resin pattern 40 (resin pattern 2) is formed in the region (that is, the groove) defined by. As shown in FIG. 1 (d), a pattern 50 (pattern 3) is formed on the light-shielding pattern 20. In FIG. 1D, the pattern 50 is formed in a region (ie, a groove) defined by a light-shielding pattern 20 that functions like a mold and a resin pattern 40. By going through the above steps, the pattern 50 can be easily formed.
Therefore, according to the method for manufacturing a structure according to the present disclosure, a pattern (preferably a conductive pattern) in which the occurrence of morphological abnormalities is reduced is formed.

In the method for producing a structure according to the present disclosure, the obtained structure has the above resin pattern 2 as a permanent film.
In the present disclosure, the "permanent film" is a film (layer) that remains even after the completion of an article having the above structure (including a product and the case where the structure itself is an article). Specific examples of the permanent film include an insulating film, a protective film, a spacer, and the like.
The structure obtained by the method for manufacturing a structure according to the present disclosure is one type of structure selected from the group consisting of, for example, a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film. It is preferably a body.

<Preparation process>
The method for producing a laminate according to the present disclosure is a transparent base material, a light-shielding pattern 1 arranged on the transparent base material, a transparent base material, and a light-shielding pattern 1 arranged on the transparent base material and the light-shielding pattern 1. The step (preparation step) of preparing a laminate having the negative type photosensitive resin layer N in contact with the transparent base material is included.
In the present disclosure, "preparation" means making an object ready for use. The laminated body may be a laminated body manufactured in advance. The laminate may be a laminate produced in the preparatory step. That is, the preparation step may include a step of manufacturing the laminate.

[Transparent substrate]
The laminate has a transparent substrate. In the present disclosure, "transparent" means that the transmittance of the exposure wavelength in the exposure step is 50% or more. The transmittance of the exposure wavelength defined by the term "transparent" is preferably 80% or more, more preferably 90%, and particularly preferably 95%. In the present disclosure, the "transmittance of an exposure wavelength" means the transmittance of a wavelength included in the light that reaches an object (for example, a transparent substrate) in the exposure process. For example, when a light source having a wavelength of 365 nm is used in the exposure step, the “transmittance of the exposure wavelength” means the transmittance of the wavelength of 365 nm. In the present disclosure, "transmittance" refers to the intensity of incident light when light is incident in a direction perpendicular to the main surface of the object to be measured (that is, in the thickness direction), and is emitted through the object to be measured. It is the ratio of the intensity of the emitted light. The transmittance is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Further, the transparent substrate preferably has a light transmittance of 80% or more at a wavelength of 400 nm to 700 nm.

The shape of the transparent base material is not limited. As the transparent base material, for example, a film-shaped or plate-shaped transparent base material is preferably used. Above all, the transparent base material is preferably a transparent film base material.

Examples of the transparent substrate include a resin substrate (for example, a resin film) and a glass substrate. The resin substrate is preferably a resin substrate that transmits visible light. Preferred components of the resin substrate that transmits visible light include, for example, polyamide-based resin, polyethylene terephthalate-based resin, polyethylene naphthalate-based resin, cycloolefin-based resin, polyimide-based resin, and polycarbonate-based resin. More preferable components of the resin substrate that transmits visible light include, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate. The transparent substrate is preferably a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer (COP), a polyethylene naphthalate film, a polyimide film, or a polycarbonate film, and more preferably a polyethylene terephthalate film.

Examples of the transparent base material include paper phenol, paper epoxy, glass composite, glass epoxy, polytetrafluoroethylene, and a rigid flexible material in which a hard material and a soft material are combined. The transparent base material may be a porous transparent base material. The transparent substrate may contain a filler and an additive.

The surface of the transparent base material may be modified by, for example, alkali treatment or energy ray irradiation.

The structure of the transparent base material may be a single-layer structure or a multi-layer structure. The transparent substrate may include, for example, a functional layer. Examples of the functional layer include an adhesive layer, a hard coat layer, and a refractive index adjusting layer.

The thickness of the transparent substrate is not limited. The thickness of the transparent substrate is preferably in the range of 10 μm to 200 μm, more preferably in the range of 20 μm to 120 μm, and particularly preferably in the range of 20 μm to 100 μm. The thickness of the transparent substrate is measured by the following method. A scanning electron microscope (SEM) is used to observe a cross section in a direction perpendicular to the main surface of the transparent substrate (ie, in the thickness direction). Based on the obtained observation image, the thickness of the transparent substrate is measured at 10 points. The average thickness of the transparent substrate is obtained by arithmetically averaging the measured values.

The total light transmittance of the transparent substrate is preferably high. The total light transmittance of the transparent substrate is preferably 50% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more. The upper limit of the total light transmittance of the transparent substrate is not limited. The total light transmittance of the transparent substrate may be determined in the range of 100% or less. The total light transmittance is measured by the method specified in JIS K 7361-1 (1997).

[Light-shielding pattern]
The laminate has a light-shielding pattern 1 on a transparent substrate. For example, as shown in FIG. 1B, when the laminate has the light-shielding pattern 1, a part of the negative photosensitive resin layer can be selectively exposed in the exposure step. In the present disclosure, "light shielding" means that the transmittance of the exposure wavelength is less than 50%. The transmittance of the exposure wavelength defined by the term "light shielding" is preferably less than 30%, more preferably less than 10%, and particularly preferably less than 1%.
Further, the light-shielding pattern 1 preferably has a light transmittance of less than 30% at a wavelength of 400 nm to 700 nm.

The light-shielding pattern 1 preferably has conductivity. The conductive light-shielding pattern 1 can function as an electric conductor (for example, a seed layer) when plating is performed in the pattern 3 forming step described later, for example. The seed layer can function as a cathode in, for example, electroplating.
Above all, the light-shielding pattern 1 preferably contains a metal.

Examples of the component of the light-shielding pattern 1 include metal. Examples of the metal include Nb (niobium), Al (aluminum), Ni (nickel), Zn (zinc), Mo (molybdenum), Ta (tantalum), Ti (titanium), V (vanadium), and Cr (chromium). , Fe (iron), Co (cobalt), W (tungsten), Cu (copper), Sn (tin), and Mn (manganese). The light-shielding pattern 1 preferably contains a metal from the viewpoint of conductivity, and is composed of Nb, Al, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn and Mn. It is more preferable to contain at least one metal selected from the group, and it is particularly preferable to contain Cu. Cu is preferable from the viewpoint of low electrical resistance and low cost. The light-shielding pattern 1 may contain one kind alone or two or more kinds of metals. The metal contained in the light-shielding pattern 1 may be a single metal or an alloy. The light-shielding pattern 1 preferably contains Cu or an alloy of Cu. When the light-shielding pattern 1 contains a metal, the metal element contained in the light-shielding pattern may be the same as or different from the metal element contained in the conductive pattern described later. The light-shielding pattern 1 preferably contains the same metal element as the metal element contained in the conductive pattern.

The light-shielding pattern 1 may contain an element other than a metal element. Examples of elements other than metal elements include C (carbon), P (phosphorus), and B (boron). Elements other than metal elements may form alloys with metal elements.

The shape of the light-shielding pattern 1 is not limited. The shape of the light-shielding pattern 1 may be determined, for example, according to the shape of the target conductive pattern.

The structure of the light-shielding pattern 1 may be a single-layer structure or a multi-layer structure. The components of each layer of the light-shielding pattern 1 having a multi-layer structure may be the same or different.

The thickness of the light-shielding pattern 1 is not limited. The average thickness of the light-shielding pattern 1 is preferably 3 μm or less, more preferably 2 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. When the average thickness of the light-shielding pattern 1 is 3 μm or less, the moldability of the light-shielding pattern can be improved. As a result, the occurrence of morphological abnormalities of the conductive pattern can be further reduced. The average thickness of the light-shielding pattern 1 is preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.3 μm or more. When the average thickness of the light-shielding pattern 1 is 0.05 μm or more, the transmittance of the exposure wavelength can be reduced. Further, when the light-shielding pattern 1 is used as the seed layer, the productivity of the conductive pattern can be improved. The average thickness of the light-shielding pattern 1 is measured by a method according to the method for measuring the average thickness of the transparent substrate.

The width of the light-shielding pattern 1 is not limited. The width of the light-shielding pattern 1 is the length of the light-shielding pattern 1 in the direction perpendicular to the longitudinal direction of the light-shielding pattern 1 in the surface direction of the transparent base material. For example, if the light-shielding pattern 1 is a line-and-space pattern, the width of the light-shielding pattern 1 is the length of the line pattern in the lateral direction. Further, for example, when the light-shielding pattern 1 has a circular or elliptical cross-sectional shape in the plane direction of the transparent base material, the width of the light-shielding pattern 1 is the minimum diameter in the circular or elliptical shape.
The width of the light-shielding pattern 1 may be determined, for example, according to the width of the conductive pattern formed in the pattern 3 forming step. The average width of the light-shielding pattern 1 is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. The average width of the light-shielding pattern 1 is preferably 0.1 μm or more, and more preferably 0.5 μm or more. The average width of the light-shielding pattern 1 is an arithmetic mean of the width of the light-shielding pattern measured at five points.

The light-shielding pattern 1 may be in contact with the transparent substrate directly or via another layer. Examples of the other layer include an adhesion layer. For example, the laminate may have an adhesion layer between the transparent substrate and the light-shielding pattern 1. The components of the adhesion layer are not limited. The components of the adhesion layer are, for example, the adhesion between the transparent base material and the light-shielding pattern 1, and the stability of the conductive pattern obtained by the method for producing the structure according to the present disclosure in the usage environment (for example, humidity and temperature). It may be decided according to the sex. The adhesion layer preferably contains at least one selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. The adhesion layer may further contain at least one selected from the group consisting of C (carbon atom), O (oxygen atom), H (hydrogen atom), and N (nitrogen atom). The adhesion layer may be a blackening layer. The blackened layer can suppress the reflection of light due to the light-shielding pattern in the exposure process. When the adhesion layer functions as a blackening layer, the adhesion layer preferably contains, for example, a Ni—Cu alloy. The adhesion layer that functions as a blackening layer may further contain at least one selected from the group consisting of C, O, H, and N. The thickness of the adhesion layer is not limited. The average thickness of the adhesion layer is preferably 3 nm to 50 nm, more preferably 3 nm to 35 nm, and particularly preferably 3 nm to 33 nm.

[Negative type photosensitive resin layer N]
The laminate has a negative photosensitive resin layer N that is arranged on the transparent base material and the light-shielding pattern 1 and is in contact with the transparent base material. The negative photosensitive resin layer N may be in contact with the light-shielding pattern 1 directly or via another layer. The negative photosensitive resin layer N is preferably in contact with the light-shielding pattern 1. As the negative type photosensitive resin layer N, a known negative type photosensitive resin layer can be used.

In a certain embodiment, the negative photosensitive resin layer N preferably contains a polymer A described later, a polymerizable compound B described later, and a photopolymerization initiator. The negative type photosensitive resin layer N includes 10% by mass to 90% by mass of the polymer A and 5% by mass to 70% by mass of the polymerizable compound B with respect to the total mass of the negative type photosensitive resin layer N. It is preferable to contain 0.01% by mass to 20% by mass of a photopolymerization initiator. In certain embodiments, the negative photosensitive resin layer N preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.

Further, the negative photosensitive resin layer N preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photoacid generator from the viewpoint of curability and developability.
Further, the negative photosensitive resin layer N preferably contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a cationic polymerization initiator from the viewpoint of strength and durability of the obtained resin pattern 2 as a permanent film. ..
Hereinafter, the negative type photosensitive resin layer N will be specifically described.

-Alkali-soluble polymer-
The negative photosensitive resin layer N preferably contains an alkali-soluble polymer.
In the present disclosure, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
The alkali-soluble polymer preferably has an acid value of 60 mgKOH / g or more from the viewpoint of developability, for example.
Further, the alkali-soluble polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with a crosslinked component by heating to form a strong film. Is more preferable, and an acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing acrylic resin) is particularly preferable.
In the present disclosure, the acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound, and the content of the structural unit is preferably 30% by mass or more with respect to the total mass of the resin. , 50% by mass or more is more preferable.
When the alkali-soluble polymer is a resin having a carboxy group, the three-dimensional crosslink density can be increased by adding a heat-crosslinkable compound such as a blocked isocyanate compound and heat-crosslinking. Further, when the carboxy group of the resin having a carboxy group is anhydrous and hydrophobized, the wet heat resistance can be improved.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known acrylic resins and used.
For example, among the polymers described in paragraphs 0025 of JP2011-95716A, carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and the polymers described in paragraphs 0033 to 0052 of JP2010-237589A. , A carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.

The alkali-soluble polymer is preferably an acrylic resin or a styrene-acrylic copolymer from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and adhesiveness of the obtained uncured film. More preferably, it is a styrene-acrylic copolymer.
In the present disclosure, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and the structural unit derived from the styrene compound and the (meth) compound. ) The total content of the constituent units derived from the acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the copolymer.
The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and 5% by mass or more and 80% by mass with respect to the total mass of the copolymer. It is particularly preferable that it is% or less.
The content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass, based on the total mass of the copolymer. It is particularly preferable that it is% or more and 95% by mass or less.
Further, examples of the (meth) acrylic compound include (meth) acrylate compound, (meth) acrylic acid, (meth) acrylamide compound, and (meth) acrylonitrile. Among them, at least one compound selected from the group consisting of (meth) acrylate compound and (meth) acrylic acid is preferable.

<< Polymer A >>
The negative photosensitive resin layer N preferably contains the polymer A. The polymer A is preferably an alkali-soluble polymer. Alkali-soluble polymers include polymers that are easily soluble in alkaline substances. In the present disclosure, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.

The acid value of the polymer A is preferably 220 mgKOH / g or less, and less than 200 mgKOH / g, from the viewpoint of more excellent resolution by suppressing the swelling of the negative photosensitive resin layer N due to the developing solution. It is more preferable, and it is particularly preferable that it is less than 190 mgKOH / g. The lower limit of acid value is not limited. The acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and 170 mgKOH / g or more, from the viewpoint of more excellent developability. It is particularly preferable that it is g or more. The acid value of the polymer A can be adjusted, for example, by the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.

In the present disclosure, the acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. In the present disclosure, the unit of acid value is described as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The weight average molecular weight (Mw) of the polymer A is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolvability and the developability. The weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, it is preferable to set the weight average molecular weight to 5,000 or more from the viewpoint of controlling the properties of the developed aggregate. The weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.

The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0.0 to 3.0. In the present disclosure, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

The polymer A preferably has a structural unit having an aromatic hydrocarbon group from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of the resolution, and the polymer A preferably contains an aromatic hydrocarbon group. It is more preferable to have a structural unit derived from the monomer having.

Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.

The content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of the polymer A. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. The upper limit of the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is not limited. The content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 95% by mass or less, preferably 85% by mass or less, based on the total mass of the polymer A. Is more preferable. When the negative photosensitive resin layer contains a plurality of types of polymers A, the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-). Vinyl benzoic acid, styrene dimer, and styrene trimmer). The monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.

Examples of the monomer having a benzyl group include a (meth) acrylate having a benzyl group (for example, benzyl (meth) acrylate and a chlorobenzyl (meth) acrylate), a vinyl monomer having a benzyl group (for example, vinylbenzyl chloride, and the like). Vinyl benzyl alcohol). The monomer having a benzyl group is preferably a benzyl (meth) acrylate.

In certain embodiments, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from the benzyl (meth) acrylate, the benzyl (meth) acrylate single amount in the polymer A is used. The content ratio of the structural unit derived from the body is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and 70% by mass, based on the total mass of the polymer A. It is more preferably% to 90% by mass, and particularly preferably 75% by mass to 90% by mass.

In a certain embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from styrene, the content ratio of the structural unit derived from styrene in the polymer A is determined. It is preferably 20% by mass to 55% by mass, more preferably 25 to 45% by mass, further preferably 30% by mass to 40% by mass, and 30% by mass, based on the total mass of the polymer A. It is particularly preferably from mass% to 35% by mass.

In a certain embodiment, the polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, a first monomer described later, and a monomer described later. It is preferable that the copolymer is obtained by polymerizing at least one selected from the group consisting of the second monomer. The copolymer is a group consisting of a structural unit derived from a monomer having an aromatic hydrocarbon group, a structural unit derived from the first monomer, and a structural unit derived from the second monomer. It has at least one selected from.

The polymer A may be a polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group. The polymer A having no structural unit derived from the monomer having an aromatic hydrocarbon group is at least one kind of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later. It is preferable that the polymer is obtained by polymerizing the above, and at least one of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later and the second simpler described later. It is more preferable that it is a copolymer obtained by polymerizing at least one of a dimer (excluding a monomer having an aromatic hydrocarbon group).

In a certain embodiment, the polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and is preferably the same as at least one of the first monomers described below. It is more preferable that the copolymer is obtained by polymerizing with at least one of the second monomers described later. The copolymer has a structural unit derived from the first monomer and a structural unit derived from the second monomer.

The first monomer is a monomer having a carboxy group and a polymerizable unsaturated group in the molecule. The first monomer may be a monomer having no aromatic hydrocarbon group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester. The first monomer is preferably (meth) acrylic acid.

The content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of the polymer A. Is more preferable, and 15% by mass to 30% by mass is particularly preferable.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. The second monomer may be a monomer having no aromatic hydrocarbon group in the molecule. Examples of the second monomer include a (meth) acrylate compound, an ester compound of vinyl alcohol, and (meth) acrylonitrile. In the present disclosure, "(meth) acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Examples thereof include tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Examples of the (meth) acrylate compound include those having an alicyclic alkyl group, a linear alkyl group, and a branched alkyl group.

Examples of the ester compound of vinyl alcohol include vinyl acetate.

The second monomer is preferably at least one selected from the group consisting of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate, and is preferably methyl (meth). More preferably, it is an acrylate.

The content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, and 15% by mass to 50% by mass, based on the total mass of the polymer A. Is more preferable, and 20% by mass to 45% by mass is particularly preferable.

The polymer A is composed of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of resolution. It is preferable to include at least one selected from the group. For example, the polymer A is a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, a structural unit derived from styrene, a structural unit derived from methacrylic acid, and methyl. It is preferably at least one selected from the group consisting of copolymers containing a structural unit derived from methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.

In a certain embodiment, the polymer A contains 25% by mass to 60% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 20% by mass or more of a structural unit derived from a first monomer. A polymer containing 55% by mass and 20% by mass to 55% by mass of a structural unit derived from the second monomer is preferable. In the polymer A, the structural unit derived from the monomer having an aromatic hydrocarbon group is 25% by mass to 40% by mass, the structural unit derived from the first monomer is 20% by mass to 35% by mass, and the like. A polymer containing 30% by mass to 45% by mass of a structural unit derived from the second monomer is more preferable.

In certain embodiments, the polymer A contains 70% by mass to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% by mass of a structural unit derived from a first monomer. It is preferably a polymer containing up to 25% by mass.

The glass transition temperature (Tg) of the polymer A is preferably 30 ° C to 135 ° C. When the Tg of the polymer A is 135 ° C. or lower in the negative photosensitive resin layer, it is possible to suppress the line width thickening and the deterioration of the resolution when the focal position is deviated during exposure. From the above viewpoint, the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. Further, it is preferable that the Tg of the polymer A is 30 ° C. or higher from the viewpoint of improving the edge fuse resistance. From the above viewpoint, the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. preferable.

The polymer A may be a commercially available product or a synthetic product. Polymer A is synthesized, for example, by diluting at least one of the above-mentioned monomers with a solvent (for example, acetone, methyl ethyl ketone, or isopropanol) and a radical polymerization initiator (for example, benzoyl peroxide or azoisobuty) in a solution. Butyronitrile) is preferably added in an appropriate amount, and then heated and stirred. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of alkali-soluble polymers.

The content ratio of the alkali-soluble polymer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the negative photosensitive resin layer N. It is particularly preferably 40% by mass to 60% by mass. It is preferable that the content ratio of the alkali-soluble polymer to the negative photosensitive resin layer N is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content ratio of the alkali-soluble polymer with respect to the negative photosensitive resin layer N is 10% by mass or more from the viewpoint of improving the edge fuse resistance.

When the negative type photosensitive resin layer N contains two or more kinds of alkali-soluble polymers, the negative type photosensitive resin layer N has two or more kinds having a structural unit derived from a monomer having an aromatic hydrocarbon group. It does not have a structural unit derived from an alkali-soluble polymer or a monomer having an aromatic hydrocarbon group, and an alkali-soluble polymer having a structural unit derived from a monomer having an aromatic hydrocarbon group. It preferably contains an alkali-soluble polymer. In the latter case, the content ratio of the alkali-soluble polymer having a structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more with respect to the total mass of the alkali-soluble polymer. , 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

-Polymerizable compound-
The negative photosensitive resin layer N preferably contains a polymerizable compound.
In the present disclosure, the "polymerizable compound" means a compound having a bond or a polymerizable group involved in a polymerization reaction and polymerizing under the action of a polymerization initiator described later.
Further, the polymerizable compound in the present disclosure is a compound different from the alkali-soluble polymer, and preferably has a molecular weight of less than 5,000.
As the polymerizable compound, an ethylenically unsaturated compound is preferable.
The ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoints of the strength of the obtained cured film, substrate adhesion, development residue inhibitory property, and rust prevention property, and will be described later. It is more preferable to contain the compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group.

The ethylenically unsaturated compound is a compound represented by the following formula (M) (simply also referred to as "Compound M") from the viewpoint of developing residue inhibitory property, rust preventive property, and bending resistance of the obtained cured film. It is preferable to include it.
Q ² -R ^¹ -Q ¹ formula (M)
In formula (M), Q ¹ and Q ² each independently represent a (meth) acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

^{It is preferable that Q 1} and Q ² in the formula (M) have the same group as ^{Q 1} and Q ² from the viewpoint of easiness of synthesis.
^{Further, Q 1} and Q ² in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
^{R 1} in the formula (M), from the viewpoint of bending resistance of the obtained cured film, an alkylene group, an alkylene oxyalkylene group ^{^{(-L 1 -O-L 1 -}} ), or, polyalkylene oxyalkylene group (- (L ^1- O) _p- L ^1- ) is preferable, and a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, and an alkylene group having 4 to 20 carbon atoms is used. It is more preferable, and it is particularly preferable that it is a linear alkylene group having 6 to 18 carbon atoms. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited, and is, for example, branched chain, cyclic, or having 1 to 5 carbon atoms. It may be any of a linear alkylene group, an arylene group, an ether bond, and a combination thereof, and from the viewpoint of bending resistance of the obtained cured film, an alkylene group or two or more alkylene groups and one or more. It is preferably a group in combination with an arylene group, more preferably an alkylene group, and particularly preferably a linear alkylene group.
Each of the above L ¹ independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

The atomic number of the connecting chain of the shortest for connecting the Q ^1, Q ² in the compound M, from the viewpoints of moisture permeability and bending resistance of the obtained cured film is preferably from 3 to 50, The number is more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.
In this disclosure, the term "Q ^1, Q atoms linking chain shortest connecting between ^two" shortest connecting the atom in R ¹ be linked to Q ¹ to atom in R ¹ be linked to Q ² Is the number of atoms in.

Specific examples of the compound M include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. 1,7-Heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1, 4-Cyclohexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, poly (ethylene glycol / propylene glycol) di (meth) acrylate, polybutylene glycol di (meth) acrylate. The ester monomer can also be used as a mixture.
Among the above compounds, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate from the viewpoint of bending resistance of the obtained cured film. It is preferably at least one compound selected from the group consisting of acrylates and neopentyl glycol di (meth) acrylates, preferably 1,6-hexanediol di (meth) acrylates and 1,9-nonanediol di (). More preferably, it is at least one compound selected from the group consisting of meta) acrylate and 1,10-decanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate and It is particularly preferable that the compound is at least one selected from the group consisting of 1,10-decanediol di (meth) acrylate.

Compound M may be used alone or in combination of two or more.
The content of compound M is 10% by mass to 90% by mass with respect to the total mass of the ethylenically unsaturated compound of the negative photosensitive resin layer N from the viewpoint of moisture permeability and bending resistance of the obtained cured film. Is more preferable, 15% by mass to 70% by mass is more preferable, 20% by mass to 50% by mass is further preferable, and 25% by mass to 35% by mass is particularly preferable.
The ethylenically unsaturated compound in the present disclosure refers to a compound having an ethylenically unsaturated group having a (weight average) molecular weight of 10,000 or less.
The content of the compound M is preferably 1% by mass to 30% by mass with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of moisture permeability and bending resistance of the obtained cured film. It is more preferably from mass% to 25% by mass, further preferably from 5% by mass to 20% by mass, and particularly preferably from 6% by mass to 14.5% by mass.

The ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound.
In the present disclosure, the "bifunctional or higher functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth) acryloyl group is preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

Examples of the ethylenically unsaturated compound include a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenic compound from the viewpoint of the strength of the cured film after curing. It is particularly preferred to include unsaturated compounds (preferably trifunctional or higher functional (meth) acrylate compounds).

<< Polymerizable Compound B >>
The negative photosensitive resin layer N preferably contains the polymerizable compound B. The polymerizable compound B is a compound different from the polymer A.
As the bond involved in the polymerization reaction in the polymerizable compound B, for example, an ethylenically unsaturated bond is preferably mentioned.

The polymerizable group in the polymerizable compound B is not limited as long as it is a group involved in the polymerization reaction. Examples of the polymerizable group in the polymerizable compound B include a group containing an ethylenically unsaturated bond (for example, a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group), and a cationically polymerizable group (for example, a cationically polymerizable group). Epoxide group and oxetane group). The polymerizable group is preferably a group containing an ethylenically unsaturated bond (hereinafter, may be referred to as an "ethylenically unsaturated group"), and more preferably an acryloyl group or a metaacryloyl group.

The polymerizable compound B is preferably a compound having an ethylenically unsaturated bond in that the negative photosensitive resin layer N is more excellent in photosensitivity, and has one or more ethylenically unsaturated groups in one molecule. It is more preferably a compound having (ie, an ethylenically unsaturated compound), and particularly preferably a compound having two or more ethylenically unsaturated groups in one molecule (ie, a polyfunctional ethylenically unsaturated compound). preferable. In addition, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, and preferably 3 or less, in terms of being excellent in resolution and peelability. It is more preferable, and it is particularly preferable that the number is two or less.
Further, the polymerizable compound B preferably contains a trifunctional or higher functional ethylenically unsaturated compound from the viewpoint of curability and the strength and durability of the obtained resin pattern 2 as a permanent film, and is pentafunctional or higher. More preferably, it contains an ethylenically unsaturated compound.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule.

The polymerizable compound B is a compound having two ethylenically unsaturated groups in one molecule (that is, 2) from the viewpoint of having a better balance of photosensitivity, resolution, and peelability in the negative photosensitive resin layer N. It is preferable to contain at least one selected from the group consisting of a functional ethylenically unsaturated compound) and a compound having three ethylenically unsaturated groups in one molecule (that is, a trifunctional ethylenically unsaturated compound). It is more preferable to contain a compound having two ethylenically unsaturated groups in one molecule.

Further, the polymerizable compound B preferably contains an ethylenically unsaturated compound having an aliphatic cyclic skeleton from the viewpoint of strength and dimensional stability after curing, and is a di (meth) acrylate having an aliphatic cyclic skeleton. It is more preferable to contain a compound, and it is particularly preferable to contain a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
Further, the polymerizable compound B preferably contains an ethylenically unsaturated compound having a dicyclopentanyl structure or a dicyclopentenyl structure from the viewpoint of strength and dimensional stability after curing.

In the negative type photosensitive resin layer N, the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is 40% by mass or more from the viewpoint of excellent peelability of the negative type photosensitive resin layer N. It is preferably 60% by mass or more, and particularly preferably more than 70% by mass. The upper limit of the content ratio of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is not limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the negative photosensitive resin layer N may be bifunctional ethylenically unsaturated compounds.

-Polymerizable compound B1-
The negative photosensitive resin layer N according to the present disclosure preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.

In the negative photosensitive resin layer, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, preferably 50% by mass or more, from the viewpoint of better resolution. It is more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited. The ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, and 90% by mass or less from the viewpoint of peelability. Is more preferable, and 85% by mass or less is particularly preferable.

Examples of the aromatic ring in the polymerizable compound B1 include an aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, and an anthracene ring) and an aromatic heterocycle (for example, a thiophene ring, a furan ring, a pyrrole ring, and an imidazole ring. Triazole ring and pyridine ring), and fused rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the negative photosensitive resin layer N due to the developing solution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (that is, 2,2-bis (4-hydroxyphenyl) propane) and bisphenol F (that is, 2,2-bis (4-hydroxyphenyl) methane). Examples include a bisphenol F structure derived from bisphenol B and a bisphenol B structure derived from bisphenol B (that is, 2,2-bis (4-hydroxyphenyl) butane). The bisphenol structure is preferably a bisphenol A structure.

Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may be directly attached to the bisphenol structure. Each polymerizable group may be attached to the bisphenol structure via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162. The contents of the above publication are incorporated herein by reference.

The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. ..

Examples of the 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.). Co., Ltd.), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-500, Shin-Nakamura Chemical Industry Co., Ltd.) )), 2,2-Bis (4- (methacryloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) ) Propane (BPE-1300, Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylation (10) Examples thereof include bisphenol A diacrylate (NK ester A-BPE-10, Shin-Nakamura Chemical Industry Co., Ltd.).

Examples of the polymerizable compound B1 include a compound represented by the following general formula (I).

In the general formula (I), R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, A represents C ₂ H ₄ , B represents C ₃ H ₆ , and n. ₁ and n ₃ are independently integers from 1 to 39, n ₁ + n ₃ are integers from 2 to 40, and n ₂ _{and n 4} are independent integers from 0 to 29, respectively. N ₂ + n ₄ is an integer of 0 to 30, and the sequence of repeating units of-(AO)-and-(BO)-is random or block. good. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side. n ₂ + n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0. n ₁ + n ₂ + n ₃ + n ₄ is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.

The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of polymerizable compounds B1.

The content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N is preferably 10% by mass or more with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of better resolution. More preferably, it is 20% by mass or more. The upper limit of the content ratio of the polymerizable compound B1 is not limited. The content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N shall be 70% by mass or less with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of transferability and edge fuse resistance. Is preferable, and 60% by mass or less is more preferable.

The negative photosensitive resin layer N may contain a polymerizable compound B1 and a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include a monofunctional ethylenically unsaturated compound (that is, a compound having one ethylenically unsaturated group in one molecule) and a bifunctional ethylenically having no aromatic ring. Unsaturated compounds (ie, compounds that do not have an aromatic ring in one molecule and have two ethylenically unsaturated groups), and trifunctional or higher functional ethylenically unsaturated compounds (ie, in one molecule). Compounds having 3 or more ethylenically unsaturated groups).

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.

Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Industry Co., Ltd.). ), 1,9-Nonandiol diacrylate (A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Industry Co., Ltd.), Examples thereof include ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.

Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and alkylene oxide modified products thereof. In the present disclosure, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept that includes tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. be. In the present disclosure, "(tri / tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the alkylene oxide-modified product of the trifunctional or higher functional ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) and Shin Nakamura Chemical Industry Co., Ltd. ( A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth) acrylate compound (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin Nakamura Chemical Industry Co., Ltd., Shin Nakamura A-9300 manufactured by Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex, ethoxylated glycerin triacrylate (for example, A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Examples thereof include Aronix (registered trademark) TO-2349 (Toa Synthetic Co., Ltd.), Aronix M-520 (Toa Synthetic Co., Ltd.), and Aronix M-510 (Toa Synthetic Co., Ltd.).

Examples of the polymerizable compound B other than the polymerizable compound B1 include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.

In certain embodiments, the negative photosensitive resin layer N preferably contains a polymerizable compound B1 and a trifunctional or higher functional ethylenically unsaturated compound, preferably the polymerizable compound B1 and two or more trifunctional or higher ethylenes. It is more preferable to contain a sex unsaturated compound. In the above embodiment, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound ([total mass of the polymerizable compound B1]: [total mass of the trifunctional or higher ethylenically unsaturated compound] is It is preferably 1: 1 to 5: 1, more preferably 1.2: 1 to 4: 1, and particularly preferably 1.5: 1 to 3: 1.

The weight average molecular weight (Mw) of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of polymerizable compounds B.

The content ratio of the polymerizable compound B in the negative photosensitive resin layer N is preferably 10% by mass to 70% by mass, preferably 20% by mass to 60% by mass, based on the total mass of the negative photosensitive resin layer N. It is more preferably%, and particularly preferably 20% by mass to 50% by mass.

-Multifunctional epoxy resin-
The negative photosensitive resin layer N preferably contains a polyfunctional epoxy resin from the viewpoint of strength and durability of the obtained pattern 2 as a permanent film, and preferably contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocation. It is more preferable to include a polymerization initiator.
Examples of the polyfunctional epoxy resin include an epoxy compound having at least two oxylan groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position in one molecule, and the like.

Examples of the epoxy compound having at least two oxylan groups in one molecule include a bisphenol F type epoxy resin (Epototo YDF-170, manufactured by Toto Kasei Co., Ltd.), a bixilenol type or a biphenol type epoxy resin (“YX4000,” Japan Epoxy Resin Co., Ltd. ”, etc.) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton, etc. (“TEPIC, manufactured by Nissan Chemical Industry Co., Ltd.”, “Araldite PT810, manufactured by Huntsman Advanced Materials Co., Ltd.”, etc.) , Bisphenol A type epoxy resin, Novolak type epoxy resin, Bisphenol F type epoxy resin, Hydrogenated Bisphenol A type epoxy resin, Bisphenol S type epoxy resin, Phenol Novolak type epoxy resin, Cresole Novolak type epoxy resin, Halogenized epoxy resin ( For example, low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy Resins, dicyclopentadiene type epoxy resins (“HP-7200, HP-7200H; manufactured by DIC Co., Ltd.”, etc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), Glydil ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydant-in type epoxy resin, alicyclic epoxy resin (3,4-epoxy) Cyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, "GT-300, GT-400, ZEHPE3150; manufactured by Daicel Co., Ltd.", etc. ,), Imid type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (Naftor Aralkill type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type d Epoxy resin, commercially available products such as "ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; manufactured by DIC Co., Ltd."), phenol compounds and divinyl A reaction product of a polyphenol compound obtained by an addition reaction with a diolefin compound such as benzene or dicyclopentadiene and epichlorohydrin, or a ring-opened polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid or the like. Bisphenol A type epoxy resin, octafunctional bisphenol A novolak type epoxy resin (eg, EPON SU-8 manufactured by Resolution Performance Products), epoxy obtained by reacting alcoholic hydroxy groups of bisphenol F type epoxy resin with epichlorohydrin Resin (eg, NER-7604 manufactured by Nippon Kayaku Co., Ltd.), epoxy resin obtained by reacting the alcoholic hydroxy group of bisphenol A type epoxy resin with epichlorohydrin (eg, NER-1302 manufactured by Nihon Kayaku Co., Ltd.) , O-cresol novolac type epoxy resin (eg, EOCN4400 manufactured by Nippon Kayaku Co., Ltd.), obtained by reacting the phenolic hydroxy group of the resin obtained by reacting di (methoxymethylphenyl) with phenol and epichlorohydrin. Biphenylphenol novolac type epoxy resin (eg NC-3000H manufactured by Nippon Kayaku Co., Ltd.), epoxy resin having a cyclic phosphorus-containing structure, α-methylstilben type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl Type liquid crystal epoxy resin, azomethinphenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP-50S, CP-50M; manufactured by Nippon Oil & Fats Co., Ltd.", etc.) , Cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin, bis (glycidyl oxyphenyl) fluorene type epoxy resin, bis (glycidyl oxyphenyl) adamantan type epoxy resin and the like. These may be used alone or in combination of two or more.

Further, in addition to the above-mentioned epoxy compound having at least two oxylan groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position in one molecule can be used, and the β-position is an alkyl group. Compounds containing an epoxy group substituted with (more specifically, a β-alkyl substituted glycidyl group, etc.) are particularly preferable.
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of the two or more epoxy groups contained in one molecule may be β-alkyl substituted glycidyl groups, and at least one epoxy group. May be a β-alkyl substituted glycidyl group.

Examples of the oxetane compound include an oxetane compound having at least two oxetanyl groups in one molecule.
Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-). 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetans such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group, and Examples include ether compounds such as novolak resin, poly (p-hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, resins having a hydroxyl group such as silsesquioxane, and the oxetane ring. Examples thereof include a copolymer of an unsaturated monomer having the above and an alkyl (meth) acrylate.

As the epoxy resin, any epoxy resin can be used as long as it has two or more epoxy groups in one molecule, but the epoxy equivalent of the epoxy resin is 100 g / g so that a sufficient curing rate can be obtained. Equivalent to 500 g / equivalent is preferable, and 100 g / equivalent to 300 g / equivalent is more preferable. The epoxy equivalent referred to here means a value measured by a method based on JIS K-7236.
As the type of epoxy resin, glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type and the like can be used, but glycidyl ether type and glycidyl ester type are preferable because of good liquid storage stability. The ether type is most preferable.
From the viewpoint of developability, the epoxy resin is preferably liquid at room temperature (25 ° C.), more preferably has a viscosity at 25 ° C. of 5,000 mPa · s or less, and is 1,000 mPa · s or less. More preferably. These epoxy resins can be used alone or in admixture of two or more.
Specific examples of the epoxy resin as described above include sorbitol polyglycidyl ether as a glycidyl ether type, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. , Resolsinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether And polypropylene glycol diglycidyl ether, and phthalic acid diglycidyl ester as a glycidyl ester type, tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester can be mentioned.

The negative photosensitive resin layer N may contain one type alone or two or more types of polyfunctional epoxy resins.
The content ratio of the polyfunctional epoxy resin in the negative photosensitive resin layer N is preferably 10% by mass to 90% by mass, preferably 20% by mass to 70% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably.

-Hydroxy group-containing compound-
The negative photosensitive resin layer N preferably contains a hydroxy group-containing compound from the viewpoint of strength and durability of the obtained pattern 2 as a permanent film.
As the hydroxy group-containing compound, a polyol compound or a phenolic compound can be appropriately used.
The polyol compound contains a hydroxy group that reacts with the epoxy group in the epoxy resin under the influence of an acid catalyst and acts as a reactive diluent. In particular, it is preferable to contain polycaprolactone polyol. By containing the polycaprolactone polyol, the dry coating film obtained by drying the solvent component after coating the resin composition is softened, so that stress induction during the production of the laminate is avoided and shrinkage is reduced. , It is possible to prevent cracks in the resin pattern 2 which is a permanent film.

As the polyol compound, a commercially available polyester polyol can be used. Specific examples include "Plaxel 205" having a molecular weight of 530 and an OH value (also referred to as "hydroxyl value") of 210 mgKOH / g, "Plaxel 210" having a molecular weight of 1,000 and an OH value of 110 mgKOH / g, and a molecular weight. "Plaxel 220" with a molecular weight of 2,000 and an OH value of 56 mgKOH / g (both trade names, manufactured by Daicel Co., Ltd.), "Capa2054" with a molecular weight of 550 and an OH value of 204 mgKOH / g, with a molecular weight of 1,000. Examples thereof include "Capa2100" having an OH value of 112 mgKOH / g and "Capa2200" having a molecular weight of 2,000 and an OH value of 56 mgKOH / g (both trade names, manufactured by Perstop).
Examples of the phenol-based compound include phenol novolac resin, cresol novolak resin, polyfunctional bisphenol A novolak resin, biphenylphenol novolac resin, phenol resin having a trishydroxyphenylmethane skeleton, phenol resin having a terpendiphenol skeleton, and bisphenol. Examples thereof include phenol resins made from various phenols such as A and bisphenol F.
The hydroxyl value of the preferred hydroxyl group-containing compound of the hydroxy group-containing compound is preferably 90 mgKOH / g to 300 mgKOH / g, and more preferably 100 mgKOH / g to 250 mgKOH / g. This hydroxy group-containing compound may be used alone or in combination of two or more.

The negative photosensitive resin layer N may contain one kind alone or two or more kinds of hydroxy group-containing compounds.
The content ratio of the hydroxy group-containing compound in the negative photosensitive resin layer N is preferably 1% by mass to 35% by mass, and 5% by mass to 25% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably.

-Photopolymerization initiator-
The negative photosensitive resin layer N preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives active light (for example, ultraviolet rays, visible light, and X-rays) to initiate polymerization of a polymerizable compound (for example, polymerizable compound B).
again,

The photopolymerization initiator is not limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable from the viewpoint of curability.
Further, the negative type photosensitive resin layer N preferably contains a photocationic polymerization initiator from the viewpoint of the strength and durability of the obtained resin pattern 2 as a permanent film.

Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.

The negative photosensitive resin layer N contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed parts, visibility of unexposed parts, and resolution. It preferably contains at least one selected from the group consisting of a mer and a derivative of the 2,4,5-triarylimidazole dimer. The two 2,4,5-triarylimidazole dimers and their derivatives may have the same or different structures.

Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 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 can be mentioned.

Examples of the photoradical polymerization initiator include the polymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783A.

Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.

Commercially available photoradical polymerization initiators include, for example, TAZ-110 (Midori Chemical Co., Ltd.), TAZ-111 (Midori Chemical Co., Ltd.), 1- [4- (Phenylthio)] phenyl-1,2-. Octandion-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Il] Etanon-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2- (dimethylamino)- 2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Omnirad 379EG, IGM Resins BV), 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1- {4- [4- (2-hydroxy-2) -Methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins VV), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butanon-1 (trade name: Omnirad 369, IGM Resins VV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins VV) ), 1-Hydroxycyclohexylphenylketone (trade name: Omnirad 184, IGM Resins VV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, IGM Resins B) V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxide (trade name: Omnirad 819, IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, DKSH Japan Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4, 4 ', 5,5'-Tetraphenyl-1,2'-biimidazole (also known as 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, trade name: B-CIM, Hampford), and Examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.).

Among them, the photoradical polymerization initiator includes at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives of 2,4,5-triarylimidazole dimer. Is preferable.

The photocationic polymerization initiator (that is, a photoacid generator) generates a cation by being irradiated with ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays, electron beams, etc., and the cations are polymerized. It is a compound that can be an initiator.
As the photocationic polymerization initiator, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable. However, the chemical structure of the photocationic polymerization initiator is not limited. In addition, a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.

Examples of the photocationic polymerization initiator include aromatic iodonium complex salts and aromatic sulfonium complex salts.
Specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and trilucmil iodonium tetrakis. Examples thereof include (pentafluorophenyl) borate (manufactured by Rhodia, trade name Rhodesyl PI2074), di (4-tershaributyl) iodonium tris (trifluoromethanesulfonyl) metanide (manufactured by BASF, trade name CGI BBI-C1) and the like. Specific examples of the aromatic sulfonium complex salt include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by San Apro, trade name CPI-101A) and thiophenyldiphenyl sulfonium tris (pentafluoroethyl) trifluoro. Phenyl phosphate (manufactured by San Apro, trade name CPI-210S), 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (manufactured by ADEKA, trade name SP-172) , 4-Phenyl Diphenyl Sulfonium Hexafluoro Antimonate-Containing Aromatic Sulfonium Hexafluoro Antimonate Mixture (ACETO Corporate USA, Trade Name CPI-6996) and Triphenyl Sulfonium Tris (Trifluoromethanesulfonyl) Metanide (BASF, trade name CGI TPS-C1), Tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tris (trifluoromethylsulfonyl) methide (BASF, trade name GSID 26-1), Tris [ 4- (4-Acetylphenyl) sulfonylphenyl] Sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate (manufactured by BASF, trade name Irgacure PAG290) and the like are preferably used.

Among the above photocationic polymerization initiators, aromatic sulfonium complex salts are preferable from the viewpoint of vertical rectangular processability and thermal stability, and 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluoro) is preferable. Phenyl) Sulfonium hexafluoroantimonate, a mixture of aromatic sulfonium hexafluoroantimonates containing 4-thiophenyldiphenyl sulfonium hexafluoroantimonate, or tris [4- (4-acetylphenyl) sulfonylphenyl] Sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate is particularly preferred.

Further, the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid having a pKa of 4 or less, and more preferably a photocationic polymerization initiator that generates an acid having a pKa of 3 or less. A photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of pKa is not limited. The pKa of the acid generated from the photocationic polymerization initiator is preferably -10.0 or more, for example.

Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.

Examples of the ionic photocationic polymerization initiator include onium salt compounds (for example, diaryliodonium salt compounds and triarylsulfonium salt compounds), and quaternary ammonium salt compounds.

Examples of the ionic photocationic polymerization initiator include the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-22149. Examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.

The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of photopolymerization initiators.

The content ratio of the photopolymerization initiator in the negative photosensitive resin layer N is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the total mass of the negative photosensitive resin layer N. It is more preferable to have it, and it is particularly preferable that it is 1.0% by mass or more. The upper limit of the content ratio of the photopolymerization initiator is not limited. The content ratio of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the negative photosensitive resin layer N.

-Metal oxidation inhibitor-
The negative photosensitive resin layer N preferably contains a metal oxidation inhibitor.
The metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom in the molecule.
Further, as the metal oxidation inhibitor, at least the aromatic ring containing a nitrogen atom is selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, and a fused ring between them and another aromatic ring. It is preferably one ring, and more preferably the aromatic ring containing a nitrogen atom is an imidazole ring or a fused ring of an imidazole ring and another aromatic ring.
The other aromatic ring may be a mono-prime ring or a heterocyclic ring, but a mono-prime ring is preferable, a benzene ring or a naphthalene ring is more preferable, and a benzene ring is further preferable.
Preferred metal oxidation inhibitors are preferably imidazole, benzimidazole, tetrazole, mercaptothiazazole, and benzotriazole, with imidazole, benzimidazole, and benzotriazole being more preferred. As the metal oxidation inhibitor, a commercially available product may be used, and for example, Johoku Chemical Industry Co., Ltd., BT120, etc. containing benzotriazole can be preferably used.

Moreover, as a metal oxidation inhibitor, a benzotriazole compound or a carboxybenzotriazole compound is preferably mentioned.
Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. Examples of commercially available products of the carboxybenzotriazole compound include CBT-1 (Johoku Chemical Industry Co., Ltd.).

The negative photosensitive resin layer N may contain one kind alone or two or more kinds of metal oxidation inhibitors.
The content of the metal oxidation inhibitor is preferably 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably, it is more preferably 1% by mass to 5% by mass.

-Arbitrary component-
The negative photosensitive resin layer N may contain components other than the above-mentioned components (hereinafter, may be referred to as “arbitrary components”). Optional components include, for example, dyes, surfactants, and additives other than the above components.

<< Dye >>
The negative photosensitive resin layer N has a maximum absorption in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. It is preferable to contain a dye having a wavelength of 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter, may be referred to as “dye NC”). Although the detailed mechanism is unknown, the inclusion of the dye NC in the negative photosensitive resin layer N improves the adhesion with the layer adjacent to the negative photosensitive resin layer N, and is more excellent in resolution.

In the present disclosure, the term "maximum absorption wavelength changes by acid, base, or radical" used with respect to a dye is a mode in which a dye in a color-developing state is decolorized by an acid, base, or radical. It may mean any aspect of a mode in which the dye in the above color is developed by an acid, a base or a radical, and a mode in which the dye in a color-developing state changes to a color-developing state of another hue.

Specifically, the dye NC may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize. In the above aspect, the dye NC may be a dye whose color development or decolorization state is changed by the action of an acid, a base, or a radical generated by exposure. Further, the dye NC is a dye whose color development or decolorization state changes by changing the state (for example, pH) in the negative photosensitive resin layer N by an acid, a base, or a radical generated by exposure. There may be. On the other hand, the dye NC may be a dye whose color development or decolorization state changes by directly receiving an acid, a base, or a radical as a stimulus without exposure.

The dye NC is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of an exposed portion, visibility of a non-exposed portion, and resolution, and the maximum absorption wavelength is changed by a radical. It is more preferable that the dye is a dye.

The negative photosensitive resin layer N is a dye NC whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, and resolution. It is preferable to include both of the above.

The dye NC is preferably a dye that develops color with an acid, a base, or a radical from the viewpoint of visibility of the exposed part and visibility of the non-exposed part.

An example of the color-developing mechanism of dye NC is by exposing a negative photosensitive resin layer N containing a photoradical polymerization initiator, a photocationic polymerization initiator (that is, a photoacid generator), or a photobase generator. Radical-reactive dyes, acid-reactive dyes, or base-reactive dyes (eg, leuco dyes) are produced by radicals, acids, or bases generated from photoradical polymerization initiators, photocationic polymerization initiators, or photobase generators. An aspect of developing color can be mentioned.

In the dye NC, the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development is preferably 550 nm or more, preferably 550 nm to 700 nm, from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. More preferably, it is particularly preferably 550 to 650 nm.

Further, the dye NC may have one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development. When the dye NC has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of the dye NC is the transmission spectrum of the solution containing the dye NC (liquid temperature 25 ° C.) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, Shimadzu Corporation) in an atmospheric atmosphere. It is measured and then measured by detecting the wavelength at which the intensity of light is minimized (maximum absorption wavelength).

Examples of the dye that develops or decolorizes by exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. The dye NC is preferably a leuco compound from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton. It has a leuco compound (diarylmethane dye) having a rhodamine lactam skeleton, a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indolyl phthalide dye), and a leuco auramine skeleton. Leuco compounds (leuco auramine dyes) can be mentioned. The leuco compound is preferably a triarylmethane dye or a fluorane dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye.

The leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion. By reacting the lactone ring, sultin ring, or sulton ring contained in the leuco compound with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, the leuco compound is changed to a closed ring state. The color can be decolorized, or the radical compound can be changed to a ring-opened state to develop a color. The leuco compound is preferably a compound having a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color. It is more preferable that the compound has, and the lactone ring is opened by a radical or an acid to develop a color.

Specific examples of leuco compounds include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malakite green lactone, benzoyl leucomethylene blue, 2 -(N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6- Methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-xylidinofluorane , 3- (N, N-diethylamino) -6-methyl-7-chlorofluorine, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7- (4-Chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-) Diethylamino) -7,8-benzofluorolane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7- Xylidinofluolane, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-) 3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3 -(4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2) -Methylindole-3-yl) phthalide and 3', 6'-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9'-[9H] xanthen-3-one can be mentioned.

Examples of the dye NC include a dye. Specific examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl. Red, Congofred, Benzopurpurin 4B, α-Naftil Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malakite Green, Parafuxin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (Hodoya Chemical Industry (Hodoya Chemical Industry) ), Oil Blue # 603 (Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (Orient Chemical Industry Co., Ltd.) ), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green # 502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.) Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfordamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2 -Carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl -4-p-diethylaminophenylimino-5-pyrazolone can be mentioned.

The dye NC is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, pattern visibility after development, and resolution, and color is developed by radicals. It is more preferable that the dye is a radical.

The dye NC is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate.

The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of dyes.

The content ratio of the dye is 0.1 with respect to the total mass of the negative photosensitive resin layer N from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. It is preferably 0% by mass or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 1% by mass. Is particularly preferable.

The content ratio of the dye NC means the content ratio of the dye when all of the dye NC contained in the negative type photosensitive resin layer N is in a colored state. Hereinafter, a method for quantifying the content ratio of dye NC will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Next, in an air atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is prepared. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the negative photosensitive resin layer N (3 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the negative photosensitive resin layer N, the content of the dye contained in the negative photosensitive resin layer N is calculated based on the calibration curve.

<< Surfactant >>
The negative photosensitive resin layer N preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.

Examples of the nonionic surfactant include a polyoxyethylene higher alkyl ether compound, a polyoxyethylene higher alkylphenyl ether compound, a higher fatty acid diester compound of polyoxyethylene glycol, a silicone-based nonionic surfactant, and a fluorine-based nonionic property. Surfactants can be mentioned.

The negative photosensitive resin layer N preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. It is considered that the negative type photosensitive resin layer N contains a fluorine-based nonionic surfactant to suppress the penetration of the etching solution into the negative type photosensitive resin layer N and reduce the side etching. Commercially available products of the fluorine-based nonionic surfactant include, for example, Megafvck (registered trademark) F-551, F-552 (DIC Corporation), and Megafvck F-554 (DIC Corporation). ..

Examples of the surfactant include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362. The surfactants described in paragraphs 0060 to 0071 of the publication are also mentioned.

The negative type photosensitive resin layer N may contain one type alone or two or more types of surfactants.

The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 3% by mass, based on the total mass of the negative photosensitive resin layer N. More preferred.

<< Additives >>
Examples of the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a resin other than those described above, and a solvent.
The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of additives.

The negative type photosensitive resin layer N may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine, or 4-methoxyphenol. Examples of the radical polymerization inhibitor other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the negative photosensitive resin layer N.

The ratio of the total content of the radical polymerization inhibitor, the benzotriazol compound, and the carboxybenzotriazol compound is 0.01% by mass to 3% by mass with respect to the total mass of the negative photosensitive resin layer N. It is preferably 0.05% by mass to 1% by mass, and more preferably 0.05% by mass to 1% by mass. It is preferable that the ratio of the total content of each of the above components is 0.01% by mass or more from the viewpoint of imparting storage stability to the negative photosensitive resin layer N. On the other hand, it is preferable that the ratio of the total content of each of the above-mentioned components is 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.

The negative type photosensitive resin layer N may contain a sensitizer. The sensitizer is not limited, and a known sensitizer can be used. In addition, dyes and pigments can also be used as the sensitizer. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclysin compounds.

The negative type photosensitive resin layer N may contain one type alone or two or more types of sensitizers.

When the negative photosensitive resin layer N contains a sensitizer, the content ratio of the sensitizer can be appropriately selected depending on the purpose, but the sensitivity to the light source is improved and the curing rate is improved by the balance between the polymerization rate and the chain transfer. From the viewpoint, it is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass with respect to the total mass of the negative type photosensitive resin layer N.

The negative photosensitive resin layer N may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.

The negative photosensitive resin layer N may contain a resin other than those described above.
Resins other than those described above include acrylic resins, styrene-acrylic copolymers (however, limited to copolymers having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, and polyesters. Examples thereof include resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The negative type photosensitive resin layer N may contain a solvent. When the negative type photosensitive resin layer N is formed by the photosensitive resin composition containing a solvent, the solvent may remain in the negative type photosensitive resin layer N. The solvent will be described later.

The negative photosensitive resin layer N has, as an additive, for example, a metal oxide particle, an antioxidant, a dispersant, an acid growth agent, a development accelerator, a conductive fiber, a thermal radical polymerization initiator, a thermal acid generator, and the like. It may contain at least one selected from the group consisting of UV absorbers, thickeners, cross-linking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors. Additives are described, for example, in paragraphs 0165 to 0184 of JP2014-85643A. The contents of the above publication are incorporated herein by reference.

-Impurities, etc.-
The negative photosensitive resin layer N may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among the above, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.

The content of impurities in the negative photosensitive resin layer N is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less on a mass basis. The content of impurities in the negative photosensitive resin layer N can be 1 ppb or more or 0.1 ppm or more on a mass basis.

As a method of setting impurities in the above range, a raw material having a low impurity content is selected as the raw material of the negative photosensitive resin layer N, prevention of contamination of impurities during the formation of the negative photosensitive resin layer N, and Cleaning the manufacturing equipment to remove impurities. By such a method, the amount of impurities can be kept within the above range.

Impurities can be quantified by a known method, for example, ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, or ion chromatography.

The content of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the negative photosensitive resin layer N is low. Is preferable. The content of the above compound in the negative photosensitive resin layer N is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis. The content of the above compound in the negative photosensitive resin layer N can be 10 ppb or more or 100 ppb or more on a mass basis. The content of the above-mentioned compound can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.

The water content in the negative photosensitive resin layer N is preferably 0.01% by mass to 1.0% by mass, preferably 0.05% by mass to 0% by mass, from the viewpoint of improving reliability and laminateability. More preferably, it is 5% by mass.

-thickness-
The thickness of the negative photosensitive resin layer N may be determined, for example, according to the thickness of the resin pattern 2 formed in the developing step described later. The thickness of the negative photosensitive resin layer N may be determined, for example, in the range of 1 μm to 100 μm.

-Transmittance-
In the negative photosensitive resin layer N, the transmittance of light having a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more from the viewpoint of being more excellent in adhesion. Is particularly preferable. The upper limit of transmittance is not limited. In the negative photosensitive resin layer N, the transmittance of light having a wavelength of 365 nm is preferably 99.9% or less.

The preparation step includes a step of preparing a laminated precursor having a transparent base material and a light-shielding pattern 1 on the transparent base material, and a negative type photosensitive on the transparent base material and the light-shielding pattern 1. It is preferable to include a step of forming the sex resin layer N. In the step of forming the negative type photosensitive resin layer N, it is preferable to form the negative type photosensitive resin layer N by using a photosensitive transfer material (also referred to as “dry film”).
That is, the negative type photosensitive resin layer N is preferably a layer formed of a photosensitive transfer material.

The preparation steps include a step of preparing a transparent base material, a step of forming a light-shielding pattern 1 on the transparent base material, and a negative type photosensitive resin layer N on the transparent base material and the light-shielding pattern 1. It is preferable to include a step of forming the above. The steps of forming the light-shielding pattern 1 include a step of forming a light-shielding layer on the transparent base material, a step of forming a photosensitive resin layer on the light-shielding layer, and a step of forming the photosensitive resin layer. It is preferable to include a step of forming a resist pattern by exposure and development, and a step of removing the light-shielding layer not covered by the resist pattern. In the step of forming the negative type photosensitive resin layer N, it is preferable to form the negative type photosensitive resin layer N by using a photosensitive transfer material.

The preparation steps include, for example, a step of preparing a transparent base material, a step of forming a light-shielding pattern 1 on the transparent base material, and a negative photosensitive resin on the transparent base material and the light-shielding pattern 1. Examples thereof include a step of forming the layer N and the like.

Further, the preparation steps include, for example, a step of preparing a laminated precursor having a transparent base material and a light-shielding layer on the transparent base material, and a step of forming a light-shielding pattern 1 from the light-shielding layer. An embodiment including a step of forming a negative type photosensitive resin layer N on the transparent base material and the light-shielding pattern 1 can be mentioned. The light-shielding layer is a layer that is a material for the light-shielding pattern 1. Examples of the method for producing a laminated precursor having a transparent base material and a light-shielding layer include a method of forming a light-shielding layer on the transparent base material.

Further, the preparatory steps include, for example, a step of forming a light-shielding layer on one surface of the transparent substrate, a step of forming a photoresist layer on the light-shielding layer, and exposing and developing the photoresist layer to form a resist pattern. Examples thereof include a step of forming and a step of etching the light-shielding layer to form the light-shielding pattern 1. The method for forming the photoresist layer is not particularly limited, and known photoresist compositions and photosensitive transfer materials can be used.

-Method of forming light-shielding pattern 1-
Hereinafter, a method for forming the light-shielding pattern 1 will be described.
Examples of the method of forming the light-shielding pattern 1 include a method of forming a light-shielding layer on a transparent base material and then processing the light-shielding layer into a pattern.

Examples of the method for forming the light-shielding layer include sputtering and plating. In sputtering, for example, a layer containing Cu, Ti, or Ni (light-shielding layer) can be formed on a transparent substrate. Among the above metals, Cu, which has low electrical resistance and is inexpensive, is preferable. The component of the layer (light-shielding layer) formed by sputtering may be Ni, Al, Nb, W, Ni-P, or Ni-B. Examples of plating include electroless plating. As a method of electroless plating, a known method can be used. For example, in electroless copper plating, copper can be deposited on a transparent substrate by the reaction of copper ions and a reducing agent. The catalyst used in electroless plating is preferably a palladium-tin mixed catalyst. The primary particle size of the catalyst is preferably 10 nm or less. The plating solution used for electroless plating preferably contains hypophosphorous acid as a reducing agent. Examples of the plating include the plating described in the section "Pattern 3 forming step" below. The structure of the light-shielding layer may be a single-layer structure or a multi-layer structure. By forming the light-shielding layer having a multi-layer structure, a conductive pattern having a multi-layer structure can be formed. Examples of the method for forming each layer included in the light-shielding layer having a multi-layer structure include electroless plating, sputtering, vapor deposition, and coating of a coupling agent.

As a method of processing the light-shielding layer into a pattern, for example, photolithography can be mentioned. As the photolithography, a known photolithography can be used. For example, a photosensitive resin layer is formed on the light-shielding layer, then a resist pattern is formed by exposure and development of the photosensitive resin layer, and then the light-shielding layer not covered by the resist pattern is removed. As a result, a light-shielding pattern can be formed.

The type of the photosensitive resin layer formed on the light-shielding layer is not limited. The photosensitive resin layer may be a positive type photosensitive resin layer or a negative type photosensitive resin layer. Examples of the negative photosensitive resin layer include the negative photosensitive resin layer described in the above section “Negative photosensitive resin layer N”. Examples of the method for forming the photosensitive resin layer include a method using a photosensitive resin composition and a method using a photosensitive transfer material. Examples of the method using the photosensitive resin composition include a method of applying the photosensitive resin composition on the light-shielding layer and then drying the photosensitive resin composition. The photosensitive resin composition is a composition containing a material for a photosensitive resin layer. Examples of the method using the photosensitive transfer material include a method of arranging the photosensitive resin layer on the light-shielding layer by laminating the photosensitive transfer material having the photosensitive resin layer and the light-shielding layer. .. For the method of forming the negative type photosensitive resin layer, the following section "Method of forming the negative type photosensitive resin layer N" can be referred to.

The exposure method of the photosensitive resin layer is not limited as long as it is a method capable of forming an exposed portion and a non-exposed portion in the photosensitive resin layer. As the exposure method, a known method can be used. The region of the photosensitive resin layer to be exposed may be determined according to the shape of the target light-shielding pattern. For the exposure conditions, the section "Exposure step" below can be referred to.

The method for developing the photosensitive resin layer is not limited as long as the photosensitive resin layer can be processed into a pattern by removing the exposed portion or the non-exposed portion of the photosensitive resin layer. In the development of the negative photosensitive resin layer, the unexposed portion of the negative photosensitive resin layer is removed. In the development of the positive photosensitive resin layer, the exposed portion of the positive photosensitive resin layer is removed. As a developing method, a known method can be used. For the development conditions, the section "Development process" below can be referred to.

A known method can be used as a method for removing the light-shielding layer (that is, the exposed light-shielding layer) that is not covered by the resist pattern. For example, when the light-shielding layer contains metal, the light-shielding layer that is not covered by the resist pattern can be removed by etching. Examples of the etching include wet etching and dry etching. The etching is preferably wet etching. Wet etching is etching using a chemical called an etching solution. Examples of the etching solution include a sulfuric acid-hydrogen peroxide aqueous solution. The composition of the sulfuric acid-hydrogen peroxide aqueous solution is not limited. Examples of the sulfuric acid-hydrogen acid aqueous solution include a sulfuric acid-hydrogen acid aqueous solution in which the concentration of sulfuric acid is 1% by volume to 10% by volume and the concentration of hydrogen peroxide is 1% by volume to 10% by volume. Be done. The temperature of the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 20 ° C. to 35 ° C. The immersion time in the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 1 minute to 10 minutes. When the light-shielding layer contains copper, the sulfuric acid-hydrogen peroxide aqueous solution can be used until the concentration of copper dissolved in the sulfuric acid-hydrogen peroxide aqueous solution becomes, for example, 50 g / L. Examples of the etching solution include a cupric chloride solution. The composition of the cupric chloride solution is not limited. As the cupric chloride solution, for example, a solution containing 20% by mass to 35% by mass of cupric chloride and 1% by mass to 7% by mass of chlorine can be preferably used. However, the etching conditions are not limited to the above conditions. For example, the temperature of the etching solution and the immersion time in the etching solution may be determined according to the composition of the light-shielding layer, the thickness of the light-shielding layer, and the type of the etching solution.

The laminated body may have an adhesion layer between the transparent base material and the light-shielding pattern 1. The adhesion layer may be formed, for example, by forming the adhesion layer on the transparent base material before forming the light-shielding pattern 1. Examples of the method for forming the adhesion layer include electroless plating, sputtering, and thin film deposition. Examples of the method for forming the adhesion layer include a method including application, drying, and sintering of a metal particle dispersion liquid in which metal particles are dispersed.

In the method for producing a laminated body, the surface of the transparent base material may be roughened by desmear treatment, if necessary, before forming the adhesion layer and the light-shielding pattern. Examples of the desmear treatment liquid (oxidizing roughening liquid) include chromium / sulfuric acid roughening liquid, alkaline permanganate roughening liquid (for example, sodium permanganate roughening liquid), and sodium fluoride / chromium / sulfuric acid crude liquid. Examples include chemicals.

-Method of forming negative photosensitive resin layer N-
Hereinafter, a method for forming the negative photosensitive resin layer N will be described. Examples of the method for forming the negative type photosensitive resin layer N include a method using a photosensitive resin composition and a method using a photosensitive transfer material.

-Photosensitive resin composition-
Examples of the method using the photosensitive resin composition include a method of applying the photosensitive resin composition on a transparent base material and a light-shielding pattern, and then drying the photosensitive resin composition.

The components of the photosensitive resin composition may be determined according to the components of the target negative photosensitive resin layer N. Preferred components of the photosensitive resin composition include, for example, the components described in the above section "Negative type photosensitive resin layer N". Examples of the photosensitive resin composition include a composition containing a polymer A, a polymerizable compound B, and a photopolymerization initiator. The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

The solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin composition (for example, the polymer A, the polymerizable compound B, and the polymerization initiator), and a known solvent can be used. can. Examples of the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (for example, methanol and ethanol), a ketone solvent (for example, acetone and methyl ethyl ketone), and an aromatic hydrocarbon solvent (for example, toluene). Examples include aprotonic polar solvents (eg, N, N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

The photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. The photosensitive resin composition comprises at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent. It is more preferable to include it. It is particularly preferable that the photosensitive resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Be done.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

As the solvent, the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used. These contents are incorporated herein by reference.

The photosensitive resin composition may contain one kind of solvent alone or two or more kinds of solvents.

The content ratio of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferable that it is a part.

The method for preparing the photosensitive resin composition is not limited. As a method for preparing the photosensitive resin composition, for example, a method of preparing a photosensitive resin composition by preparing a solution in which each component is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio. Can be mentioned. The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the negative photosensitive resin layer.

The method for applying the photosensitive resin composition is not limited, and a known method can be used. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

-Photosensitive transfer material-
As a method of using the photosensitive transfer material, for example, a photosensitive transfer material having a negative photosensitive resin layer N and a transparent base material having a light-shielding pattern are bonded to each other to form a transparent base material and a light-shielding pattern. A method of arranging the negative type photosensitive resin layer N on the surface can be mentioned. In the method of laminating a photosensitive transfer material having a negative photosensitive resin layer N and a transparent base material having a light-shielding pattern, the photosensitive transfer material and the transparent base material are superposed on each other, and a roll or the like is used. It is preferable to pressurize and heat by means. For bonding, a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used. Hereinafter, the components of the photosensitive transfer material will be described.

－－Photosensitive resin layer －－
The photosensitive transfer material has a negative photosensitive resin layer N. The negative type photosensitive resin layer N is as described in the above section “Negative type photosensitive resin layer N”.

－－Temporary support －－
The photosensitive transfer material preferably has a temporary support. The temporary support is a support that can be peeled off from the photosensitive transfer material. The temporary support can support at least the negative photosensitive resin layer N. The temporary support may be peeled off before the exposure step. After irradiating light without peeling the temporary support in the exposure step, the temporary support may be peeled off. By irradiating light without peeling off the temporary support in the exposure process, the influence of dust and dirt in the exposure environment can be avoided.

As the temporary support, a temporary support having light transmission can be used. In the present disclosure, "having light transmittance" means that the transmittance of light having a wavelength used for pattern exposure is 50% or more. In the temporary support, the transmittance of light having a wavelength (preferably a wavelength of 365 nm) used for pattern exposure is preferably 60% or more from the viewpoint of improving the exposure sensitivity of the negative photosensitive resin layer N, which is 70. % Or more is more preferable.

Examples of the temporary support include a glass substrate, a resin film, and paper. The temporary support is preferably a resin film from the viewpoint of strength, flexibility, and light transmission.

Examples of the resin film include polyethylene terephthalate film (that is, PET film), cellulose triacetate film, polystyrene film, and polycarbonate film. The resin film is preferably a PET film, more preferably a biaxially stretched PET film.

The thickness of the temporary support is not limited. The average thickness of the temporary support may be determined, for example, according to the strength of the temporary support, the light transmittance, the material, and the flexibility required for bonding the photosensitive transfer material and the transparent base material. .. The average thickness of the temporary support is preferably 5 μm to 100 μm. Further, the average thickness of the temporary support is preferably 5 μm to 50 μm, more preferably 5 μm to 20 μm, and further preferably 10 μm to 20 μm from the viewpoint of ease of handling and versatility. It is particularly preferably 10 μm to 16 μm.

The arithmetic mean roughness Ra of the surface of the temporary support on the side on which the negative photosensitive resin layer N is arranged is preferably 0.1 μm or less, more preferably 0.05 μm or less, and 0.02 μm. The following is particularly preferable. The lower limit of the arithmetic mean roughness Ra is not limited. The arithmetic mean roughness Ra of the surface of the temporary support on the side on which the negative photosensitive resin layer N is arranged may be determined, for example, in the range of 0 μm or more.

Arithmetic mean roughness Ra is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), a surface profile of the object to be measured is obtained under the following conditions. As the measurement and analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the object to be measured is obtained. When the surface of the object to be measured is in contact with the surface of another layer, the arithmetic mean roughness Ra of the surface of the exposed object to be measured may be measured by peeling the object to be measured from the other layer. ..

It is preferable that the temporary support (particularly the resin film) is free from, for example, deformation (for example, wrinkles), scratches, and defects. From the viewpoint of transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, defects, and precipitates contained in the temporary support is small. In the temporary support, the number of fine particles, foreign substances, and defects having a diameter of 1 μm or more ^{is preferably 50 pieces / 10 mm 2} or less, more preferably 10 pieces / 10 mm ² or less, and 3 pieces / It is more preferably 10 mm ² or less, and particularly preferably ^{0/10 mm 2.}

Regarding preferred embodiments of the provisional support, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019 to paragraph 0026 of JP-A-2016-27363, and paragraphs 0041 to International Publication No. 2012/081680. It is described in paragraph 0057, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of JP-A-2019-101405. The contents of these publications are incorporated herein by reference.

－－Cover film －－
The photosensitive transfer material may have a cover film (also referred to as a protective film). According to the cover film, the surface of the layer in contact with the cover film (for example, the negative photosensitive resin layer N) can be protected. The photosensitive transfer material preferably includes a temporary support, a negative photosensitive resin layer N, and a cover film in this order. The photosensitive transfer material preferably has a cover film in contact with the surface of the negative photosensitive resin layer N opposite to the side on which the temporary support is arranged.

Examples of the cover film include a resin film and paper. The cover film is preferably a resin film from the viewpoint of strength and flexibility.

Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. The resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

The thickness of the cover film is not limited. The average thickness of the cover film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 10 μm to 20 μm.

The arithmetic mean roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is preferably 0.3 μm or less, preferably 0.1 μm or less, from the viewpoint of excellent resolution. Is more preferable, and 0.05 μm or less is particularly preferable. When the arithmetic mean roughness of the surface on the side where the negative photosensitive resin layer N of the cover film is arranged is within the above range, the thickness of the negative photosensitive resin layer and the formed resin pattern can be made uniform. improves. The lower limit of the arithmetic mean roughness Ra is not limited. The arithmetic average roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is preferably 0.001 μm or more. The arithmetic mean roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is measured by a method according to the method for measuring the arithmetic mean roughness Ra described in the above section "Temporary Support". ..

－－Thermoplastic resin layer －－
The photosensitive transfer material according to the present disclosure may have a thermoplastic resin layer N. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the negative type photosensitive resin layer N. When the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the negative type photosensitive resin layer N, the followability to the adherend is improved, and the space between the adherend and the photosensitive transfer material is improved. This is because, as a result of suppressing the mixing of air bubbles, the adhesion between layers is improved.

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, and polyimide resin. Examples thereof include polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

The alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion to a layer adjacent to the thermoplastic resin layer. Here, the "acrylic resin" is selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one kind.

In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the ratio of the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass. In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. %, More preferably 50% by mass to 100% by mass.

Further, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferable.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of acid value is not limited. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not limited and can be appropriately selected from known resins and used. Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716. Described in paragraphs 0033 to 0052 of Japanese Patent Application Laid-Open No. 2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and paragraphs 0053 to 0068 of JP-A-2016-224162. Among the binder polymers of the above, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be mentioned.

The content ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total mass of the carboxy group-containing acrylic resin. It is more preferable, and it is particularly preferable that it is 12% by mass to 30% by mass.

The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoint of developability and adhesion to a layer adjacent to the thermoplastic resin layer.

The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Reactive groups include, for example, ethylenically unsaturated groups, polycondensable groups (eg, hydroxy and carboxy groups), and polyaddition reactive groups (eg, epoxy groups and (blocking) isocyanate groups). Be done.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one type alone or two or more types of alkali-soluble resins.

The content ratio of the alkali-soluble resin is 10% by mass to 99% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. It is more preferably 20% by mass to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.

The thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, and the maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter referred to as “dye B”). In some cases), it is preferable to include. The preferred embodiment of the dye B is the same as the preferred embodiment of the dye NC described above, except for the points described later.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of the exposed part, visibility of the non-exposed part, and resolution, and the maximum absorption wavelength is changed by the acid. It is more preferable that the dye is a radical.

The thermoplastic resin layer is composed of a dye whose maximum absorption wavelength is changed by an acid as dye B and a compound which generates an acid by light, which will be described later, from the viewpoints of visibility of an exposed part, visibility of a non-exposed part, and resolution. And, preferably.

The thermoplastic resin layer may contain one type alone or two or more types of dye B.

The content ratio of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. It is more preferably% to 6% by mass, further preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.

Here, the content ratio of the dye B means the content ratio of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content ratio of dye B will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Next, in an air atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is prepared. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, may be referred to as "compound C"). Compound C is preferably a compound that receives active rays (for example, ultraviolet rays and visible rays) to generate acids, bases, or radicals. Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

The thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution. Examples of the photoacid generator include a photocationic polymerization initiator that may be contained in the negative-type photosensitive resin layer described above, and the same preferred embodiments are used except for the points described below.

From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and has sensitivity, resolution and adhesion. From the viewpoint, it is more preferable to contain an oxime sulfonate compound.

It is also preferable that the photoacid generator is a photoacid generator having the following structure.

The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, and bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane , N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6 -Dimethyl-3,5-diacetyl-4- (2-nitrophenyl) -1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4- (2,4-dinitrophenyl) -1, 4-Dihydropyridine can be mentioned.

The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the negative photosensitive resin layer described above, and the preferred embodiment is also the same.

The thermoplastic resin layer may contain one kind alone or two or more kinds of compound C.

The content ratio of the compound C is 0.1% by mass to 10% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion, the visibility of the non-exposed portion, and the resolution. It is preferable, and it is more preferable that it is 0.5% by mass to 5% by mass.

The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

The molecular weight of the plasticizer (the molecular weight of the oligomer or polymer is the weight average molecular weight (Mw); the same applies hereinafter in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

The plasticizer is not limited as long as it is a compound that develops plasticity by being compatible with an alkali-soluble resin. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

The plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to the layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.

Examples of the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described in the above-mentioned "Polymerizable Compound B" section. In the photosensitive transfer material, when the thermoplastic resin layer and the negative type photosensitive resin layer are arranged in direct contact with each other, the thermoplastic resin layer and the negative type photosensitive resin layer are each the same (meth) acrylate compound. Is preferably included. This is because the thermoplastic resin layer and the negative photosensitive resin layer N each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, the (meth) acrylate compound may not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. preferable.

In certain embodiments, the (meth) acrylate compound used as a plasticizer is composed of two or more (meth) acrylate compounds in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to a thermoplastic resin layer, and developability. It is preferably a (meth) acrylate compound having a meta) acryloyl group.

In certain embodiments, the (meth) acrylate compound used as a plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.

The thermoplastic resin layer may contain one type alone or two or more types of plasticizers.

The content ratio of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability. It is preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.

The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include a surfactant that may be contained in the negative photosensitive resin layer N described above, and the preferred embodiment is also the same.

The thermoplastic resin layer may contain one type alone or two or more types of surfactants.

The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizer that may be contained in the negative photosensitive resin layer described above.

The thermoplastic resin layer may contain one type alone or two or more types of sensitizers.

The content ratio of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed part, and the visibility of the non-exposed part. %, More preferably 0.05% by mass to 1% by mass.

The thermoplastic resin layer may contain known additives in addition to the above components, if necessary.

Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of the above publication are incorporated herein by reference.

The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolvability, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components. Examples of the method for forming the thermoplastic resin layer include a method in which the thermoplastic resin composition is applied to the surface of the temporary support and the coating film of the thermoplastic resin composition is dried.

Examples of the thermoplastic resin composition include a composition containing the above components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

The solvent contained in the thermoplastic resin composition is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the thermoplastic resin layer. Examples of the solvent include a solvent that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.

The thermoplastic resin composition may contain one kind alone or two or more kinds of solvents.

The content ratio of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. It is more preferable that it is a part.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the above-mentioned method for preparing the photosensitive resin composition and the method for forming the negative type photosensitive resin layer N. For example, a thermoplastic resin composition was prepared by preparing a solution in which each component contained in the thermoplastic resin layer was dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio, and then obtained. The thermoplastic resin layer can be formed by applying the thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition. Further, after forming the negative type photosensitive resin layer N on the cover film, the thermoplastic resin layer may be formed on the surface of the negative type photosensitive resin layer N.

－－Intermediate layer －－
The photosensitive transfer material preferably has an intermediate layer between the thermoplastic resin layer and the negative photosensitive resin layer N. According to the intermediate layer, it is possible to suppress the mixing of components when forming a plurality of layers and during storage.

The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application. In the present disclosure, "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.

Examples of the intermediate layer include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724. Since the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved. The oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers. The oxygen blocking layer used as the intermediate layer is preferably an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.).

The intermediate layer preferably contains a resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and copolymers thereof. Can be mentioned. The resin contained in the intermediate layer is preferably a water-soluble resin.

The resin contained in the intermediate layer is a polymer A contained in the negative photosensitive resin layer N and a thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer from the viewpoint of suppressing mixing of components between a plurality of layers. ), It is preferable that the resin is different from any of the above.

The intermediate layer preferably contains polyvinyl alcohol, and preferably contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. Is more preferable.

The intermediate layer may contain one kind of resin alone or two or more kinds of resins.

The content ratio of the resin in the intermediate layer is 50% by mass with respect to the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. It is preferably ~ 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass. preferable.

Further, the intermediate layer may contain an additive if necessary. Examples of the additive include a surfactant.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen blocking property is not deteriorated, the mixing of the components at the time of forming a plurality of layers and at the time of storage can be suppressed, and the intermediate layer at the time of development can be suppressed. The increase in removal time can be suppressed.

The method of forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method for forming the intermediate layer, for example, a method of applying the composition for the intermediate layer to the surface of the thermoplastic resin layer or the negative photosensitive resin layer N and then drying the coating film of the composition for the intermediate layer is used. Can be mentioned.

Examples of the composition for the intermediate layer include a composition containing a resin and an optional additive. The composition for the intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for the intermediate layer and facilitate the formation of the intermediate layer. The solvent is not limited as long as it is a solvent that can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

Further, the photosensitive transfer material may further have another layer such as a refractive index adjusting layer.
The refractive index adjusting layer is not particularly limited, and a known refractive index adjusting layer can be used.
The refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive layer from the viewpoint of suppressing the visibility of wiring.
The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.70 or more. preferable.
The upper limit of the refractive index of the refractive index adjusting layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less. It is particularly preferably 74 or less.
The thickness of the refractive index adjusting layer is not particularly limited.
The thickness of the refractive index adjusting layer is preferably 50 nm or more and 500 nm or less, more preferably 55 nm or more and 110 nm or less, and further preferably 60 nm or more and 100 nm or less.
The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, a metal salt and a resin. A method using a complex with and the like can be mentioned.
The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used.
Specifically, the metal oxide particles are selected from the group consisting of _{zirconium oxide particles (ZrO 2} particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles), and silicon dioxide particles (SiO _{2 particles).} At least one kind is preferable.
Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles from the viewpoint that the refractive index of the second resin layer can be easily adjusted to 1.6 or more. Is more preferable.

--Average thickness ---
The average thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and particularly preferably 20 μm to 40 μm. The average thickness of the photosensitive transfer material is measured by a method according to the method for measuring the average thickness of the transparent substrate.

--shape--
The shape of the photosensitive transfer material is not limited. The shape of the photosensitive transfer material is preferably roll-shaped from the viewpoint of versatility and transportability. By winding the photosensitive transfer material, the shape of the photosensitive transfer material can be made into a roll.

-Manufacturing method of photosensitive transfer material-
The method for producing the photosensitive transfer material is not limited. Examples of the method for producing the photosensitive transfer material include a step of forming a negative photosensitive resin layer N by applying a photosensitive resin composition on a temporary support, and the above-mentioned negative photosensitive resin layer N. A method including a step of arranging a cover film on the surface and a method including the step of placing the cover film on the surface can be mentioned. In the above method, the photosensitive resin composition applied on the temporary support may be dried, if necessary. The drying method is not limited, and a known drying method can be used. Examples of the method of arranging the cover film on the negative type photosensitive resin layer N include a method of crimping the cover film to the negative type photosensitive resin layer N.

<Exposure process>
In the method for producing a structure according to the present disclosure, a part of the negative photosensitive resin layer N is irradiated with light from a surface of the transparent base material opposite to the surface on which the light-shielding pattern 1 is provided. Includes process (exposure process).
In the exposure step, light is irradiated from the surface of the transparent substrate opposite to the surface on which the light-shielding pattern 1 is provided. In the present disclosure, the "surface provided with the light-shielding pattern 1 of the transparent base material" means the surface of the transparent base material on the side having the light-shielding pattern 1. For example, in FIG. 1B, the “surface provided with the light-shielding pattern 1 of the transparent base material” refers to the surface of the transparent base material 10 in contact with the light-shielding pattern 20, that is, the surface to be exposed 10a. Refers to the side facing the other side. For example, as shown in FIG. 1B, when light is applied to the surface of the transparent substrate opposite to the surface facing the light-shielding pattern, the negative-type photosensitive resin layer N is formed by the light-shielding pattern. By blocking a part of the reaching light, a part of the negative photosensitive resin layer N can be selectively exposed. The exposed portion of the negative photosensitive resin layer N has reduced solubility in a developing solution. Further, as compared with the case of irradiating light in the direction from the negative type photosensitive resin layer N toward the transparent substrate, the surface of the transparent substrate is irradiated with light on the surface opposite to the surface facing the light-shielding pattern. This makes it possible to accelerate the curing of the negative photosensitive resin layer N in the vicinity of the transparent substrate. As a result, the resolution of the resin pattern can be improved in the developing process described later. Further, it is possible to form a resin pattern having a side wall having high linearity.

The light source used in the exposure step may be a light source that irradiates the negative photosensitive resin layer N with light having a wavelength that allows exposure (for example, 365 nm or 405 nm). Specific examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

The light irradiated in the exposure step preferably contains a wavelength included in the wavelength range of 200 nm to 1,500 nm, more preferably contains a wavelength included in the wavelength range of 250 nm to 450 nm, and has a wavelength range of 300 nm to 410 nm. It is preferable to include the wavelength contained in, and it is more preferable to include the wavelength of 365 nm.

The exposure amount is ^{preferably 5 mJ / cm 2} to 200 mJ / cm ² , and more preferably 10 mJ / cm ² to 100 mJ / cm ² .

In the exposure step, a part of the negative photosensitive resin layer N can be selectively exposed by the light-shielding pattern, so that the surface of the transparent base material is opposite to the surface on which the light-shielding pattern 1 is provided. You may irradiate the whole area of.

<Development process>
The method for producing a structure according to the present disclosure includes a step (development step) of forming a resin pattern 2 on the transparent substrate by developing the negative photosensitive resin layer N irradiated with light.
In the developing step, the negative type photosensitive resin layer N is developed to form the resin pattern 2 in the region defined by the transparent base material and the light-shielding pattern. For example, as shown in FIG. 1C, in the developing step, the non-exposed portion of the negative photosensitive resin layer N is removed to correspond to the shape of the exposed portion of the negative photosensitive resin layer N. A resin pattern having a shape is formed.

As a developing method, a known method can be used. The negative photosensitive resin layer N can be developed using, for example, a developing solution. The type of developer is not limited as long as the non-exposed portion of the negative photosensitive resin layer N can be removed. As the developing solution, a known developing solution (for example, the developing solution described in JP-A-5-72724) can be used.

The developer is preferably an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain a water-soluble organic solvent and / or a surfactant. As the developing solution, the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.

The development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which an exposed portion or a non-exposed portion is removed by spraying a developing solution onto the photosensitive resin layer after exposure by a shower.

After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.

The temperature of the developer is not limited. The liquid temperature of the developing solution is preferably 20 ° C. to 40 ° C.

The average thickness of the resin pattern 2 is preferably larger than the average thickness of the light-shielding pattern 1. When the average thickness of the resin pattern 2 is larger than the average thickness of the light-shielding pattern, a thick light-shielding pattern 1 can be formed. The ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 ([average thickness of the resin pattern 2] / [average thickness of the light-shielding pattern 1]) must be 1.1 or more. It is preferably 1.5 or more, and particularly preferably 3 or more. The ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 may be 4, 5, or 10. The average thickness of the resin pattern 2 is assumed by a method according to the method for measuring the average thickness of the transparent base material.

The average thickness of the resin pattern 2 is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably more than 2 μm. Further, the average thickness of the resin pattern is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The upper limit of the thickness of the resin pattern 2 is not limited. The average thickness of the resin pattern may be determined, for example, in the range of 100 μm or less.

The average width of the resin pattern 2 is preferably 50 μm or less, and more preferably 5 μm or less. The average width of the resin pattern 2 is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The average width of the resin pattern 2 is measured by a method according to the method for measuring the average width of the light-shielding pattern 1.

<Pattern 3 forming process>
The method for producing a structure according to the present disclosure includes a step of forming a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2 (pattern 3 forming step).
In the pattern 3 forming step, the pattern 3 is formed on the light-shielding pattern 1. For example, as shown in FIG. 1D, in the pattern 3 forming step, the pattern 3 is formed in the region defined by the light-shielding pattern 1 and the resin pattern 2.
Pattern 3 is preferably conductive from the viewpoint of more exerting the effects in the present disclosure.
Further, from the viewpoint of pattern formability and dimensional stability of the obtained pattern 3, it is preferable that the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.

As a method for forming the pattern 3, a known method can be used. As the material of the pattern 3 having conductivity, a material having conductivity suitable for an application can be used. The conductive pattern 3 material preferably contains Cu or an alloy of Cu. The alloy of Cu is preferably an alloy of Cu and at least one selected from the group consisting of Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W. The pattern 3 formed by using the above-mentioned material contains the above-mentioned metal element. The pattern 3 obtained in the pattern 3 forming step may be a conductive pattern made of Cu.
Further, from the viewpoint of pattern formability and dimensional stability of the obtained pattern 3, it is preferable that the light-shielding pattern 1 and the pattern 3 contain the same kind of material. For example, it is more preferable to contain the same metal element, and it is particularly preferable that the same metal or an alloy containing the same metal element is used.

As a method of forming the pattern 3 on the light-shielding pattern 1, a known method can be used. The pattern 3 is preferably a pattern formed by a plating method. As the plating, known plating can be used. Examples of plating include electroplating and electroless plating. The plating is preferably electroplating, more preferably electrocopper plating.

In electroplating, for example, a light-shielding pattern 1 that can function as a seed layer is used as a cathode, and a metal is stacked on the light-shielding pattern to form a conductive pattern 3 on the light-shielding pattern 1. can do.

Examples of the components of the plating solution used in electroplating include water-soluble copper salts. As the water-soluble copper salt, a water-soluble copper salt usually used as a component of a plating solution can be used. The water-soluble copper salt is preferably at least one selected from the group consisting of, for example, an inorganic copper salt, an alkane sulfonic acid copper salt, an alkanol sulfonic acid copper salt, and an organic acid copper salt. Examples of the inorganic copper salt include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of the alkane sulfonic acid copper salt include copper methane sulfonate and copper propane sulfonate. Examples of the alkanol sulfonate copper salt include copper isethionic acid and copper propanol sulfonate. Examples of the organic acid copper salt include copper acetate, copper citrate, and copper tartrate.

The plating solution may contain sulfuric acid. Since the plating solution contains sulfuric acid, the pH of the plating solution and the sulfate ion concentration can be adjusted.

The electroplating method and conditions are not limited. For example, by supplying the transparent base material after the developing step to the plating tank to which the plating solution is added, the pattern 3 having conductivity can be formed on the light-shielding pattern 1. In electroplating, for example, by controlling the current density and the transport speed of the transparent substrate, the pattern 3 having conductivity can be formed.

The temperature of the plating solution used for electroplating is generally 70 ° C. or lower, preferably 10 ° C. to 40 ° C. The current density in electroplating is generally 0.1 A / dm ² to 100 A / dm ² , preferably 0.5 A / dm ² to 20 A / dm ^2. By increasing the current density, the productivity of the conductive pattern can be improved. By lowering the current density, the uniformity of the thickness of the conductive pattern can be improved.

In the method of forming the pattern 3 having conductivity by plating, a plurality of metals may be continuously plated. For example, in the pattern 3 formed of a metal such as copper, deterioration of visibility or aesthetics may be a problem due to reflection. Examples of the method for reducing the reflectance of the surface of the pattern 3 include oxidation treatment, sulfurization treatment, nitriding treatment, chlorination treatment, formation of a blackened layer film, and black plating. For example, by performing chrome plating after copper plating, a layer containing a black material can be formed on the surface of the pattern 3. The method for reducing the reflectance of the surface of the pattern 3 is preferably an oxidation treatment or a sulfurization treatment. The oxidation treatment can obtain a more excellent antiglare effect, and is also preferable from the viewpoint of simplicity of waste liquid treatment and environmental safety.

After forming the pattern 3, the post-baking process may be performed. In the post-baking step, the insulation reliability, the curing property, or the plating adhesion can be improved by completely heat-curing the unreacted thermosetting component. The heating temperature is preferably 80 ° C. to 240 ° C. The heating time is preferably 5 minutes to 120 minutes.

After forming the pattern 3, the surface of the pattern 3 may be protected by a resin layer. For example, after forming the pattern 3, the surface of the pattern 3 can be protected by forming a resin layer on the conductive pattern. Examples of the components of the resin layer include an acrylic resin, a polyester resin, a polyvinyl acetal resin layer, a polyimide resin, and an epoxy resin. Examples of the method for forming the resin layer include coating and thermocompression bonding.

The structure of pattern 3 may be a single-layer structure or a multi-layer structure. The components of each layer of the pattern 3 having a multi-layer structure may be the same or different.

The thickness of pattern 3 is not limited. The thickness of the pattern 3 may be determined, for example, according to the application. When the pattern 3 is used as the wiring, the average thickness of the pattern 3 may be determined according to, for example, the magnitude of the current supplied to the wiring and the wiring width. From the viewpoint of conductivity, the average thickness of the pattern 3 is preferably 0.5 μm or more, more preferably 1 μm or more, and particularly preferably 2 μm or more. Further, the average thickness of the pattern 3 is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The average thickness of the pattern 3 is measured by a method according to the method for measuring the average thickness of the transparent substrate.

The width of pattern 3 is preferably narrow. Specifically, the average width of the pattern 3 is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. When the average width of the pattern 3 is 5 μm or less, the visibility of the pattern 3 in a device sensitive to visibility such as a touch panel can be reduced. From the viewpoint of conductivity, the average width of the pattern 3 is preferably 0.1 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. The average width of the pattern 3 is measured by a method according to the method for measuring the average width of the light-shielding pattern 1.

The surface resistance value of the conductive pattern 3 is preferably less than 0.2 Ω / □, and more preferably less than 0.15 Ω / □. The surface resistance value of the conductive pattern 3 is measured by the 4-probe method. When the pattern size is fine and difficult to measure, the surface resistance value of the conductive layer having the same composition and thickness may be measured.

In the pattern 3 forming step, the interface between the pattern 3 and the light-shielding pattern 1 may not be clearly observed. For example, when the light-shielding pattern 1 is used as a seed layer and the pattern 3 is formed by plating, the interface between the light-shielding pattern 1 and the pattern 3 may not be clearly observed. However, the fact that the interface between the pattern 3 and the light-shielding pattern 1 is not clearly observed does not preclude the object of the present disclosure.

<Post-exposure process and post-heating process>
The method for producing a structure according to the present disclosure further includes a step of performing at least one of post-exposure and post-heating on the resin pattern 2 from the viewpoint of improving the strength and durability of the resin pattern 2 which is a permanent film. Is preferable.
The method for producing a structure according to the present disclosure preferably includes a step of post-exposure the resin pattern 2 (also referred to as a “post-exposure step”) after the development step, and after the pattern 3 forming step, It is more preferable to include a step of post-exposing the resin pattern 2.
Further, the method for producing a structure according to the present disclosure may further include a step of heating (post-heating) the resin pattern 2 (also referred to as a “post-heating step”), if necessary.
Since the resin pattern 2 is an exposed portion of the negative photosensitive resin layer N, by performing the post-exposure or the post-heating, the remaining polymerization initiator, the polymerizable compound, and the like further cause a polymerization reaction and the like. The strength of the resin pattern 2 and the durability such as heat resistance, light resistance, and moisture resistance are improved.

The light source used for exposure in the post-exposure step is not particularly limited, and a known exposure light source can be used. From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as that in the resin pattern forming step.

The exposure amount in the post-exposure step, from the viewpoint of removability is ^preferably 5mJ / cm 2 ~ 5,000mJ / cm 2, more preferably 10mJ / cm 2 ~ 3,000mJ / cm 2, and particularly preferably ^{100mJ / cm 2 ~ 1,500mJ / cm} 2.

From the viewpoint of removability, the exposure amount in the post-exposure step is preferably equal to or more than the exposure amount in the resin pattern forming step, and more preferably larger than the exposure amount in the resin pattern forming step.

The method for producing a structure according to the present disclosure may include a post-heating step a plurality of times.
The heating temperature and heating time in the post-heating step are not particularly limited and can be appropriately selected.
The method of post-heating is not particularly limited, and a known method can be used. For example, the method may be performed by means provided in the exposure apparatus and the developing apparatus, or may be performed by using a hot plate or the like.

<Other processes>
The method for producing a structure according to the present disclosure may include any steps (other steps) other than those described above. The other steps are not particularly limited, and examples thereof include known steps.
Further, as an example of the resin pattern forming step and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.
In addition, the method for producing a structure according to the present disclosure may include a step of polishing the obtained pattern, a step of cleaning the obtained pattern, and the like.
Further, the method for manufacturing a structure according to the present disclosure may include a step of providing a member according to each application, which will be described later.

<< Applications >>
The structure obtained by the method for producing a structure according to the present disclosure can be applied to various uses. Applications of the structure obtained by the method for manufacturing the structure according to the present disclosure include, for example, a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, and a conductive heating element. In the above-mentioned applications, the structure obtained by the method for producing a structure according to the present disclosure can function as, for example, an electric conductor. Further, in the above-mentioned applications, the structure obtained by the method for producing a structure according to the present disclosure can exhibit various functions depending on the characteristics of the formed patterns (resin pattern 2, pattern 3, etc.). ..

<Touch sensor>
The touch sensor according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure. In the touch sensor according to the present disclosure, the conductive pattern of the structure (for example, the light-shielding pattern 1 and the conductive pattern 3, etc., the same applies hereinafter) can be used as, for example, a transparent electrode or a frame wiring. can. The components of the touch sensor according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known touch sensor can be used. The touch sensor is described in, for example, Japanese Patent No. 6486341 and Japanese Patent Application Laid-Open No. 2016-155978. The above publications are incorporated herein by reference. The method for manufacturing a touch sensor according to the present disclosure is not limited as long as it is a method for manufacturing a touch sensor having a structure obtained by the method for manufacturing a structure according to the present disclosure.

<Electromagnetic wave shield>
The electromagnetic wave shield according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure. In the electromagnetic wave shield according to the present disclosure, the conductive pattern of the structure can be used as, for example, an electromagnetic wave shield body. The components of the electromagnetic wave shield according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known electromagnetic wave shield can be used. The electromagnetic wave shield is described in, for example, Japanese Patent No. 6486382 and Japanese Patent Application Laid-Open No. 2012-163951. The above publications are incorporated herein by reference. The method for manufacturing an electromagnetic wave shield according to the present disclosure is not limited as long as it is a method for manufacturing an electromagnetic wave shield having a structure obtained by the method for manufacturing a structure according to the present disclosure.

<Antenna>
The antenna according to the present disclosure is an antenna having a structure obtained by the method for manufacturing the structure according to the present disclosure. In the antenna according to the present disclosure, the conductive pattern of the structure can be used as, for example, a transmission / reception unit or a transmission line unit. The components of the antenna according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known antenna can be used. The antenna is described in, for example, Japanese Patent Application Laid-Open No. 2016-219999. The above publications are incorporated herein by reference. The method for manufacturing an antenna according to the present disclosure is not limited as long as it is a method for manufacturing an antenna having a structure obtained by the method for manufacturing a structure according to the present disclosure.

<Wiring board>
The wiring board according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure. In the wiring board according to the present disclosure, the conductive pattern of the structure can be used, for example, as wiring for a printed wiring board. The components of the wiring board according to the present disclosure are not limited except that the components obtained by the method for manufacturing the structure according to the present disclosure are included. As a component other than the above structure, a component included in a known wiring board can be used. The wiring board is described in, for example, Japanese Patent No. 5774686 and Japanese Patent Application Laid-Open No. 2017-204538. The above publications are incorporated herein by reference. The method for manufacturing a wiring board according to the present disclosure is not limited as long as it is a method for manufacturing a wiring board having a structure obtained by the method for manufacturing a structure according to the present disclosure.

<Conductive heating element>
The conductive heating element according to the present disclosure has a structure obtained by the method for producing the structure according to the present disclosure. In the conductive heating element according to the present disclosure, the conductive pattern of the structure can be used as a heating element, for example. The components of the conductive heating element according to the present disclosure are not limited except that the structure obtained by the method for producing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known conductive heating element can be used. The conductive heating element is described in, for example, Japanese Patent Application Laid-Open No. 6486382. The above publications are incorporated herein by reference. The method for manufacturing a conductive heating element according to the present disclosure is not limited as long as it is a method for manufacturing a conductive heating element having a structure obtained by the method for manufacturing a structure according to the present disclosure.

(Structure)
The structure according to the present disclosure is arranged adjacent to the transparent base material, the light-shielding pattern 1 arranged on the transparent base material, and the light-shielding pattern 1 on the transparent base material, and It has a resin pattern 2 in contact with the transparent substrate, a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2, and the average thickness of the light-shielding pattern 1 is 2 μm or less. The average thickness of the resin pattern 2 exceeds 2 μm, the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1, and the resin pattern 2 is a permanent film. According to the above aspect, a structure having a conductive pattern in which the occurrence of morphological abnormalities is reduced is provided.
Further, the structure according to the present disclosure is preferably a structure manufactured by the method for manufacturing the structure according to the present disclosure.

Other than the above, preferred embodiments of the transparent base material, the light-shielding pattern 1, the resin pattern 2, and the pattern 3 in the structure according to the present disclosure are the transparent base material and the light-shielding material in the above-described method for producing the structure according to the present disclosure. This is the same as the preferred embodiment of the sex pattern 1, the resin pattern 2, and the pattern 3.

The structure A according to the present disclosure will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view showing an example of the structure according to the present disclosure. The structure 200 shown in FIG. 2 has a transparent base material 11, a pattern 21 (light-shielding pattern 1), a resin pattern 41 (resin pattern 2), and a pattern 51 (pattern 3). The light-shielding pattern 21 is arranged on the transparent base material 11. The light-shielding pattern 21 is in contact with the transparent base material 11. However, the light-shielding pattern 21 may come into contact with the transparent base material 11 via another layer (not shown). The resin pattern 41 is arranged on the transparent base material 11 next to the light-shielding pattern 21 and is in contact with the transparent base material 11. Further, the pattern 51 is arranged on the light-shielding pattern 21 and between the resin patterns 41.

Hereinafter, the present disclosure will be described in detail by way of examples. However, the present disclosure is not limited to the following examples.

<Synthesis of tetrahydrofuran-2-yl (ATHF) acrylate>
Acrylic acid (72.1 g, 1.0 mol) and hexane (72.1 g) were added to the three-necked flask and cooled to 20 ° C. After adding camphorsulfonic acid (7.0 mg, 0.03 mmol) and 2-dihydrofuran (77.9 g, 1.0 mol), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours and then heated to 35 ° C. And stirred for 2 hours. After laying Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite powder, manufactured by Kyowa Chemical Industry Co., Ltd.) on Nutche in this order, A filtered solution was obtained by filtering the reaction solution. Hydroquinone monomethyl ether (MEHQ, 1.2 mg) was added to the obtained filtrate and then concentrated under reduced pressure at 40 ° C. to obtain 140.8 g of tetrahydrofuran-2-yl acrylate (ATHF) as a colorless oil. (Yield 99.0%).

<Synthesis of polymer A-1>
PGMEA (75.0 g) was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. ATHF (40.0 g), AA (2.0 g), EA (20.0 g), MMA (22.0 g), CHA (16.0 g), V-601 (4.0 g), and PGMEA (75.0 g) ) Was added dropwise to a three-necked flask solution maintained at 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropping, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain polymer A-1 (solid content concentration: 40.0% by mass). Table 1 shows the content of each structural unit in the polymer A-1. The acid value of polymer A-1 is 15.6 mgKOH / g.
The above abbreviations represent the following compounds, respectively.
"AA": Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
"CHA": Cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"EA": Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"MMA": Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"PGMEA": Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
"V-601": 2,2'-azobis (2-methylpropionate) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Synthesis of polymer A-2>
A solution containing the polymer A-2 (solid content concentration: 40.0% by mass) was obtained in the same manner as the polymer A-1 except that the amount of the monomer used was changed according to the following. The weight average molecular weight of the polymer A-2 was 60,000.
(1) Styrene: 52.0 g
(2) Methacrylic acid: 29.0 g
(3) Methyl methacrylate: 19.0 g

<Synthesis of polymer A-3>
Polymer A-3 is contained in the same manner as in polymer A-1, except that the monomers (styrene, methacrylic acid, and methyl methacrylate) used in the synthesis of polymer A-1 are changed to the following monomers. A solution (solid content concentration: 40.0% by mass) was obtained. The weight average molecular weight of the polymer A-3 was 40,000.
(1) Benzyl methacrylate: 81.0 g
(2) Methacrylic acid: 19.0 g

<Preparation of negative photosensitive resin composition>
After mixing the components selected according to the description in Table 1, negative type photosensitive resin compositions NR1 to NR6 (solid content concentration: 25% by mass) were prepared by adding methyl ethyl ketone.

The unit of the numerical value in each component column in Table 1 is a mass part.
The details of the abbreviations shown in Table 1 are shown below.
BPE-500: ethoxylated bisphenol A dimethacrylate (addition of 10 mol of ethylene oxide), manufactured by Shin-Nakamura Chemical Industry Co., Ltd. BPE-200: ethoxylated bisphenol A dimethacrylate (addition of 4 mol of ethylene oxide), Shin-Nakamura Chemical Industry Co., Ltd. M-270: Polypropylene glycol diacrylate, A-TMPT: Trimethylol propantriacrylate, SR-454: Trimethylol propantriacrylate ethoxylated (ethylene oxide 3) (Molar addition), SR-502 manufactured by Alchema: Trimethylol propantriacrylate ethoxylated (addition of 9 mol of ethylene oxide), A-9300-CL1: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate manufactured by Alchema , Shin-Nakamura Chemical Industry Co., Ltd. B-CIM: Photoradical generator (photopolymerization initiator), Hampford, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis (diethylamino) benzophenone, manufactured by Sanyo Trading Co., Ltd. CBT-1: rust preventive, carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd. TDP-G: polymerization inhibitor, phenothiazine, Irganox 245 manufactured by Kawaguchi Chemical Industry Co., Ltd .: polymerization inhibitor, hindered phenol compound, F-552 manufactured by BASF, fluorosurfactant, Megafuck F552, manufactured by DIC Co., Ltd.

<Preparation of positive photosensitive resin composition PR1>
By mixing PGMEA with polymer A-1, photoacid generator B-1, surfactant C-1, and basic compound D-1, weighed according to the composition shown in Table 2 below, the solid content concentration A 10% by mass mixture was obtained. The above mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a positive photosensitive resin composition PR1.

The unit of the numerical value in each component column in Table 2 is a mass part.
In addition, the details of each component other than those described above shown in Table 2 are shown below.

The photoacid generator B-1 is a compound having the following structure (the compound described in paragraph 0227 of JP2013-47765A, synthesized according to the method described in paragraph 0227).

Surfactant C-1 is a compound having the following structure.

Basic compound D-1 is a compound having the following structure.

<Preparation of Negative Photosensitive Resin Compositions N1 to N8>
After mixing the components selected according to the description in Table 3 or Table 4, the negative photosensitive resin compositions N1 to are added by adding a 1: 1 (mass ratio) mixed solvent of 1-methoxy-2-propyl acetate and methyl ethyl ketone. N8 (solid content concentration: 29% by mass) was prepared.

The unit of the numerical value of the content of each component in Tables 3 and 4 is the mass part.
In addition, the details of each component shown in Table 3 are shown below.
-Ethylene unsaturated compound-
M-1: A-NOD-N (1,9-nonanediol diacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
M-2: Dipentaerythritol hexaacrylate (A-DPH, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
M-3: A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
M-4: Aronix TO-2349 (polyfunctional ethylenically unsaturated compound having a carboxylic acid group, manufactured by Toagosei Co., Ltd.)
M-5: Urethane acrylate 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.)

-Alkali-soluble polymer-
P-1: The following resin, styrene-derived structural unit (St) / dicyclopentanyl methacrylate-derived structural unit (DCPMA) / methacrylic acid-derived structural unit (MAA) / methacrylic acid-derived structural unit glycidyl methacrylate (GMA-MAA) = 41.0 / 15.2 / 23.9 / 19.9 (mol%), Mw = 17,000)

-Photopolymerization initiator-
D-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethanone-1- (O-acetyloxime) (Irgacure OXE-02, manufactured by BASF)
D-2: 2-Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, manufactured by BASF)
D-3: B-CIM (photoradical generator (photopolymerization initiator), manufactured by Hampford, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer): 0.89 parts by mass

-Thermal crosslinkable compound-
E-1: Duranate WT32-B75P (blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Co., Ltd.): 12.50 parts

-Other ingredients-
AD-1: Hydrogen donating compound (N-phenylglycine, manufactured by Junsei Chemical Co., Ltd.)
AD-2: Styrene / maleic anhydride = 4: 1 (molar ratio) copolymer (AD-2, SMA EF-40, acid anhydride price 1.94 mmol / g, weight average molecular weight 10,500, Cray Valley) Made)
AD-3: Fluorosurfactant (Mega Fvck F551A, manufactured by DIC Corporation)
AD-4: Sensitizer (4,5'-bis (diethylamino) benzophenone, SB-PI 701, manufactured by Sanyo Trading Co., Ltd.)
AD-5: Dye (Leuko Crystal Violet, manufactured by Yamada Chemical Co., Ltd.)
AD-6: Polymerization inhibitor (phenothiazine, TDP-G manufactured by Kawaguchi Chemical Industry Co., Ltd.)
AD-7: Rust inhibitor (carboxybenzotriazole, CBT-1 manufactured by Johoku Chemical Industry Co., Ltd.)
AD-8: Fluorine-based surfactant (Mega Fvck F552, manufactured by DIC Corporation)

(Example 1)
<Preparation of photosensitive transfer material (dry film) 1>
As a temporary support, a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm: arithmetic average roughness Ra: 0.02 μm) was prepared. A negative photosensitive resin composition NR1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value shown in Table 5. It was applied. A resist layer was formed by drying the coating film of the formed negative photosensitive resin composition NR1 at 90 ° C. for 100 seconds. A photosensitive transfer material 1 was prepared by pressure-bonding a polyethylene film (Tamapoli Co., Ltd., GF-818, thickness: 19 μm) as a cover film on the surface of the formed resist layer. By winding the obtained photosensitive transfer material 1, a roll-shaped photosensitive transfer material 1 was produced.

<Formation of light-shielding pattern 1 (copper pattern)>
A PET film with a copper layer was produced by forming a copper layer having a thickness of 0.05 μm on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering. After peeling the cover film from the photosensitive transfer material 1, the photosensitive transfer material 1 was attached to the PET film with a copper layer. The bonding step was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min. Next, the resist layer was exposed by irradiating light with a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm) via a photomask. After peeling off the temporary support, the resist layer is shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. to form a resin pattern (line / space = 5.5 μm / 4.5 μm). bottom. The copper layer not covered with the resin pattern was etched with an etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.). The residual resin pattern was removed using a stripping solution (10 mass% sodium hydroxide aqueous solution). By the above procedure, a PET film with a copper pattern (line / space = 5 μm / 5 μm) was produced. The copper pattern functions as the light-shielding pattern 1. Table 5 shows the average thickness of the light-shielding pattern 1.

<Preparation of photosensitive transfer material 2>
As a temporary support, a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm: arithmetic average roughness Ra: 0.02 μm) was prepared. A negative photosensitive resin composition N1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value shown in Table 5. It was applied. The coating film of the formed negative photosensitive resin composition N1 was dried at 90 ° C. for 100 seconds.

After that, a polyethylene film (Tamapoli Co., Ltd., GF-818, thickness: 19 μm) was pressure-bonded as a cover film to prepare a photosensitive transfer material 2. By winding up the obtained photosensitive transfer material 2, a roll-shaped photosensitive transfer material 2 was produced.

<Formation of pattern 3 (copper pattern)>
After peeling the cover film from the photosensitive transfer material 2, the PET film with a copper pattern and the photosensitive transfer material 2 were bonded together. The bonding step was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min. The obtained laminate has a PET film, a copper pattern (light-shielding pattern 1), a negative photosensitive resin layer N, and a temporary support in this order. Light is emitted to the surface of the PET film opposite to the surface facing the copper pattern (light-shielding pattern 1) using a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Irradiated. The exposure amount was 70 mJ / cm ² . After peeling off the temporary support, the negative type photosensitive resin layer N was shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. to form a resin pattern 2. The space portion (that is, the groove) of the copper pattern (light-shielding pattern 1) was filled with the resin pattern 2. Table 2 shows the average thickness of the resin pattern 2. Copper was deposited by electrolytic copper plating on a copper pattern (light-shielding pattern 1) not covered by the resin pattern 2 to form a conductive pattern 3. The current density in electrolytic copper plating was 1.8 ASD. The processing time in electrolytic copper plating was 6 minutes. The PET film after electrolytic copper plating was heated at 130 ° C. for 30 minutes. By the above procedure, a structure having a copper pattern (line (L) / space (S) = 5 μm / 5 μm) was produced. Table 5 shows the average thickness of the copper pattern (conducting pattern 3) precipitated by electrolytic copper plating.

(Examples 2 to 13)
Type and thickness of base material, thickness of light-shielding pattern 1 (average thickness), type of photosensitive resin composition forming light-shielding pattern 1, dry coating thickness of photosensitive resin composition (thickness of resist layer), The shape of the light-shielding pattern 1, the exposure method at the time of forming the photosensitive pattern 1 (including the presence or absence of peeling of the temporary support), the method of forming the negative photosensitive resin layer N, the negative photosensitive composition used, and the like. A structure having a copper pattern was prepared by the same procedure as in Example 1 except that the type of the layer, the thickness (average thickness) of the pattern 3, and the presence or absence of the curing treatment were appropriately changed according to the description in Table 5. Made. The average thickness of copper deposited by electrolytic copper plating can be increased by extending the treatment time.

In Example 2, a polyimide (PI) film having a thickness of 100 μm was used as the base material to be used, and after pattern 3 was formed, a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd.) was used. , Main wavelength: 365 nm) was used to irradiate light with an exposure amount of ^{1,000 mJ / cm 2 to perform post-exposure.}

In Example 3, as the base material to be used, a base material (COP) in which an indium tin oxide (ITO) film having a thickness of 0.1 μm is formed by a sputtering method on a polycycloolefin (COP) film having a thickness of 100 μm. A base material with a copper layer was prepared by forming a copper layer having a thickness of 0.03 μm on / ITO) by a sputtering method.
Further, in Example 3, instead of the negative photosensitive resin composition N1, N10 in which a high refractive index layer was laminated was formed on the following negative photosensitive resin composition N1.
As a temporary support, a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm: arithmetic average roughness Ra: 0.02 μm) was prepared. The negative photosensitive resin composition N1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was 3 μm. The negative-type photosensitive resin layer N was formed by drying the coating film of the formed negative-type photosensitive resin composition N1 at 90 ° C. for 100 seconds.
Next, on the negative photosensitive resin layer N described above, a coating liquid (composition N9) for an overcoat layer composed of the following formulation 201 was applied using a slit-shaped nozzle to a thickness of 0.2 μm after drying. The overcoat layer (OC) is arranged so that it has a thickness, is applied, dried with a hot air convection dryer having a temperature gradient of 40 ° C. to 95 ° C. to remove the solvent, and is arranged in direct contact with the photosensitive layer. Layer) was formed. The refractive index of the overcoat layer was 1.68 at a wavelength of 550 nm at 25 ° C.
Here, Formulation 201 is prepared using a resin having an acid group and an aqueous ammonia solution. The resin having an acid group is neutralized with the aqueous ammonia solution, and an aqueous resin composition containing an ammonium salt of the resin having an acid group. A coating solution for the overcoat layer, which is a product, was prepared.

-Coating liquid for overcoating: Formulation 201 (water-based resin composition)-
Acrylic resin (ZB-015M, manufactured by Fujifilm Fine Chemicals Co., Ltd., methacrylic acid / allyl methacrylate copolymer resin, weight average molecular weight 25,000, composition ratio (molar ratio) = 20/80, solid content 5. 00%, aqueous ammonia): 4.92 parts, polyfunctional ethylenically unsaturated compound having a carboxylic acid group (Aronix TO-2349, manufactured by _{Toa Synthetic Co., Ltd.): 0.04 parts, ZrO 2} particles (Nano Youth OZ- S30M, solid content 30.5%, methanol 69.5%, refractive acid 2.2, average particle size: about 12 nm, manufactured by Nissan Chemical Industry Co., Ltd .: 4.34 parts, rust preventive (benzotriazole derivative) , BT-LX, manufactured by Johoku Chemical Industry Co., Ltd.): 0.03 parts ・ Surfactant (fluorine-based surfactant, Megafuck F444, manufactured by DIC Co., Ltd.): 0.01 parts ・ Distilled water: 24. 83 parts, methanol: 65.83 parts

A photosensitive transfer material 2 was prepared by pressure-bonding a polyethylene film (manufactured by Tamapoli Co., Ltd., GF-818, thickness: 19 μm) as a cover film on the surface of the formed overcoat layer. By winding up the obtained photosensitive transfer material 2, a roll-shaped photosensitive transfer material 2 was produced.

Further, in Example 4, exposure was performed by a direct drawing exposure (DI exposure) method using a direct drawing exposure apparatus (manufactured by Via Mechanics, Ltd., DE-1DH, main wavelength 405 nm).
Further, in Example 7, a base material laminated with a photosensitive transfer material is fixed on a 4-inch silicon wafer with a tape, and then reduced projection exposure is performed using an i-wire stepper (NSR-2009i9C) manufactured by Nikon Corporation. After forming the pattern 3, heating was performed at 145 ° C. for 20 minutes.
Further, in Examples 9 and 10, the positive photosensitive resin composition PR1 shown in Table 5 was applied without using the photosensitive transfer material 1, dried at 90 ° C. for 100 seconds, and shown in Table 5. A resist layer having the same thickness was formed.
Further, in Examples 8 and 11, the negative photosensitive resin composition shown in Table 5 was applied without using the photosensitive transfer material 2, dried at 90 ° C. for 100 seconds, and shown in Table 5. A negative photosensitive resin layer N having a thickness was formed.

In Example 12, the light-shielding pattern 1 was formed as follows.
A PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness: 75 μm) was prepared. A printer was prepared in which the ink in the ink cartridge of the monochrome inkjet printer PX-K100 (manufactured by Seiko Epson Corporation) was transferred to silver nano ink (DryCure Ag-J manufactured by C-INK Co., Ltd.). A wiring pattern was formed by performing a printing operation on this printer via a printer driver, and then the printer was heated at 60 ° C. for 2 minutes. A PET film with a silver wiring pattern (line / space = 50 μm / 50 μm) was produced.
Further, after forming the resin pattern 2, the copper pattern 3 was formed as shown below.
An electroless copper plating solution (ARG copper manufactured by Okuno Pharmaceutical Industry Co., Ltd.) was prepared in a Cu plating bath according to the procedure described in the instruction manual, and then placed in a constant temperature bath at 45 ° C. for temperature control. A copper pattern was formed by electroless plating by impregnating the plating bath with a substrate.

In Example 13, the light-shielding pattern 1 was formed as follows.
After peeling the cover film from the photosensitive transfer material 1 on a polyimide (PI) film having a thickness of 100 μm, the photosensitive transfer material 1 was attached to a PET film with a copper layer. The above bonding was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min. Next, the resist layer was exposed by irradiating light with a maskless drawing apparatus (DWL66 + manufactured by Heidelberg, main wavelength: 405 nm). After peeling off the temporary support, the resist layer was shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. to form a resin pattern (line / space = 15 μm / 15 μm). Next, after forming a copper layer between the resist patterns and on the resist pattern by sputtering, the resin pattern and the copper layer on the resin pattern were removed using a stripping solution (10 mass% triethylamine aqueous solution). By the above procedure, a PI film with a copper pattern (line / space = 15 μm / 15 μm) was produced. The copper pattern functions as the light-shielding pattern 1.
Other operations were carried out in the same manner as in Example 1 except that a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution was used as the developing solution in the development of the resin pattern 2.

(Comparative Example 1)
In the step described in the section of "Formation of pattern 3 (copper pattern)", an attempt was made to produce a structure having a copper pattern by the same procedure as in Example 1 except that the light irradiation method was changed. Specifically, in a laminate having a PET film, a copper pattern (light-shielding pattern), a negative photosensitive resin layer N, and a temporary support in this order, the negative photosensitive resin layer N of the temporary support is arranged. After the photomask was brought into contact with the surface opposite to the surface, the negative photosensitive resin layer N was irradiated with light via the photomask. However, in the process of irradiating light, a misalignment of the copper pattern (light-shielding pattern), which is considered to be caused by the shrinkage of the PET film, was observed, so that the position of the opening of the photomask and the copper pattern (light-shielding pattern) were observed. ) Was difficult to align with the space. As a result, the resin pattern could not be formed in the space portion of the copper pattern (light-shielding pattern).

<Evaluation>
[Pattern formation]
Using an optical microscope, any 100 fields of view of the structure having the obtained pattern 3 were observed. The range of each field of view was 200 μm × 200 μm. Based on the number of visual fields in which the abnormal portion was observed in pattern 3, the formability of the conductive pattern was evaluated according to the following criteria. The abnormal portion refers to a portion in which morphological abnormalities such as cracking, peeling, and chipping are observed in the pattern 3. The evaluation results are shown in Table 5.
A: The number of visual fields in which the abnormal part is observed is less than 20.
B: The number of visual fields in which the abnormal portion is observed is 20 or more.

In addition, N9 in the negative type photosensitive composition column used in Example 3 of Table 5 indicates an overcoat coating liquid (composition N9).
From the results shown in Table 5, it can be seen that the method for producing the structure of Examples 1 to 13 can form a pattern in which the occurrence of morphological abnormalities is reduced as compared with the method for producing the structure of Comparative Example 1. ..

The disclosure of Japanese Patent Application No. 2020-080716 filed on April 30, 2020 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

10, 11: Transparent base material 10a: Exposed surface 20, 21: Light-shielding pattern (light-shielding pattern 1)
30: Negative type photosensitive resin layer (negative type photosensitive resin layer N)
30a: Exposed parts 40, 41: Resin pattern (resin pattern 2)
50, 51: Pattern (Pattern 3)
100: Laminated body 200: Structure

Claims

A transparent base material, a light-shielding pattern 1 arranged on the transparent base material, and a negative photosensitive resin arranged on the transparent base material and the light-shielding pattern 1 and in contact with the transparent base material. A step of preparing a laminate having a layer N,
A step of irradiating a part of the negative photosensitive resin layer N with light from a surface of the transparent substrate opposite to the surface on which the light-shielding pattern 1 is provided.
A step of forming the resin pattern 2 on the transparent substrate by developing the negative photosensitive resin layer N irradiated with light, and
The step of forming the pattern 3 in the region defined by the light-shielding pattern 1 and the resin pattern 2 is included.
A method for producing a structure in which the obtained structure has the resin pattern 2 as a permanent film.
The method for manufacturing a structure according to claim 1, wherein the light-shielding pattern 1 contains a metal.
The method for manufacturing a structure according to claim 1 or 2, wherein the pattern 3 has conductivity.
The method for manufacturing a structure according to any one of claims 1 to 3, wherein the pattern 3 is a pattern formed by a plating method.
The method for producing a structure according to any one of claims 1 to 4, wherein the light-shielding pattern 1 and the pattern 3 contain the same kind of material.
The method for producing a structure according to any one of claims 1 to 5, wherein the negative photosensitive resin layer N contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.
The method for producing a structure according to claim 6, wherein the ethylenically unsaturated compound contains a trifunctional or higher functional ethylenically unsaturated compound.
The method for producing a structure according to claim 6 or 7, wherein the ethylenically unsaturated compound contains a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
The method for producing a structure according to any one of claims 1 to 5, wherein the negative photosensitive resin layer N contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocationic polymerization initiator.
The method for producing a structure according to any one of claims 1 to 9, wherein the negative photosensitive resin layer N contains a metal oxidation inhibitor.
A process of forming a light-shielding layer on one surface of a transparent substrate,
A process of forming a photoresist layer on a light-shielding layer,
A step of exposing and developing the photoresist layer to form a resist pattern, and
The method for producing a structure according to any one of claims 1 to 10, further comprising a step of etching the light-shielding layer to form the light-shielding pattern 1.
The method for manufacturing a structure according to any one of claims 1 to 11, wherein the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
The method for producing a structure according to any one of claims 1 to 12, wherein the transparent base material is a transparent film base material.
The method for producing a structure according to any one of claims 1 to 13, further comprising a step of performing at least one of post-exposure and post-heating on the resin pattern 2.
The method for producing a structure according to any one of claims 1 to 14, wherein the negative photosensitive resin layer N is a layer formed of a photosensitive transfer material.
Any of claims 1 to 15, wherein the obtained structure is one type of structure selected from the group consisting of a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film. The method for producing a structure according to item 1.
With a transparent base material
The light-shielding pattern 1 arranged on the transparent substrate and
A resin pattern 2 arranged adjacent to the light-shielding pattern 1 on the transparent substrate and in contact with the transparent substrate,
The pattern 3 is provided in a region defined by the light-shielding pattern 1 and the resin pattern 2.
The average thickness of the light-shielding pattern 1 is 2 μm or less.
The average thickness of the resin pattern 2 exceeds 2 μm,
The average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
A structure having the resin pattern 2 as a permanent film.