JP2019128445A - Photosensitive transfer material and manufacturing method thereof, and resin pattern manufacturing method and circuit wiring manufacturing method - Google Patents

Abstract

To provide a photosensitive transfer material excellent in slipperiness on a mask during contact exposure, and a manufacturing method thereof; and a resin pattern manufacturing method and a circuit wiring manufacturing method that use the photosensitive transfer material.SOLUTION: A photosensitive transfer material comprises, on a cover film, a photosensitive layer, an adhesive layer and a temporary support in this order. The photosensitive layer contains particles. The photosensitive layer and the adhesive layer are in contact with each other, and can be separated from each other. A surface of the photosensitive layer after the separation of the photosensitive layer and the adhesive layer has unevenness formed by the particles.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a photosensitive transfer material and a manufacturing method thereof, a resin pattern manufacturing method, and a circuit wiring manufacturing method.

In a display device (organic electroluminescence (EL) display device, liquid crystal display device, etc.) provided with a touch panel such as a capacitance type input device, an electrode pattern corresponding to a sensor of a visual recognition portion, wiring of peripheral wiring portions and extraction wiring portions And the like are provided inside the touch panel.
In general, for forming a patterned layer, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material since the number of steps for obtaining a required pattern shape is small. With respect to (also referred to as "photosensitive layer"), a method of developing after exposure through a mask having a desired pattern is widely used.

  As such a photosensitive transfer material, for example, Patent Document 1 has a structure in which a support film, a cushion layer, a photosensitive layer, and a protective film are laminated in this order. The interlayer adhesion between the support layer and the protective film is greater than the interlayer adhesion between the photosensitive layer and the protective film, and the interlayer adhesion between the support film and the cushion layer is the cushion layer and the photosensitive layer. The thermal shrinkage rate of the protective film at 120 ° C. for 20 minutes is 5.0% or less in the vertical direction and 3.0% or less in the horizontal direction. Describes a photosensitive film characterized in that it is a layer formed by applying a photosensitive resin composition for forming the photosensitive layer onto the protective film and drying it.

Unexamined-Japanese-Patent No. 2007-41216

When forming a photosensitive layer on a substrate using a photosensitive transfer material, a laminate comprising at least a substrate, a photosensitive layer, and a temporary support is formed by affixing the photosensitive transfer material to the substrate. Be done. After exposing such a laminate, the photosensitive layer is developed to form a resin pattern.
Here, the temporary support of the laminate was peeled off after the temporary support was peeled off in the exposure for the purpose of improving the resolution of the obtained resin pattern, eliminating the influence of foreign substances in the temporary support, etc. It is considered to perform exposure (also referred to as “contact exposure”) by bringing a mask having a pattern into contact with the side surface.
When exposure is performed by bringing the mask into contact with the laminate after peeling off the temporary support as described above, the mask adheres to the surface of the laminate, and the mask once brought into contact hardly moves. In some cases, mask alignment may be difficult.
In the present disclosure, the above-mentioned state in which the mask once contacted is difficult to move is also referred to as “poor to mask sliding property (poor)”, and it is easy to move the mask once contacted again. It is also referred to as "high anti-mask slipperiness (excellent)".

The problem to be solved by the embodiments of the present invention is to provide a photosensitive transfer material excellent in anti-slip property to a mask at the time of contact exposure and a method for producing the same.
Another problem to be solved by the other embodiments of the present invention is to provide a method of manufacturing a resin pattern using the photosensitive transfer material and a method of manufacturing a circuit wiring.

Means for solving the above problems include the following aspects.
<1> On a cover film, it has a photosensitive layer, an adhesive layer, and a temporary support in this order,
The photosensitive layer contains particles,
The photosensitive layer and the adhesive layer are in contact,
The photosensitive layer and the adhesive layer are peelable,
The photosensitive transfer material which has the unevenness | corrugation in which the surface of the said photosensitive layer after peeling the said photosensitive layer and the said adhesive layer was formed with the said particle | grain.
<2> The photosensitive transfer material according to <1>, wherein the particles include at least one particle selected from the group consisting of silica particles, alumina particles, and organic polymer particles.
The photosensitive transfer material as described in said <1> or <2> whose average particle diameter of <3> above-mentioned particle | grains is 10 nm-200 nm.
<4> The photosensitive transfer material according to any one of <1> to <3>, wherein the content of the particles with respect to the total mass of the photosensitive layer is 1% by mass to 80% by mass.
<5> The photosensitive polymer according to any one of <1> to <4>, wherein the photosensitive layer further comprises a binder polymer having an acid group protected by an acid-degradable group, and a photoacid generator. Photosensitive transfer material.
The photosensitive transfer material as described in any one of said <1>-<4> in which the <6> above-mentioned photosensitive layer further contains the binder polymer which has an acidic radical, a polymeric compound, and a photoinitiator.
<7> A step of applying a photosensitive layer-forming composition containing at least particles on a cover film to form a photosensitive layer
Bonding a temporary support having an adhesive layer so that the adhesive layer is in contact with the photosensitive layer. A method for producing a photosensitive transfer material.
<8> A step of peeling the cover film in the photosensitive transfer material according to any one of <1> to <6> above,
The outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off is brought into contact with and bonded to a support having a conductive layer;
A step of peeling the temporary support and the adhesive layer, and the photosensitive layer;
Bringing an exposure mask into contact with the photosensitive layer, and exposing the photosensitive layer to a pattern through the exposure mask;
And a step of developing the photosensitive layer to form a resin pattern in this order.
<9> A step of peeling the cover film in the photosensitive transfer material according to any one of <1> to <6> above,
The outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off is brought into contact with and bonded to a support having a conductive layer;
A step of peeling the temporary support and the adhesive layer, and the photosensitive layer;
Bringing an exposure mask into contact with the photosensitive layer, and exposing the photosensitive layer to a pattern through the exposure mask;
Developing the photosensitive layer to form a resin pattern;
And etching the conductive layer using the formed resin pattern as a mask in this order.

According to the embodiment of the present invention, it is possible to provide a photosensitive transfer material excellent in anti-slip property to a mask at the time of contact exposure and a method for producing the same.
In addition, according to another embodiment of the present invention, it is possible to provide a method for producing a resin pattern using the photosensitive transfer material and a method for producing a circuit wiring.

FIG. 2 is a schematic view showing an example of a layer configuration of a photosensitive transfer material according to the present disclosure. FIG. 6 is a schematic view showing a pattern A. FIG. 7 is a schematic view showing a pattern B.

The contents of the present disclosure will be described below. In addition, although it demonstrates, referring an attached drawing, a code | symbol may be abbreviate | omitted.
Moreover, the numerical range represented using "-" in this indication means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
Also, in the present disclosure, “(meth) acrylic” represents both or either of acrylic and methacrylic, and “(meth) acrylate” represents both or any of acrylate and methacrylate.
Furthermore, in the present disclosure, the amount of each component in the composition is the total amount of the plurality of corresponding substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Means
In the present disclosure, the term "step" is included in the term if the intended purpose of the step is achieved, even if it can not be distinguished clearly from the other steps, as well as independent steps.
In the notation of groups (atomic groups) in the present disclosure, notations not describing substitution and non-substitution include 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).
In addition, the chemical structural formula in the present disclosure may be described as a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Moreover, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all are trade names manufactured by Tosoh Corp.) unless otherwise noted. It is a molecular weight which is detected using a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and a polystyrene as a standard substance.

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has a photosensitive layer, an adhesive layer, and a temporary support in this order on a cover film, the photosensitive layer includes particles, and the photosensitive layer and the adhesive Layer is in contact, the photosensitive layer and the adhesive layer are peelable, and the surface of the photosensitive layer after the photosensitive layer and the adhesive layer are peeled off is formed by the particles. Have.

  When the contact exposure is performed using the transfer film described in Patent Document 1, the present inventors have a low anti-mask slip property, and after changing the mask once, changing the mask position for alignment. I have found that it can be difficult.

Therefore, as a result of intensive investigations, the present inventors have found that when the photosensitive transfer material according to the present disclosure described above is used, it is excellent in anti-mask slippage during contact exposure.
Although the detailed mechanism by which the said effect is acquired is unknown, it estimates as follows.
The photosensitive transfer material according to the present disclosure peels at the interface between the adhesive layer and the photosensitive layer when the temporary support is peeled. Therefore, the mask and the photosensitive layer come into contact during contact exposure.
Here, since the surface of the photosensitive layer according to the present disclosure has unevenness formed by particles contained in the photosensitive layer, the mask is easily slipped even after being in contact with the photosensitive layer once, and considered to be excellent in anti-mask sliding properties. It is done.
By using such a photosensitive transfer material excellent in anti-slip property at the time of contact exposure, alignment of the mask at the time of contact exposure becomes easy, and it is thought that the pattern by the photosensitive layer is easily formed at the target position. Be

  Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.

FIG. 1 schematically shows an example of the layer configuration of a photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, the temporary support 10, the adhesive layer 18, the photosensitive layer 14, and the cover film 16 are laminated in this order.
The photosensitive layer 14 contains particles, and irregularities due to the particles are formed on the surface of the photosensitive layer 14 at the interface between the photosensitive layer 14 and the adhesive layer 18 (not shown).
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described.

<Temporary support>
The temporary support is a support that supports the adhesive layer and the photosensitive layer, and is peeled off together with the adhesive layer at an arbitrary timing before exposure after transfer of the photosensitive layer and the like.
The temporary support used in the present disclosure may or may not have light transparency.
As a temporary support body, a glass substrate, a resin film, paper etc. are mentioned, A resin film is especially preferable from a viewpoint of intensity | strength, flexibility, etc. As a resin film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film etc. are mentioned. Among them, a polyethylene terephthalate film is preferable, and a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, and is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm in terms of handleability, versatility, and the like.
The thickness of the temporary support may be selected according to the material from the viewpoint of strength as the support, flexibility required for bonding with the wiring formation substrate, and the like.

  Preferred embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, and the contents of this publication are incorporated herein.

<Adhesive layer>
The adhesive layer is peeled off together with the temporary support at the time of peeling off the temporary support.
The peel strength between the temporary support and the adhesive layer is preferably 0.001 N / 25 mm or more in order to prevent peeling at the interface between the temporary support and the adhesive layer.
Further, in order to enable peeling at the interface between the adhesive layer and the photosensitive layer, the peeling force between the adhesive layer and the photosensitive layer is preferably 0.5 N / 25 mm or less.
The peeling force is measured by conducting a 180 ° peeling test at a tensile speed of 300 mm / min under a room temperature environment (23 ° C.).

There is no restriction | limiting in particular as a material of an adhesive layer, According to the objective, it can select suitably, For example, the layer containing a well-known adhesive or an adhesive agent is mentioned.

[Adhesive agent]
Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. Examples of pressure-sensitive adhesives include “acrylic pressure-sensitive adhesives” described in Chapter 2 of “Characteristic Evaluation and Control Technology of Release Paper / Peeling Films and Pressure-sensitive Tapes”, Information Technology, 2004, Chapter 2. Agents, silicone pressure-sensitive adhesives and the like. In addition, an acrylic adhesive means the adhesive containing the polymer ((meth) acrylic polymer) of a (meth) acrylic monomer.
When an adhesive is included, a tackifier may be further included.

〔adhesive〕
As an adhesive agent, a urethane resin adhesive, a polyester adhesive, an acrylic resin adhesive, ethylene vinyl acetate resin adhesive, a polyvinyl alcohol adhesive, a polyamide adhesive, a silicone adhesive etc. are mentioned, for example. A urethane resin adhesive or an acrylic resin adhesive is preferable from the viewpoint that the adhesive strength is relatively high and that the adhesive strength can be easily controlled by introducing a thermal crosslinking or photocrosslinking structure.

[Method of forming adhesive layer]
The method for forming the adhesive layer is not particularly limited, and a method of laminating the temporary support on which the adhesive layer is formed such that the adhesive layer and the photosensitive layer are in contact with each other, the adhesive layer alone may be used as the photosensitive layer. The method of laminating so that it may contact | connect, the method of apply | coating the composition containing the said adhesive or adhesive on a photosensitive layer, etc. are mentioned.
As the temporary support on which the adhesive layer is formed, a commercially available product may be used. For example, E-MASK AW303D, E-MASK RP207 (both manufactured by Nitto Denko Corporation), PanaProtect HP25, PanaProtect MK38S (both Panac Co., Ltd.) and the like.

[Characteristics of adhesive layer]
The thickness of the adhesive layer in the photosensitive transfer material according to the present disclosure is preferably 0.01 μm to 50 μm, more preferably 0.1 μm to 20 μm, and most preferably 0.2 μm to 10 μm. When the thickness of the adhesive layer is 0.01 μm or more, the particles may be prevented from being buried in the photosensitive layer at the time of lamination, and good slip properties may easily be exhibited at the time of mask contact. Moreover, when it is 50 micrometers or less, the peelability of an adhesive layer and a photosensitive layer may become favorable.

<Photosensitive layer>
The photosensitive layer in the photosensitive transfer material according to the present disclosure includes particles.
Further, in the photosensitive transfer material according to the present disclosure, the photosensitive layer and the adhesive layer are in contact with each other, the photosensitive layer and the adhesive layer can be peeled off, and the photosensitive layer and the adhesive layer And the surface of the photosensitive layer after peeling off the surface has irregularities formed by the particles.
The contact between the photosensitive layer and the adhesive layer means that at least a part of the photosensitive layer and the adhesive layer are in contact, and the entire photosensitive layer and the adhesive layer may be in contact with each other. The photosensitive layer and the adhesive layer are preferably in contact with each other at least at the portion where the mask and the photosensitive layer are in contact exposure.

[Concavity and convexity]
The surface of the photosensitive layer after peeling off the photosensitive layer and the adhesive layer has irregularities formed by particles, the unevenness derived from the shape of the particles is formed on the surface of the photosensitive layer after the peeling. It means that.
The unevenness may be formed by exposing the particles from the layer of the binder polymer contained in the photosensitive layer, or may be formed by covering a part or all of the particles with the binder polymer.
In the present disclosure, it is confirmed by observing the surface of the photosensitive layer after peeling using a scanning electron microscope (SEM) that the surface of the photosensitive layer after peeling has irregularities formed by particles. It is possible.

〔particle〕
The particles contained in the photosensitive layer are preferably metal oxide particles or organic polymer particles from the viewpoint of anti-mask slip properties, and are at least selected from the group consisting of silica particles, alumina particles and organic polymer particles. More preferably, it contains one type of particle.
Silica particles (refractive index: 1.4 to 1.5), alumina particles (refractive index: 1.6 to 1.65) and organic polymer particles (refractive index: 1.4 to 1.7) have their refractive indexes. However, since it is close to the refractive index of an organic substance (refractive index: 1.4 to 1.6) such as resin contained in the photosensitive layer, it is preferable because light scattering is suppressed and the linearity of the resist pattern is improved.

-Metal oxide particles-
The metal of the metal oxide particles in the present disclosure also includes semimetals such as B, Si, Ge, As, Sb, and Te.
As metal oxide particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B And oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferable, and silica, alumina, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide Or, antimony / tin oxide is more preferable, silica, alumina, titanium oxide, titanium composite oxide, or zirconium oxide is more preferable, and silica or alumina is particularly preferable.

-Organic polymer particles-
Examples of organic polymer particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters, and cellulose polymers such as nitrocellulose, methyl cellulose, ethyl cellulose and cellulose acetate , Polyethylene, polypropylene, polystyrene, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl pyrrolidone, polyvinyl butyral, copolymer of vinyl polymer such as polyvinyl alcohol and vinyl compound, polyester, polyurethane, polyamide A polymer obtained by polymerizing and crosslinking a photopolymerizable or thermopolymerizable compound such as an epoxy compound, a condensation polymer such as butadiene-styrene copolymer, or a rubber-based thermoplastic polymer such as butadiene-styrene copolymer. Melamine compounds and the like.
Among these, as the organic polymer particles, acrylic resin particles are preferably mentioned, and polymethyl methacrylate particles are more preferably mentioned.

-Surface treatment-
The particles used in the present disclosure can also be surface-treated with an organic or inorganic material to impart dispersion stability. The particles are preferably particles having a hydrophobic surface. For example, particles produced by a method such as hydrophobizing the surface of the particles may be used.

-Particle size-
The average particle diameter of the above particles is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm, still more preferably 30 nm to 100 nm, from the viewpoint of improving anti-mask slip property, and further preferably 50 nm to 80 nm. Is particularly preferred.
The average particle size of the particles can be determined as an arithmetic average value by measuring the diameter of 20 particles observed for a section of the coated film using a transmission electron microscope.

The photosensitive layer may contain particles alone or in combination of two or more.
The content of the particles with respect to the total mass of the photosensitive layer is preferably 1% by mass to 80% by mass, and 2% by mass to 30% by mass from the viewpoint of mask slipperiness and linearity of the resist pattern. The content is more preferably 5% by mass to 10% by mass.

[Type of photosensitive layer]
The photosensitive layer in the present disclosure may be a positive photosensitive layer or a negative photosensitive layer.
When it is a positive photosensitive layer, the photosensitive layer is preferably a chemically amplified positive photosensitive layer.
The photo acid generators such as onium salts and oxime sulfonate compounds described later are protected in the binder polymer having an acid group protected with an acid decomposable group and an acid generated in response to actinic radiation (actinic ray). Since the acid acts as a catalyst for the deprotection of the acid groups, the acid generated by the action of one photon contributes to a large number of deprotection reactions, and the quantum yield is more than 1, for example, a power of 10 As a result of so-called chemical amplification, high sensitivity is obtained.
On the other hand, when a quinonediazide compound (NQD) is used as a photoacid generator sensitive to actinic radiation, a carboxy group is produced by successive photochemical reactions, but its quantum yield is necessarily 1 or less, and the chemical amplification type is Not applicable.

When the photosensitive layer is a positive photosensitive layer, the photosensitive layer preferably contains a binder polymer and a photoacid generator from the viewpoint of pattern formability. The binder polymer preferably further contains a binder polymer having an acid group protected with an acid-decomposable group from the viewpoint of pattern formation, and is a structural unit having an acid group protected with an acid-decomposable group. It is more preferable to further contain a polymer having
Moreover, when the said photosensitive layer is a negative photosensitive layer, it is preferable that the said photosensitive layer further contains the binder polymer which has an acid group, a polymeric compound, and a photoinitiator from a viewpoint of pattern formation. .
When the photosensitive layer is a negative photosensitive layer, for example, a photosensitive resin composition layer described in JP-A-2006-224162 may be used as the negative photosensitive layer.

[A polymer component containing a polymer having a structural unit having an acid-degradable group-protected acid group]
When the photosensitive layer in the present disclosure is a positive photosensitive layer, the photosensitive layer preferably contains a binder polymer having an acid-degradable group-protected acid group.
The binder polymer having an acid group which is protected by the acid decomposable group is a polymer having a structural unit (also referred to as a “structural unit A”) which has an acid group which is protected by the acid decomposable group (“specific polymer” It is preferable that it is also ".
In addition to the polymer having the constituent unit A, the positive photosensitive layer may contain other polymers. In the present disclosure, the polymer having the structural unit A and the other polymers are collectively referred to as a “polymer component”.
In the specific polymer, the structural unit A having an acid group protected by an acid-degradable group in the specific polymer is subjected to a deprotection reaction to become an acid group by the action of a catalytic amount of an acidic substance generated by exposure, Development by is possible.
The preferable aspect of the structural unit A is demonstrated below.

The photosensitive layer may further contain a polymer other than the polymer having a structural unit having an acid group protected by an acid degradable group.
Moreover, it is preferable that all the polymers contained in the said polymer component are polymers which each have a structural unit which has an acidic radical mentioned later at least.
The photosensitive layer may further contain other polymers. The above-mentioned polymer component in the present disclosure is intended to mean one including other polymers added as needed, unless otherwise stated. In addition, even if it is a high molecular compound, the compound applicable to the crosslinking agent and dispersing agent mentioned later shall not be contained in the said polymer component.

  The specific polymer is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof. In addition, you may have structural units other than (meth) acrylic acid or structural units derived from its ester, for example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, etc.

The photosensitive layer preferably contains, as a polymer component, a polymer having a structural unit A1 represented by the following formula A1 as the structural unit A, from the viewpoint of solubility in a developer and transferability, and a polymer As a component, it is preferable to include a specific polymer having a constituent unit A1 represented by the following formula A as the constituent unit A and having a glass transition temperature of 90 ° C. or less, and as the polymer component, the constituent unit A It is further preferable to include a specific polymer having a structural unit A1 represented by the following formula A1 and a structural unit B having an acid group described later, and having a glass transition temperature of 90 ° C. or less.
The specific polymer contained in the photosensitive layer may be only one type, or two or more types.

-Structural unit A-
It is preferable that the said polymer component contains the polymer which has at least the structural unit A which has an acidic group protected by the acid-degradable group. When the polymer component contains a polymer having the structural unit A, it is possible to obtain a highly sensitive chemically amplified positive type photosensitive layer.
As the “acid-degradable group-protected acid group” in the present disclosure, those known as an acid group and an acid-degradable group can be used without particular limitation. As a specific acid group, a carboxy group and a phenolic hydroxyl group are preferably mentioned. The acid group protected with an acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester protected with a group represented by the formula A1). An acetal functional group such as a group) and a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Can do.
Among these, as the above-mentioned acid-decomposable group, a group having a structure protected in the form of acetal is preferable.

<< Constituent Unit A1 >>
The structural unit A having an acid group which is protected by an acid decomposable group is preferably a structural unit A1 represented by the following formula A1 from the viewpoint of sensitivity and resolution.

In formula A1, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or R ³¹ or R ³² and R ³³ may combine to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group.

In Formula A1, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferred. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula A1, R ³³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Moreover, the alkyl group and aryl group in R < ³¹ > -R < ³³ > may have a substituent.
In formula A1, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and it is preferable that R ³¹ or R ³² and R ³³ link to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In formula A1, X ⁰ represents a single bond or an arylene group, and a single bond is preferred. The arylene group may have a substituent.
The constituent unit A1 represented by the above-mentioned formula A1 is a constituent unit having a carboxy group protected by an acid decomposable group. When the specific polymer contains the structural unit A1 represented by the formula A1, the sensitivity at the time of pattern formation is excellent, and is superior to the resolution.

In formula A1, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the specific polymer can be further lowered.
More specifically, with respect to the total amount of the structural units A1 contained in the specific polymer is preferably the structural unit R ³⁴ in formula A is a hydrogen atom is at least 20 mass%.
Incidentally, in the structural unit A1, the content of the structural unit ^{R 34} is a hydrogen atom in the formula A1 (content: weight ratio) ^is calculated by the usual method from the 13 C- nuclear magnetic resonance spectra (NMR) measurements It can be confirmed by the intensity ratio of the peak intensity.

  Among the structural units A1 represented by the formula A1, a structural unit represented by the following formula A2 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In Formula A2, R ³⁴ represents a hydrogen atom or a methyl group, and R ^{35 to} R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A2, R ³⁴ is preferably a hydrogen atom.
In formula A2, R ^{35 to} R ⁴¹ are preferably hydrogen atoms.

The following structural unit can be illustrated as a preferable specific example of structural unit A1 which has a carboxy group protected with an acid degradable group represented by Formula A1. R ³⁴ represents a hydrogen atom or a methyl group.

<< Constituent Unit A3 >>
Further, as the structural unit A, a structural unit A3 represented by the following formula A3 is preferable from the viewpoint of suppressing deformation of the pattern shape.

In Formula A3, R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R ^B1 and R ^B2 is an alkyl group or an aryl group, and R ^B3 is an alkyl group or Represents an aryl group, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, and X ^B represents a single bond or a divalent linking group; R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In Formula A3, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ^B1 or R ^B2 is an aryl group, a phenyl group is preferred. R ^B1 and R ^B2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A3, R ^B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Moreover, the alkyl group and aryl group in R ^{B1 to} R ^B3 may have a substituent.
In formula A3, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, and R ^B1 or R ^B2 and R ^B3 are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula A3, X ^B represents a single bond or a divalent linking group, and is a single bond or an alkylene group, —C (═O) O—, —C (═O) NR ^N —, —O—, or a combination thereof. Is preferred, and a single bond is more preferred. The alkylene group may be linear, branched or cyclic and may have a substituent. 1-10 are preferable and, as for carbon number of an alkylene group, 1-4 are more preferable. If X ^B -C where (= O) containing O- a, -C (= O) and carbon atoms contained in the ^O-, embodiments the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. When ^{containing, -C (= O) NR N} - - is ^{X B -C (= O) NR} N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In Formula A3, the group containing R ^{B1 to} R ^B3 and X ^B are preferably bonded to each other at the para position.
In formula A3, R ^B12 represents a substituent, preferably an alkyl group or a halogen atom. 1-10 are preferable and, as for carbon number of an alkyl group, 1-4 are more preferable.
In Formula A3, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

In formula A3, R ^B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of being able to lower the Tg of the specific polymer.
More specifically, it is preferable that the structural unit whose R ^B4 in the formula A3 is a hydrogen atom is 20% by mass or more with respect to the total content of the structural unit A contained in the specific polymer.
In addition, content (content ratio: mass ratio) of the structural unit whose R ^B4 in Formula A3 is a hydrogen atom in the structural unit A is calculated by ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement according to a conventional method. It can be confirmed by the intensity ratio of the peak intensity.

  Among the structural units represented by the formula A3, the structural unit represented by the following formula A4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.

In Formula A4, R ^B4 represents a hydrogen atom or a methyl group, R ^{B5 to} R ^B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and n is 0 Represents an integer of ~ 4.
In formula A4, R ^B4 is preferably a hydrogen atom.
In Formula A4, R ^{B5 to} R ^B11 are preferably hydrogen atoms.
In formula A4, R ^B12 represents a substituent, preferably an alkyl group or a halogen atom. 1-10 are preferable and, as for carbon number of an alkyl group, 1-4 are more preferable.
In Formula A4, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

The following structural unit can be illustrated as a preferable specific example of structural unit A4 represented by Formula A4. R ^B4 represents a hydrogen atom or a methyl group.

<< Content of Structural Unit A >>
The constituent unit A contained in the specific polymer may be one type or two or more types.
The content of the structural unit A in the specific polymer is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and more preferably 30% by mass with respect to the total mass of the specific polymer. More preferably, it is 70 mass%.
The content (content ratio: mass ratio) of the structural unit A in the specific polymer can be confirmed by the intensity ratio of peak intensities calculated from ¹³ C-NMR measurement by a conventional method.
In addition, the ratio of the structural unit A is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer component after all the polymer components are decomposed into constituent units (monomer units), The content is more preferably 10% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.

[Constituent unit B]
It is preferable that the said specific polymer contains the structural unit B which has an acidic radical.
The structural unit B is a structural unit that includes a protective group, for example, an acid group that is not protected by an acid-degradable group, that is, an acidic group that does not have a protective group. When the specific polymer contains the structural unit B, the sensitivity at the time of pattern formation becomes good, and it becomes easily soluble in an alkaline developer in the development step after pattern exposure, and the development time can be shortened.
The term "acid group" as used herein means a proton dissociative group having a pKa of 12 or less. The acid group is usually incorporated into the polymer as a structural unit (structural unit B) containing an acid group, using a monomer capable of forming an acid group. From the viewpoint of sensitivity improvement, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Moreover, it is preferable that pKa of an acidic radical is -5 or more.

  The specific polymer contains the specific polymer by including, as a copolymerization component, the structural unit A and the structural unit B having an acid group that is not protected by a protecting group, and having a glass transition temperature of 90 ° C. or lower. The positive photosensitive layer has better resolution and sensitivity during pattern formation while maintaining good transferability and peelability from the cover film.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group. Among them, at least one acid group selected from the group consisting of a carboxylic acid group and a phenolic hydroxyl group is preferable.
The introduction of a structural unit having an acid group into a specific polymer can be carried out by copolymerizing a monomer having an acid group.
The structural unit containing an acid group, which is the structural unit B, is a structural unit derived from styrene or a structural unit derived from a vinyl compound, or a structural unit derived from a (meth) acrylic acid. It is more preferable that it is a unit.

As the structural unit B, a structural unit having a carboxylic acid group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that the sensitivity at the time of pattern formation is better.
The monomer having an acid group capable of forming the structural unit B is not limited to the examples described above.

The constituent unit B contained in the specific polymer may be only one type or two or more types.
The specific polymer preferably contains 0.1% by mass to 20% by mass, and 0.5% by mass to 15% by mass of the structural unit having an acid group (the structural unit B) with respect to the total mass of the specific polymer. It is more preferable to contain 1% by mass to 10% by mass. Within the above range, pattern formability becomes better.
Content (content ratio: mass ratio) of the structural unit B in a specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

[Other constituent units]
The specific polymer does not impair the effects of the photosensitive transfer material according to the present disclosure other structural units (hereinafter, may be referred to as structural unit C) other than the structural unit A and the structural unit B described above. You may include in the range.
There is no restriction | limiting in particular as a monomer which forms the structural unit C, For example, Styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester , Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds Saturated compounds can be mentioned.
Various characteristics of the specific polymer can be adjusted by adjusting at least one of the kind and the content using the structural unit C. In particular, by appropriately using the structural unit C, the Tg of the specific polymer can be easily adjusted to 90 ° C. or less.
The specific polymer may contain only one type of the structural unit C, or may contain two or more types.

  Specifically, the structural unit C is styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Mention may be made of structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, or the like. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Moreover, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specifically as a monomer which forms these structural units, styrene, tert- butoxystyrene, methylstyrene, alpha-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate and the like. Among them, as the structural unit C, structural units derived from cyclohexyl (meth) acrylate are preferably mentioned.

  Moreover, as a monomer which forms the structural unit C, (meth) acrylic-acid alkylester is preferable from an adhesive viewpoint, for example. Among these, (meth) acrylic acid alkyl esters having an alkyl group having 4 to 12 carbon atoms are more preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  70 mass% or less is preferable with respect to the total mass of a specific polymer, as for content of the structural unit C, 60 mass% or less is more preferable, and 50 mass% or less is still more preferable. The lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, resolution and adhesion are further improved.

It is also preferable that the specific polymer contains a structural unit having an ester of an acid group in the structural unit B as the structural unit C from the viewpoint of optimizing the solubility in a developer and the physical properties of the photosensitive layer.
Among them, the specific polymer preferably contains, as the structural unit B, a structural unit having a carboxylic acid group, and further preferably contains a structural unit C containing a carboxylic acid ester group as a copolymerization component, for example, (meth) acrylic acid The polymer containing the structural unit B derived from and the structural unit (c) derived from (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl or (meth) acrylic acid n-butyl is more preferable.
Hereinafter, although the preferable example of the specific polymer in this indication is given, this indication is not limited to the following illustrations. In addition, the ratio of the structural unit in the following exemplary compounds and the weight average molecular weight are suitably selected in order to obtain preferable physical properties.

[Glass transition temperature of polymer: Tg]
It is preferable that the glass transition temperature (Tg) of the specific polymer in this indication is 90 degrees C or less. When the Tg is 90 ° C. or less, the photosensitive layer has high adhesion and is more excellent in transferability.
The Tg is more preferably 60 ° C. or less, still more preferably 40 ° C. or less.
Moreover, there is no restriction | limiting in particular in the lower limit of said Tg, However, -20 degreeC or more is preferable and -10 degreeC or more is more preferable. When the Tg of the specific polymer is −20 ° C. or higher, good pattern formability is maintained. For example, when a cover film is used, a decrease in peelability when the cover film is peeled is suppressed.
Furthermore, the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or less, more preferably 60 ° C. or less, and 40 ° C. or less from the viewpoint of transferability. Is more preferred.

The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
The specific measuring method followed the method as described in JISK7121 (1987) or JISK6240 (2011). The glass transition temperature in the present disclosure uses an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig).
The method of measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after maintaining the apparatus at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus is stabilized, the heating rate is about 20 ° C./min and about 30 times higher than the temperature at which the glass transition is completed. Heat to a high temperature and draw a DTA curve or a DSC curve.
Extrapolation glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line extending the baseline on the low temperature side in the DTA curve or DSC curve to the high temperature side, and the step change portion of the glass transition It is determined as the temperature at the point of intersection with the tangent drawn at the point where the slope of the curve is at a maximum.

As a method of adjusting the Tg of the polymer to the preferable range described above, for example, the FOX formula is used as a guideline from the Tg of the homopolymer of each constitutional unit of the target polymer and the mass ratio of each constitutional unit It is possible to control the Tg of the target specific polymer.
Regarding FOX Formula The Tg of the homopolymer of the first constitutional unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constitutional unit is W1, and the Tg of the homopolymer of the second constitutional unit Is Tg2 and the mass fraction of the copolymer of the second structural unit is W2, the Tg0 (K) of the copolymer containing the first structural unit and the second structural unit is It is possible to estimate according to the equation.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
The type and mass fraction of each structural unit contained in the copolymer can be adjusted using the above-described FOX formula to obtain a copolymer having a desired Tg.
Moreover, it is also possible to adjust Tg of a polymer by adjusting the weight average molecular weight of a polymer.

[Molecular weight of polymer: Mw]
The molecular weight of the specific polymer is preferably 60,000 or less in terms of weight average molecular weight in terms of polystyrene. When the weight average molecular weight of the specific polymer is 60,000 or less, the melt viscosity of the photosensitive layer can be suppressed low, and bonding at a low temperature (for example, 130 ° C. or less) can be realized when bonding to the substrate.
Moreover, it is preferable that the weight average molecular weights of a specific polymer are 2,000-60,000, and it is more preferable that it is 3,000-50,000.
In addition, the weight average molecular weight of a polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as a measuring apparatus, and the contents of the apparatus and the measuring technique It is known to those skilled in the art.
The measurement of the weight average molecular weight by gel permeation chromatography (GPC) is carried out using HLC (registered trademark) -8220GPC (manufactured by Tosoh Corp.) as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) as a column. .6 mm ID x 15 cm, Tosoh Corp. product, Super HZ 4000 (4.6 mm ID x 15 cm, Tosoh Corp. product), Super HZ 3000 (4.6 mm ID x 15 cm, Tosoh Corp. product), Super HZ 2000 (4.6 mm ID) It is possible to use THF (tetrahydrofuran) as an eluent using one obtained by connecting in series each one x 15 cm, manufactured by Tosoh Corp., in series.
In addition, as measurement conditions, the sample concentration is 0.2% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, and the measurement temperature is 40 ° C., using a differential refractive index (RI) detector be able to.
The calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using any one of 7 samples of “A-2500” and “A-1000”.

  The ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight of the specific polymer is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

[Method of producing specific polymer]
The method for producing the specific polymer (synthetic method) is not particularly limited, but one example is formation of a polymerizable monomer for forming the structural unit A1 represented by the formula A, and a structural unit B having an acid group May be synthesized by polymerization using a polymerization initiator in an organic solvent containing a polymerizable monomer for forming the polymer and, if necessary, a polymerizable monomer for forming the other constituent unit C. it can. Moreover, it can also be synthesized by so-called polymer reaction.

The photosensitive layer in the present disclosure contains the polymer component at a ratio of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive layer, from the viewpoint of expressing good adhesion to the substrate. Is preferable, and it is more preferable to contain in the ratio of 70 mass%-98 mass%.
In addition, the photosensitive layer contains the specific polymer at a ratio of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive layer, from the viewpoint of expressing good adhesion to the substrate. Preferably, 70% by mass to 98% by mass is more preferable.

[Other polymers]
The photosensitive layer contains, as a polymer component, a polymer that does not contain the structural unit (a) represented by the formula A as long as the effects of the photosensitive transfer material according to the present disclosure are not impaired in addition to the specific polymer (“other And the like) may be further included. When the photosensitive layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on all the polymer components, and 20% by mass. It is further more preferable that the content is% or less.

The photosensitive layer may contain only one type of other polymer in addition to the specific polymer, or may contain two or more types.
As other polymers, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all, manufactured by Sartmar) , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 6 , Joncryl 67, and Joncryl 586 (above, manufactured by BASF Corp.) can also be used.

[Photo acid generator]
When the photosensitive layer in the present disclosure is a positive photosensitive layer, the photosensitive layer preferably contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid upon irradiation with radiation such as ultraviolet light, far ultraviolet light, X-ray, and charged particle beam.
The photoacid generator used in the present disclosure is preferably a compound that responds to actinic radiation having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and generates an acid, but its chemical structure is not limited. In addition, a photoacid generator which does not directly react to actinic light having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that responds to actinic light having a wavelength of 300 nm or more by using it in combination with a sensitizer. It can be preferably used in combination.
The photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a pKa of 2 or less Particularly preferred are photoacid generators which generate an acid of The lower limit value of pKa is not particularly limited, but is preferably, for example, -10.0 or more.

As a photo-acid generator, an ionic photo-acid generator and a nonionic photo-acid generator can be mentioned.
Further, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound More preferably,

  Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound in terms of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. As a specific example of trichloromethyl-s-triazines and a diazomethane derivative, the compound as described in stage 0083-stage 0088 of Unexamined-Japanese-Patent No. 2011-221494 can be illustrated.

  As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.

In formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site to another atom or another group.

In the compound having an oxime sulfonate structure represented by the formula (B1), any group may be substituted, and the alkyl group in R ²¹ may be linear or branched, It may have a ring structure. The permissible substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ is a bridged alicyclic group such as an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group (7, 7-dimethyl-2-oxonorbornyl group, etc. , Preferably a bicycloalkyl group or the like) or a halogen atom.
As the aryl group for R ^21, an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group and a halogen atom.

  The compound having an oxime sulfonate structure represented by the formula (B1) is also preferably the oxime sulfonate compound described in paragraph 0078 to paragraph 0111 of JP-A-2014-85643.

  Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Among these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.

  As the ionic photoacid generator, ionic photoacid generators described in paragraphs 0114 to 0133 of JP 2014-85643 A can also be preferably used.

A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the photosensitive layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive layer from the viewpoint of sensitivity and resolution. It is more preferable that it is -5 mass%.

[Polymerizable compound]
When the photosensitive layer in the present disclosure is a negative photosensitive layer, the photosensitive layer preferably contains a polymerizable compound.
As a polymerizable compound, an ethylenically unsaturated compound is preferable.
The ethylenically unsaturated compound is a component that contributes to the photosensitivity (i.e., photocurability) of the photosensitive layer and the strength of the cured film.
In addition, the ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.

The photosensitive layer preferably contains, as the ethylenically unsaturated compound, a difunctional or more ethylenically unsaturated compound.
Here, the bifunctional or more ethylenic unsaturated compound means a compound having two or more ethylenic unsaturated groups in one molecule.
As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

There is no restriction | limiting in particular as a bifunctional ethylenic unsaturated compound, It can select suitably from well-known compounds.
Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. Examples include diol di (meth) acrylate.
More specifically, as the bifunctional ethylenically unsaturated compound, tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin Nakamura Chemical Industry Co., Ltd. product etc. are mentioned.
Moreover, as a bifunctional ethylenically unsaturated compound, the bifunctional ethylenically unsaturated compound which has a bisphenol structure is also used suitably.
As a bifunctional ethylenically unsaturated compound which has a bisphenol structure, the compound as described in stage 0072-stage 0080 of Unexamined-Japanese-Patent No. 2016-224162 is mentioned.
Specific examples include alkylene oxide-modified bisphenol A di (meth) acrylate, and 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2-bis (4- (methacryloxyethoxy). Propoxy) phenyl) propane and the like are preferred.

There is no restriction | limiting in particular as an ethylenically unsaturated compound more than trifunctional, It can select suitably from well-known compounds.
Examples of the trifunctional or higher ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) Acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, (meth) acrylate compound of glycerin tri (meth) acrylate skeleton, and the like can be mentioned.

  Here, “(tri / tetra / penta / hexa) (meth) acrylate” is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate "(Tri / tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

  Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (manufactured by Nippon Kayaku Co., Ltd. KAYARAD (registered trademark) DPCA-20, Shin-Nakamura Chemical Co., Ltd. A-9300-1CL, etc.), Alkylene oxide modified compound of (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd. Etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

As an ethylenically unsaturated compound, a urethane (meth) acrylate compound (preferably a urethane (meth) acrylate compound having three or more functional groups) is also mentioned.
Examples of the trifunctional or higher urethane (meth) acrylate compounds include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), UA-1100H (Shin-Nakamura Chemical Co., Ltd.) And the like.

Moreover, it is preferable that an ethylenically unsaturated compound contains the ethylenically unsaturated compound which has an acid group.
As an acid group, a phosphoric acid group, a sulfonic acid group, and a carboxy group are mentioned, for example, A carboxy group is preferable.
Examples of the ethylenically unsaturated compound having an acid group include 3 to 4 functional ethylenically unsaturated compounds having an acid group (one having a carboxy group introduced into a pentaerythritol tri and tetraacrylate (PETA) skeleton (acid value = 80 mg KOH / g to 120 mg KOH / g), 5 to 6 functional ethylenically unsaturated compounds having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) skeleton introduced with a carboxy group (acid value = 25 mg KOH / g To 70 mg KOH / g)) and the like.
The trifunctional or higher ethylenically unsaturated compound having an acid group may be used in combination with the bifunctional ethylenically unsaturated compound having an acid group, if necessary.

As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of a carboxy group-containing bifunctional or more ethylenically unsaturated compound and its carboxylic acid anhydride is preferable.
The bifunctional or more ethylenically unsaturated compound containing a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
As a bifunctional or more ethylenically unsaturated compound containing a carboxy group, for example, Allonix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Allonix M-520 (manufactured by Toagosei Co., Ltd.), or Aronix M-510 (manufactured by Toagosei Co., Ltd.) can be preferably used.

  The ethylenically unsaturated compound having an acid group is also preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated herein.

The weight average molecular weight (Mw) of the polymerizable compound used in the present disclosure is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and 300 to 2,200. Particularly preferred.
In the polymerizable compound used in the photosensitive layer, the content ratio of the polymerizable compound having a molecular weight of 300 or less is 30% by mass or less based on all the ethylenically unsaturated compounds contained in the photosensitive layer. Is preferable, 25 mass% or less is more preferable, and 20 mass% or less is still more preferable.

The polymerizable compounds may be used alone or in combination of two or more.
The content of the polymerizable compound in the photosensitive layer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and more preferably 20% by mass to 60% by mass with respect to the total mass of the photosensitive layer. More preferred is 20% by mass to 50% by mass.

When the photosensitive layer contains a bifunctional ethylenic unsaturated compound and a trifunctional or more ethylenically unsaturated compound, the content of the bifunctional ethylenic unsaturated compound is the same as that contained in the photosensitive layer. 10 mass%-90 mass% are preferable with respect to the ethylenic unsaturated compound of 20, 20 mass%-85 mass% are more preferable, and 30 mass%-80 mass% are still more preferable.
In this case, the content of the trifunctional or higher ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, and more preferably 15% by mass to 80% by mass with respect to all the ethylenically unsaturated compounds contained in the photosensitive layer. More preferably, it is 20% by mass to 70% by mass.
In this case, the content of the bifunctional or higher ethylenic unsaturated compound is 40% by mass or more to 100% of the total content of the bifunctional ethylenic unsaturated compound and the trifunctional or higher ethylenic unsaturated compound. The content is preferably less than mass%, more preferably 40 mass% to 90 mass%, still more preferably 50 mass% to 80 mass%, and particularly preferably 50 mass% to 70 mass%. .

When the photosensitive layer contains a bifunctional or more ethylenically unsaturated compound, the photosensitive layer may further contain a monofunctional ethylenically unsaturated compound.
Furthermore, when the photosensitive layer contains a bifunctional or more ethylenically unsaturated compound, in the ethylenically unsaturated compound contained in the photosensitive layer, the bifunctional or more ethylenically unsaturated compound is the main component. preferable.
Specifically, in the case where the photosensitive layer contains a bifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional or higher functional ethylenically unsaturated compound is the ethylenically unsaturated compound contained in the photosensitive layer. 60 mass%-100 mass% are preferable with respect to total content of, 80 mass%-100 mass% are more preferable, 90 mass%-100 mass% are especially preferable.

  When the photosensitive layer contains an ethylenic unsaturated compound having an acid group (preferably, a bifunctional or higher ethylenic unsaturated compound containing a carboxy group or a carboxylic acid anhydride thereof), the photosensitive layer has an acid group. 1 mass%-50 mass% are preferable with respect to the said photosensitive layer, as for content of an ethylenically unsaturated compound, 1 mass%-20 mass% are more preferable, and 1 mass%-10 mass% are still more preferable.

[Binder polymer having an acid group]
When the photosensitive layer in the present disclosure is a negative photosensitive layer, the photosensitive layer preferably contains a binder polymer having an acid group.
As a binder polymer which has an acidic radical, alkali-soluble resin is preferable.
As an acid group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group etc. are mentioned.
Among them, preferred as the acid group is a carboxy group.
The acid value of the binder polymer having an acid group is not particularly limited, but from the viewpoint of alkali developability, an alkali-soluble resin having an acid value of 60 mg KOH / g or more is preferable, and a carboxy group having an acid value of 60 mg KOH / g or more It is especially preferable that it is a containing acrylic resin.

The carboxy group-containing acrylic resin having an acid value of 60 mg KOH / g or more (hereinafter, may be referred to as specific polymer A) is not particularly limited as long as the above acid value conditions are satisfied. Can be used.
For example, among the polymers described in paragraph 0025 of JP-A-2011-95716, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mg KOH / g or more, paragraphs 0033 to 0052 of JP-A-2010-237589. Carboxy group-containing acrylic resin having an acid value of 60 mg KOH / g or more among the polymers described in the above, a carboxy group having an acid value of 60 mg KOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A 2016-224162. Containing acrylic resin etc. can be preferably used as specific polymer A in this indication.
Here, the (meth) acrylic resin refers to a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.
30 mol% or more is preferable and, as for the sum total ratio of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in (meth) acrylic resin, 50 mol% or more is more preferable.

A preferable range of the copolymerization ratio of the monomer having a carboxy group in the specific polymer A is 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and more preferably 100% by mass of the polymer. Preferably, it is in the range of 12% by mass to 30% by mass.
The specific polymer A may have a reactive group, and means for introducing the reactive group into the specific polymer A include a hydroxyl group, a carboxy group, a primary, secondary amino group, an acetoacetyl group, and a sulfonic acid. Examples include a method of reacting an epoxy compound, blocked isocyanate, isocyanate, vinyl sulfone compound, aldehyde compound, methylol compound, carboxylic acid anhydride, and the like.
As the specific polymer A, the compound A shown below is preferable. In addition, the content ratio of each structural unit shown below can be suitably changed according to the objective.

The acid value of the binder polymer having an acid group used in the present disclosure is preferably 60 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, from the viewpoint of alkali developability. More preferably, it is 60 mgKOH / g-110 mgKOH / g.
In the present disclosure, the acid value means a value measured according to the method described in JIS K 0070 (1992).

  The weight average molecular weight of the binder polymer having an acid group is preferably 1,000 or more, more preferably 10,000 or more, and still more preferably 20,000 to 100,000.

  In addition to the specific polymer A, the binder polymer having an acid group can be used by appropriately selecting any film-forming resin depending on the purpose. For example, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, etc. can be mentioned preferably.

The binder polymer having an acid group may be used singly or in combination of two or more.
From the viewpoint of photosensitivity, the content of the binder polymer having an acid group in the photosensitive layer is preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass with respect to the total mass of the photosensitive layer. % Or less is more preferable, and 30% by mass or more and 70% by mass or less is even more preferable.

[Photopolymerization initiator]
When the photosensitive layer in the present disclosure is a negative photosensitive layer, the photosensitive layer preferably contains a photopolymerization initiator. The photopolymerization initiator receives the actinic light such as ultraviolet light and visible light to initiate polymerization of the polymerizable compound (ethylenically unsaturated compound).
There is no restriction | limiting in particular as a photoinitiator, A well-known photoinitiator can be used.
As the photopolymerization initiator, a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, "α- Also referred to as aminoalkylphenone photopolymerization initiators), photopolymerization initiators having an α-hydroxyalkylphenone structure (hereinafter also referred to as “α-hydroxyalkylphenone polymerization initiators”), and acyl phosphine oxide structures. Photopolymerization initiator (hereinafter, also referred to as “acyl phosphine oxide photopolymerization initiator”), photopolymerization initiator having an N-phenylglycine structure (hereinafter, “N-phenylglycine photopolymerization initiator” Or the like)).

  The photopolymerization initiator is at least selected from the group consisting of an oxime photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, an α-hydroxyalkylphenone polymerization initiator, and an N-phenylglycine photopolymerization initiator. It is preferable to include one, and it is more preferable to include at least one selected from the group consisting of an oxime photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, and an N-phenylglycine photopolymerization initiator. .

  Moreover, as a photoinitiator, it is also preferable to contain at least 1 sort (s) selected from the group which consists of a 2,4,5-triaryl imidazole dimer and its derivative (s). The 2,4,5-triarylimidazole dimer and its derivative may be a compound represented by the following formula PI.

In formula PI, it is preferable that at least one of X ¹ and X ^{2 be} a chlorine atom. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have a substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and 1 Is more preferred. In addition, when Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have a substituent, the substitution position is not particularly limited, and it is preferable that the position is an ortho position or a para position. p and q are each independently an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.

  As a compound represented by the formula PI, 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, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer is mentioned. In addition, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same and give the target compound, or differently give an asymmetric compound.

  In addition, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP 2011-95716 A and paragraphs 0064 to 0081 of JP 2015-014783 A may be used. .

  As commercially available products of the photopolymerization initiator, 1- [4- (phenylthio)]-1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF AG) Product), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379 EG, manufactured by BASF), 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-H Roxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: IRGACURE 1173) , Manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF) ), An oxime ester photopolymerization initiator (trade name: Lunar 6, D KSH Japan Ltd.) 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole 2 (Product name: B-CIM, manufactured by Hampford) and the like.

The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. % Or more is more preferable.
Moreover, 10 mass% or less is preferable with respect to the total mass of a photosensitive layer, and, as for content of a photoinitiator, 5 mass% or less is more preferable.

[Other additives]
The photosensitive layer in the present disclosure may further contain known additives, if necessary, in addition to the components described above.

-Surfactant-
The photosensitive layer in the present disclosure preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.).
Moreover, the weight average of polystyrene conversion measured by the gel permeation chromatography at the time of using tetrahydrofuran (THF) as a solvent contains the structural unit A and the structural unit B which are represented by following formula I-1 as surfactant. A copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferred example.

In formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon. Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and * represents a bonding site with another structure. Represent.

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

  The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

  In addition, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP 2009-237362 A can also be used.

The surfactant may be used alone or in combination of two or more.
The addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, relative to the total mass of the photosensitive layer, and 0.01% by mass to More preferably, it is 3 mass%.

-Polymerization inhibitor-
When the photosensitive layer according to the present disclosure is a negative photosensitive layer, the photosensitive layer may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, a thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Among these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

  When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.01% by mass to 1% by mass with respect to the total mass of the photosensitive layer. % Is more preferable, and 0.01% by mass to 0.8% by mass is more preferable.

-Solvent-
The photosensitive layer may contain a solvent.
In addition, the composition for forming a photosensitive layer forming the photosensitive layer is made to contain a solvent once to adjust the viscosity of the composition for forming a photosensitive layer in order to easily form the photosensitive layer, thereby forming a photosensitive layer containing a solvent. The photosensitive composition can be suitably formed by applying and drying the composition.
A well-known solvent can be used as a solvent used for this indication. As a solvent, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol mono alkyl ether acetates, propylene glycol mono alkyl ethers, propylene glycol dialkyl ethers, propylene glycol mono alkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Moreover, the solvent as described in stage 0174-stage 0178 of Unexamined-Japanese-Patent No. 2011-221494 is also mentioned as a specific example of a solvent, and these content is integrated in this specification.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate can also be added.
The solvent may be used alone or in combination of two or more.
The solvents that can be used in the present disclosure may be used alone or in combination of two. When two or more solvents are used, for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetate Preferably used in combination with a class.

The solvent is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and Propylene glycol methyl-n-propyl ether (boiling point 131 ° C.) can be exemplified.
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.) There can be exemplified.

The content of the solvent when the composition for forming a photosensitive layer is applied is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass with respect to 100 parts by mass of the total solid content in the composition for forming a photosensitive layer. More preferably, it is part to 900 parts by mass.
The content of the solvent in the photosensitive layer is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass or less based on the total mass of the photosensitive layer. Is more preferred.

-Plasticizer-
The photosensitive layer in the present disclosure may contain a plasticizer for the purpose of improving the plasticity.
The plasticizer preferably has a weight average molecular weight smaller than that of a binder polymer having an acid-degradable group-protected acid group or a binder polymer having an acid group.
The weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the specific polymer to exhibit plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

  In the above formula, R represents an alkyl group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding site with another atom.

  In addition, for example, a chemically amplified positive type photosensitive layer obtained by mixing the compound X, a specific polymer and a photoacid generator even with a compound having an alkyleneoxy group of the above structure (referred to as “compound X”) If the forming composition does not improve plasticity as compared with the chemically amplified positive photosensitive layer forming composition formed without the compound X, it does not fall under the plasticizer in the present disclosure. For example, surfactants that are optionally added are not generally used as plasticizers in the present disclosure because they are not used in amounts that provide plasticity to the composition for forming a photosensitive layer.

  Examples of the plasticizer include compounds having the following structure, but are not limited thereto.

The content of the plasticizer is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 20% by mass, with respect to the total mass of the photosensitive layer, from the viewpoint of adhesion.
The photosensitive layer may contain only one type of plasticizer, or may contain two or more types.

-Sensitizer-
When the photosensitive layer in the present disclosure is a positive photosensitive layer, the photosensitive layer can further contain a sensitizer.
The sensitizer absorbs an actinic ray to be in an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photoacid generator to produce actions such as electron transfer, energy transfer and heat generation. Thus, the photoacid generator chemically changes and decomposes to generate an acid.
Exposure sensitivity can be improved by containing a sensitizer.

As the sensitizer, compounds selected from the group consisting of anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyryl benzene derivatives are preferable, and anthracene derivatives are more preferable.
As the anthracene derivative, anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene or 9,10-dimethoxyanthracene is preferred.

  Examples of the sensitizer include the compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.

The photosensitive layer in the present disclosure may contain one type of sensitizer alone or two or more types in combination.
The content of the sensitizer is preferably 0% by mass to 10% by mass, and more preferably 0.1% by mass to 10% by mass, with respect to the total mass of the photosensitive layer.

-Sensitizing dye-
When the photosensitive layer in the present disclosure is a negative photosensitive layer, the photosensitive layer can further contain a sensitizing dye.

  Examples of the sensitizing dye include known sensitizing dyes, dyes, and pigments. The sensitizing dyes may be used alone or in combination of two or more.

  Examples of sensitizing dyes include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1, 2 , 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

  As a dye or pigment, for example, fuchsin, phthalocyanine green, auramine base, calcocoside green S, paramadieneta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE GREEN), Basic Blue 20, Diamond Green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH) and the like.

  As the dye, a coloring dye can be used. The coloring dye is a compound having a function of developing a color by light irradiation. Examples include leuco dyes and fluoran dyes. Of these, leuco dyes are preferred.

  The content of the sensitizing dye can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, 0.01% by mass with respect to the total mass of the photosensitive layer. % To 5% by mass is preferable, and 0.05% to 1% by mass is more preferable.

-Hydrogen donor-
When the photosensitive layer in the present disclosure is a negative photosensitive layer, the photosensitive layer can further include a hydrogen donor.

  The hydrogen donor is not particularly limited as long as it can give hydrogen to the photopolymerization initiator during the reaction in the exposed part, and examples thereof include bis [4- (dimethylamino) phenyl] methane and bis [4- ( Diethylamino) phenyl] methane, leucocrystal violet and the like. These can be used singly or in combination of two or more.

  When the photosensitive resin composition contains a hydrogen donor, the content thereof is preferably 0.01% by mass to 10% by mass, and 0.05% by mass to 5% by mass with respect to the total mass of the photosensitive layer. %, More preferably 0.1% by mass to 2% by mass.

-Basic compounds-
When the photosensitive layer in the present disclosure is a positive photosensitive layer, the photosensitive layer preferably further contains a basic compound.
As the basic compound, any one of basic compounds used in a chemical amplification resist can be selected and used. For example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids can be mentioned. Specific examples thereof include the compounds described in paragraphs [0204] to [0207] of JP-A-2011-221494, the contents of which are incorporated herein.

Specifically, as aliphatic amines, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of aromatic amines include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] And -7-undesen.
Examples of quaternary ammonium hydroxides include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, and tetra-n-hexyl ammonium hydroxide.
Examples of quaternary ammonium salts of carboxylic acids include tetramethyl ammonium acetate, tetramethyl ammonium benzoate, tetra-n-butyl ammonium acetate, and tetra-n-butyl ammonium benzoate.

The above basic compounds may be used alone or in combination of two or more.
The content of the basic compound is preferably 0.001% by mass to 5% by mass, and more preferably 0.005% by mass to 3% by mass, with respect to the total mass of the photosensitive layer.

-Heterocyclic compound-
The photosensitive layer in the present disclosure can contain a heterocyclic compound.
There is no particular limitation on the heterocyclic compound in the present disclosure. For example, a compound having an epoxy group or an oxetanyl group in the molecule described below, an alkoxymethyl group-containing heterocyclic compound, various cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones), nitrogen-containing monomers such as cyclic amines and oxazolines Furthermore, heterocyclic monomers having d electrons such as silicon, sulfur and phosphorus can be added.

  When the heterocyclic compound is added, the addition amount of the heterocyclic compound in the photosensitive layer is preferably 0.01% by mass to 50% by mass, and 0.1% by mass with respect to the total mass of the photosensitive layer. % To 10% by mass is more preferable, and 1% to 5% by mass is even more preferable. It is preferable in the viewpoint of adhesiveness and etching tolerance as it is the said range. The heterocyclic compound may be used alone or in combination of two or more.

  Specific examples of the compound having an epoxy group in the molecule include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, aliphatic epoxy resin and the like.

Compounds having an epoxy group in the molecule are commercially available. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and the like, such as a commercial product described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212 , EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX -121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (made by Nagase Chemtech Inc.), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Cellbiners B0134, B0177 (manufactured by Daicel Corporation), and the like.
The compound which has an epoxy group in a molecule may be used individually by 1 type, and may use 2 or more types together.

  Among the compounds having an epoxy group in the molecule, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.

  Specific examples of the compound having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei) Co., Ltd. can be used.

  Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

  In the photosensitive layer in the present disclosure, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

-Alkoxysilane compound-
The photosensitive layer may contain an alkoxysilane compound. As an alkoxysilane compound, a trialkoxysilane compound is mentioned preferably.
As the alkoxysilane compound, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl alkyldialkoxysilane, γ-methacryloxypropyl Trialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It can be mentioned. Among these, γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane is more preferable, γ-glycidoxypropyltrialkoxysilane is further preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used singly or in combination of two or more.

-Other ingredients-
In the photosensitive layer in the present disclosure, metal oxide particles, an antioxidant, a dispersant, an acid multiplying agent, a development accelerator, a conductive fiber, a colorant, a thermal radical polymerization initiator, a thermal acid generator, an ultraviolet absorber, Further known additives such as thickeners, crosslinkers and organic or inorganic suspending agents can be added.
Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP 2014-85643 A, and the contents of this publication are incorporated in this specification.

-Average film thickness of photosensitive layer-
The average film thickness of the photosensitive layer is preferably 1.0 μm or more, more preferably 1.5 μm or more, and still more preferably 2.0 μm or more from the viewpoint of transferability (lamination). The average film thickness of the photosensitive layer is preferably 20 μm or less, more preferably 15 μm or less, from the viewpoint of production suitability.

-Method of forming photosensitive layer-
The components and a solvent may be mixed in any proportion and in any method and stirred and dissolved to prepare a photosensitive layer-forming composition for forming a photosensitive layer. For example, after preparing each solution as a solution in which each component is previously dissolved in a solvent, the resulting solution can be mixed at a predetermined ratio to prepare a composition. The composition prepared as described above can also be used after being filtered using a filter with a pore size of 0.2 μm or the like.

The photosensitive transfer material according to the present disclosure having a photosensitive layer on a temporary support can be obtained by applying the composition for forming a photosensitive layer on a cover film and drying it.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, or ink jet coating.
Moreover, after forming the other layer mentioned later on a cover film, a photosensitive layer can also be formed.

<Cover film>
The photosensitive transfer material according to the present disclosure also has a cover film.
As a cover film, a resin film, a paper, etc. are mentioned, A resin film is especially preferable from a viewpoint of intensity | strength, flexibility, etc. As a resin film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film etc. are mentioned. Among them, a polyethylene terephthalate film is preferable, and a biaxially stretched polyethylene terephthalate film is particularly preferable.

  The thickness of a cover film is not specifically limited, For example, the thing of 1 micrometer-2 mm is mentioned preferably.

<Other layers>
The photosensitive transfer material according to the present disclosure may have a layer other than the temporary support, the adhesive layer, the photosensitive layer, and the cover film (hereinafter sometimes referred to as “other layer”). Other layers may include a contrast enhancement layer, a peeling layer and the like.

-Contrast enhancement layer-
The photosensitive transfer material according to the present disclosure can have a contrast enhancement layer in addition to the photosensitive layer.
A material with a contrast enhancement layer (Contrast Enhancement Layer; CEL) that absorbs significantly to the exposure wavelength before exposure but gradually decreases as it is exposed, that is, the light transmittance increases (photo-decoloring (Referred to as a sex pigment component). As the photobleachable dye component, diazonium salts, stilbazolium salts, aryl nitroso salts and the like are known. A phenolic resin etc. are used as a film formation component.
In addition, as the contrast enhancement layer, paragraph 0004 to paragraph 0051 of JP-A-6-97065, paragraph 0012 to paragraph 0055 of JP-A-6-332167, photopolymer handbook, photopolymer conference, industry research meeting ( 1989), photopolymer technology, Yamaoka, Nagamatsu edition, Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

-Release layer-
In order to improve the releasability of the cover film and the photosensitive layer, a release layer may be provided between the cover film and the photosensitive layer.
The release layer is not particularly limited, and it is possible to use a release layer known in the field of transfer films and the like.
As a peeling layer, the layer containing a thermoplastic resin is mentioned, for example, The thermoplastic resin layer etc. which are described in Unexamined-Japanese-Patent No. 4502784 are used suitably as a peeling layer.
The method for forming the release layer is not particularly limited, and it may be formed by a method such as applying a composition containing a thermoplastic resin described in paragraphs 0189 to 0193 of JP-A-2014-85643 to a cover film. Moreover, you may obtain and use the cover film in which the peeling layer was formed previously.
When a release layer is provided between the cover film and the photosensitive layer, the photosensitive layer is also preferably formed on the release layer in the step of forming the photosensitive layer.

(Method of producing photosensitive transfer material)
A method of producing a photosensitive transfer material according to the present disclosure is
Applying a photosensitive layer-forming composition on a cover film to form a photosensitive layer (photosensitive layer-forming step);
It is preferable to include a step of bonding the temporary support having the adhesive layer such that the adhesive layer is in contact with the photosensitive layer (temporary support bonding step).
As the composition for forming a photosensitive layer in the method for producing a photosensitive transfer material, the above-described ones described for the photosensitive transfer material are preferably used.
According to the method for producing a photosensitive transfer material according to the present disclosure, it is easy to obtain a photosensitive transfer material having irregularities formed by particles on the surface of the photosensitive layer after peeling off the adhesive layer and the photosensitive layer.
Moreover, it is preferable that the manufacturing method of the photosensitive transfer material which concerns on this indication is a method for obtaining the photosensitive transfer material which concerns on this indication.

<Photosensitive layer formation process>
The method for producing a photosensitive transfer material according to the present disclosure preferably includes the step of applying a composition for forming a photosensitive layer on a cover film to form a photosensitive layer.
The method for applying the photosensitive composition is not particularly limited, and a known method may be used, and examples thereof include known methods such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, as a formation method of a photosensitive layer, it is as above-mentioned.

Temporary support bonding process
The method for producing a photosensitive transfer material according to the present disclosure preferably includes a step of bonding a temporary support having an adhesive layer so that the adhesive layer is in contact with the photosensitive layer.
The step of laminating the temporary support is not particularly limited, and a known method may be used. For example, a method of laminating the temporary support so that the adhesive layer and the photosensitive layer are in contact with each other can be mentioned.
The term "laminate" in the present disclosure refers to laminating a temporary support having an adhesive layer so as to be in contact with the photosensitive layer so as to prevent air bubbles from entering between the photosensitive layer and the adhesive layer. From the viewpoints of suppressing the adhesion and improving the adhesion between the photosensitive layer and the adhesive layer, it is preferable to use bonding of at least one of heating and pressing.

As an apparatus used when laminating a temporary support having an adhesive layer to be in contact with a photosensitive layer, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further enhancing productivity can be used. It can be used.
The laminator preferably comprises any heatable roller, such as a rubber roller, and is capable of pressing and heating.

  The temperature at the time of laminating is not particularly limited, but it is preferable that the temperature of the temporary support can be 60 ° C. to 150 ° C., more preferably 65 ° C. to 130 ° C., 70 ° C. It is particularly preferred that the temperature be in the range of -100 ° C.

<Other process>
The method for producing a photosensitive transfer material according to the present disclosure may further include other steps.
Other steps include the step of forming other layers contained in the photosensitive transfer material described above.
It does not specifically limit as a formation method of said other layer, What is necessary is just to form by a well-known method.

(Method of manufacturing resin pattern and method of manufacturing circuit wiring)
The method for producing a resin pattern according to the present disclosure is not particularly limited,
Peeling the cover film in the photosensitive transfer material according to the present disclosure;
The outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off is brought into contact with and bonded to a support having a conductive layer;
Separating the temporary support, the adhesive layer, and the photosensitive layer, contacting the photosensitive layer with an exposure mask, and exposing the photosensitive layer to a pattern through the exposure mask.
It is preferable to include the process of developing the said photosensitive layer and forming a resin pattern in this order.
Further, the method of manufacturing a circuit wiring according to the present disclosure is not particularly limited as long as it is a method of manufacturing a circuit wiring using the photosensitive transfer material according to the present disclosure.
Peeling the cover film in the photosensitive transfer material according to the present disclosure;
The outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off is brought into contact with and bonded to a support having a conductive layer;
A step of peeling the temporary support and the adhesive layer, and the photosensitive layer;
Bringing an exposure mask into contact with the photosensitive layer, and exposing the photosensitive layer to a pattern through the exposure mask;
Developing the photosensitive layer to form a resin pattern;
It is preferable to include, in this order, a step of etching the conductive layer using the formed resin pattern as a mask.
In the present disclosure, “the outermost layer on the photosensitive layer side” in the photosensitive transfer material is a photosensitive transfer material according to the present disclosure having a temporary support, an adhesive layer, and a photosensitive layer in this order. Needless to say, this is the outermost layer on the photosensitive layer side.
Moreover, the said support body is also called "a base material", Moreover, the support body which has an electroconductive layer in the said surface is also called a "board | substrate."

  Conventionally, the photosensitive layer is classified into a negative type in which a portion irradiated with actinic rays is left as an image and a positive type in which a portion not irradiated with actinic rays is left as an image due to differences in photosensitive systems. In the positive type, the solubility of the exposed area is enhanced by irradiating an actinic ray, for example, using a photosensitizer that emits an actinic ray to generate an acid, so that both the exposed area and the unexposed area are exposed at the pattern exposure time. In the case where the pattern shape obtained without curing is poor, the substrate can be reused (reworked) by overall exposure or the like. Therefore, from the viewpoint of so-called reworkability, a positive type is preferable. Moreover, since the technique of exposing the remaining photosensitive layer again to produce a different pattern can not be realized unless it is a positive photosensitive layer, the method for producing a resin pattern according to the present disclosure or the circuit wiring according to the present disclosure When a positive photosensitive layer is used in the production method of the invention, an embodiment in which exposure is performed twice or more is also preferably mentioned.

<Cover film peeling process>
The method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure preferably includes a step (cover film peeling step) of peeling the cover film in the photosensitive transfer material according to the present disclosure .
There is no restriction | limiting in particular as a peeling method, What is necessary is just to peel by a well-known method. For example, there is a method in which a part of the temporary support is gripped and peeled off using an instrument such as a finger or tweezers.

<Lamination process>
In the method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure, the outermost layer on the photosensitive layer side in the photosensitive transfer material from which the cover film is peeled off is a conductive layer. It is preferable to include the process (pasting process) which is made to contact and have a support body to have.
In the bonding step, the substrate and the photosensitive transfer material from which the cover film has been peeled are preferably crimped so that the conductive layer and the outermost layer on the photosensitive layer side are in contact with each other. According to the above aspect, the patterned photosensitive layer after exposure and development can be suitably used as an etching resist when etching the conductive layer.
There is no particular limitation on the method of pressure-bonding the substrate and the photosensitive transfer material from which the cover film is peeled off, and a known transfer method and lamination method can be used.
Specifically, the substrate and the photosensitive transfer material are overlapped so that the outermost layer on the photosensitive layer side of the photosensitive transfer material is in contact with the conductive layer, and pressing with a roll or the like or pressing and heating is performed. The method to be carried out is preferably mentioned. For lamination, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further enhancing productivity can be used.
The pressure and temperature of the pressure bonding in the bonding step are not particularly limited, and may be appropriately selected depending on the material of the surface of the support to be bonded, for example, the materials of the conductive layer and the photosensitive layer, the transport speed, and the pressure bonding machine used. It can be set. When the cover film is provided on the photosensitive layer of the photosensitive transfer material, the cover film may be removed from the photosensitive layer and then pressure-bonded.
When the said base material is a resin film, you may pressure-bond by roll-to-roll.

[Support (Base Material)]
The substrate in which a plurality of conductive layers are laminated on a support is preferably a glass substrate or a film substrate, and more preferably a film substrate. When the method for producing a circuit wiring according to the present disclosure is a wiring for a touch panel, it is particularly preferable that the support is a sheet-like resin composition.
The support is preferably transparent.
The refractive index of the support is preferably 1.50 to 1.52.
The support may be made of a translucent base material such as a glass base material, and for example, tempered glass represented by Gorilla glass of Corning Co., Ltd. can be used. Moreover, as the above-mentioned transparent substrate, the materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate with less optical distortion and a substrate with high transparency, and as a specific material, polyethylene terephthalate (PET), Examples include polyethylene naphthalate, polycarbonate, triacetyl cellulose and cycloolefin polymers.

[Conductive layer]
As the plurality of conductive layers formed on the support, any conductive layer used for general wiring or touch panel wiring can be mentioned.
Examples of the material of the conductive layer include metals and metal oxides.
As the metal oxide, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), may be mentioned SiO ₂ and the like. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo and the like.

In the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, it is preferable that at least one of the plurality of conductive layers includes a metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition unit used for a capacitive touch panel or a wiring of a peripheral extraction unit.

〔substrate〕
The substrate (wiring formation substrate) used in the present disclosure is preferably a substrate having a conductive layer on the surface of the base material. Wiring is formed by patterning the conductive layer. In this example, it is preferable that a plurality of conductive layers such as metal oxides and metals be provided on a film substrate such as PET.

<Temporary support peeling process>
A resin pattern manufacturing method according to the present disclosure or a circuit wiring manufacturing method according to the present disclosure includes a step of peeling the temporary support and the adhesive layer from the photosensitive layer (temporary support peeling step). Is preferred.
The method for peeling off the temporary support in the temporary support peeling step is not particularly limited, and the peeling may be performed by a known method.

<Exposure process>
A resin pattern manufacturing method according to the present disclosure or a circuit wiring manufacturing method according to the present disclosure includes a step of bringing an exposure mask into contact with the photosensitive layer and pattern exposing the photosensitive layer through the exposure mask (exposure step). Is preferred.
By performing exposure by bringing an exposure mask into contact with the photosensitive layer, there are advantages that the distance between the photosensitive layer and the mask is reduced, thereby improving the resolution of the pattern and eliminating the influence of foreign matter in the temporary support.
At the said exposure process, it is preferable to irradiate an actinic light through the mask which has a pattern with respect to the base material in which the photosensitive layer was formed at least.
When the photosensitive layer is positive, in this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-degradable group contained in the coating film component is hydrolyzed to form an acid group such as a carboxy group or a phenolic hydroxyl group.
When the photosensitive layer is negative, the polymerizable compound is polymerized in this step.
In the present disclosure, the detailed arrangement and specific size of the pattern in the mask are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) provided with an input device having a circuit board manufactured in the present disclosure and to minimize the area occupied by the extraction wiring, at least a part of the pattern (especially the touch panel) Preferably, the electrode pattern and the part of the lead-out wiring are thin lines of 100 .mu.m or less, and more preferably 70 .mu.m or less.

As the actinic ray, visible light, ultraviolet light, and electron beam may be mentioned, and visible light or ultraviolet light is preferable, and ultraviolet light is particularly preferable.
A low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used as an exposure light source by actinic light, g ray (436 nm), i ray (365 nm) An actinic ray having a wavelength of 300 nm or more and 450 nm or less such as h ray (405 nm) can be preferably used. In addition, it is also possible to adjust the irradiation light through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed.
As an exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a laser exposure, and the like can be used.
Exposure dose, depending on the photosensitive layer to be used may be appropriately ^selected, but is preferably from ^{5mJ / cm 2 ~200mJ / cm 2} , more preferably ^{10mJ / cm 2 ~100mJ / cm 2} .
Further, it is also preferable to carry out heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By means of a process called so-called PEB (Post Exposure Bake), it is possible to reduce roughness of the pattern edge due to standing waves generated in the photosensitive layer at the time of exposure.

<Development process>
The method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure preferably includes the step of developing the photosensitive layer to form a resin pattern (developing step).
When the photosensitive layer is positive, the exposed portion in the photosensitive layer is removed by development. When the photosensitive layer is negative, the unexposed area in the photosensitive layer is removed by development.
The development of the exposed photosensitive layer in the development step can be performed using a developer.
The developer is not particularly limited as long as the photosensitive layer can be developed. For example, a known developer such as the developer described in JP-A-5-72724 can be used. The developer is preferably a developer in which the part of the photosensitive layer to be removed has a dissolution type development behavior. The developer is preferably an alkaline aqueous solution, for example, more preferably an alkaline aqueous solution containing a compound with pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. As a developing solution preferably used in the present disclosure, for example, a developing solution described in paragraph 0194 of WO 2015/093271 can be mentioned.

The developing method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, dip development and the like. Here, in the shower development, the exposed portion can be removed by spraying a developer onto the photosensitive layer after exposure. In addition, after development, it is preferable to remove a development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The solution temperature of the developer is preferably 20 ° C to 40 ° C.
Although development may be carried out immediately after exposure, the time from exposure to development may be about 0.5 hours to several hours after exposure.
Further, the method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure is known, such as a step of washing with water after development and a step of drying a support having the obtained pattern. May be included.

Furthermore, it may have a post-baking step of subjecting the pattern obtained by development to heat treatment.
Post-baking heating is preferably performed under an environment of 8.1 kPa or more, more preferably 50.66 kPa or more. On the other hand, it is preferably performed under an environment of 121.6 kPa or less, more preferably under an environment of 111.46 kPa or less, and particularly preferably under an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
Post-baking may be performed in an air environment or in a nitrogen-substituted environment.

  The transport speed of the support in each step of the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure is not particularly limited. It is preferable that it is min-10m / min, and it is more preferable that it is 2.0m / min-8.0m / min except at the time of exposure.

<Etching process>
It is preferable that the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching process) which carries out the etching process of the said conductive layer by setting the said formed said resin pattern as a mask.
In the etching step, the pattern formed from the photosensitive layer in the developing step is used as an etching resist to etch the conductive layer.
Etching of the conductive layer can be performed by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A or a dry etching method such as a known plasma etching. .
For example, as a method of etching, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be mentioned. The etching solution used for wet etching may be appropriately selected from acid type or alkaline type etching solution in accordance with the object of etching.
As an acid type etching solution, an aqueous solution of only an acidic component such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid or phosphoric acid, an acidic component and ferric chloride, ammonium fluoride or permanganate A mixed aqueous solution of salts such as potassium acid and the like are exemplified. An acidic component may use the component which combined the several acidic component.
As an alkaline type etching solution, an aqueous solution of only an alkaline component such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or a salt of an organic amine such as tetramethyl ammonium hydroxide, an alkaline component and potassium permanganate And the like. As the alkali component, a component obtained by combining a plurality of alkali components may be used.

  The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or less. In the present disclosure, a pattern used as an etching mask (etching pattern) preferably exhibits particularly excellent resistance to an acidic and alkaline etching solution in a temperature range of 45 ° C. or less. Therefore, the peeling of the pattern during the etching process is prevented, and the portion where the pattern does not exist is selectively etched.

After the etching step, in order to prevent contamination of the process line, a step of washing the support having the etched conductive layer (washing step) as needed, and a support having the etched conductive layer You may perform the process (drying process) of drying a body. For the cleaning step, for example, cleaning the substrate with pure water at normal temperature (10 ° C. to 35 ° C.) for 10 seconds to 300 seconds may be mentioned. For the drying step, for example using the air blowing may be performed dried by appropriately adjusting the air blow pressure ^{(0.1kg / cm 2 ~5kg / cm} 2 or so).

<Etching resist peeling process>
It is preferable that the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching resist peeling process) which peels the said photosensitive layer using peeling liquid after the said etching process.
After completion of the etching process, the patterned photosensitive layer remains. If the photosensitive layer is unnecessary, all remaining photosensitive layers may be removed.
As a method of peeling using a stripping solution, for example, a substrate having the photosensitive layer or the like in the stripping solution being stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 5 minutes to 30 minutes. There is a method of soaking for a minute.
As the stripping solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as tertiary amine or quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And a stripping solution dissolved in a mixed solution thereof. A peeling solution may be used, and peeling may be performed by a spray method, a shower method, a paddle method, or the like.

Moreover, the manufacturing method of the circuit wiring which concerns on this indication may repeat an exposure process, a image development process, and an etching process twice or more as needed.
As examples of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

  The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure may include other optional steps. For example, although the following processes are mentioned, it is not limited to these processes.

<Step of reducing visible light reflectance>
The method of manufacturing a circuit wiring according to the present disclosure includes the step of reducing the visible light reflectance of the surface of the conductive layer, for example, part or all of the surface of the conductive layer on the support. It is possible.
An oxidation process etc. can be mentioned as a process which reduces the visible light reflectance. For example, by oxidizing copper to form copper oxide, the visible light reflectance can be reduced by blackening.
About the preferable aspect of the process to which the visible light reflectance is reduced, Paragraph 0017-Paragraph 0025 of Unexamined-Japanese-Patent No. 2014-150118, and Paragraph 0041, Paragraph 0042, Paragraph 0048 and Paragraph 0058 of Unexamined-Japanese-Patent No. 2013-206315. The contents of this publication are incorporated herein by reference.

<Step of Forming Insulating Film on Support Having Etched Conductive Layer, and Step of Forming New Conductive Layer on Insulating Film>
A method of manufacturing a circuit wiring according to the present disclosure comprises the steps of: forming an insulating film on a support having the conductive layer, for example, on a formed wiring (the conductive layer etched); It is also preferable to include the step of forming a conductive layer.
There is no restriction | limiting in particular about the process of forming an insulating film, The method of forming a well-known permanent film can be mentioned. Alternatively, an insulating film with a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
There is no particular limitation on the step of forming a new conductive layer on the insulating film. A photosensitive material having conductivity may be used to form a new conductive layer of a desired pattern by photolithography.

Further, in the method for producing a circuit wiring according to the present disclosure, the above-mentioned new conductive layer may be etched by forming an etching resist by the same method as described above, or may be separately etched by a known method Good.
The wiring board obtained by the method for manufacturing a circuit wiring according to the present disclosure may have a wiring of only one layer on the substrate or may have a wiring of two or more layers.

  Further, in the method of manufacturing circuit wiring according to the present disclosure, the support has a plurality of conductive layers on both surfaces, and the circuit is sequentially or simultaneously applied to the conductive layers formed on both surfaces of the support. It is also preferable to form. Wiring having a first conductive pattern (first wiring) formed on one surface of the support and a second conductive pattern (second wiring) formed on the other surface by such a configuration, preferably for a touch panel Wiring can be formed.

(Wiring and wiring board)
The wiring according to the present disclosure is a wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure. Moreover, as said wiring, a circuit wiring is mentioned preferably.
The wiring substrate according to the present disclosure is a substrate having a wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure.
Although the use of the wiring board which concerns on this indication is not limited, For example, it is preferable that it is a wiring board for touch panels.

(Input device and display device)
As an apparatus provided with the wiring manufactured by the manufacturing method of the circuit wiring which concerns on this indication, an input device is mentioned.
The input device according to the present disclosure may be an input device having at least a wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure, and is preferably a capacitive touch panel.
The display device according to the present disclosure preferably includes the input device according to the present disclosure. The display device according to the present disclosure is preferably an image display device such as an organic EL display device and a liquid crystal display device.

(Touch panel and touch panel display device)
The touch panel according to the present disclosure is a touch panel having at least a wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure. In addition, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least a wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure, and is preferably a touch panel display device having a touch panel according to the present disclosure.
As a detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among them, the capacitance method is preferable.

  As a touch panel type, a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), a so-called on-cell type (for example, JP-A 2013-168125) 19 described in Japanese Patent Application Laid-Open No. 2012-89102 (FIG. 1 or FIG. 5), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (e.g. The other structures (for example, the ones described in FIG. 6 of JP-A-2013-164871), various out-cell types (so-called GG, G1 · G2, GFF, GFF, etc.) GF2, GF1, G1F etc. can be mentioned.

  As the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, “the latest touch panel technology” (issued on July 6, 2009, Techno Times Inc.), supervised by Yuji Mitani, “the touch panel technology and development” (the The configuration disclosed in December 2004, CMC Publishing Co., Ltd., FPD International 2009 Forum T-11 Lecture Text Book, Cypress Semiconductor Corporation Application Note AN2292 and the like can be applied.

  Hereinafter, the embodiments of the present invention will be more specifically described by way of examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the embodiment of the present invention. Accordingly, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.

Example 1
<Preparation of Photosensitive Resin Composition 1>
The following components were mixed and filtered with a polytetrafluoroethylene filter having a pore size of 0.2 μm to obtain a photosensitive resin composition 1 (a composition for forming a photosensitive layer).
Propylene glycol-1-monomethyl ether-2-acetate (PGMEA): 425.1 parts by mass Polymer A-1: 236.0 parts by mass Photoacid generator B-1: 5.0 parts by mass Surfactant E-1 : 0.1 parts by mass Basic compound F-1: 0.5 parts by mass Particles C-1: 17.5 parts by mass

Synthesis Example of Polymer A-1
PGMEA (75.0 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. ATHF (25.0 parts by mass), MAA (10.0 parts by mass), CHMA (35.0 parts by mass), CHA (30.0 parts by mass), V-601 (4.1 parts by mass), PGMEA (75 The solution to which .0 parts by mass was added was added dropwise over 2 hours into the three-necked flask solution maintained in the temperature range of 90 ° C ± 2 ° C. After completion of the dropwise addition, the mixture was stirred for 2 hours in a temperature range of 90 ° C. ± 2 ° C. to obtain a polymer A-1 (solid content concentration 40.0 mass%).
The polymer A-1 is a binder polymer having an acid-degradable group-protected acid group.

ATHF: tetrahydrofuran-2-yl acrylate (synthetic product)
MAA: methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHMA: cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

-Synthesis of ATHF-
Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to a three-necked flask and cooled to 20 ° C. After adding camphorsulfonic acid (0.0070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. Then, the temperature was raised to 35 ° C. and stirred for 2 hours. The reaction liquid is filtered after laying in order of KNU ward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and KYOWARD 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) in Nutsche. The filtrate was obtained by doing. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts by mass) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 140.8 parts by mass of tetrahydrofuran-2-yl acrylate (ATHF) was a colorless oil. The product was obtained as a product (yield 99.0%).

[Photo acid generator]
Photoacid generator B-1: Compound having the structure shown below (the compound described in paragraph 0227 of JP2013-047765A and synthesized according to the method described in paragraph 0204)

[Surfactant]
Surfactant E-1: Compound of the structure shown below

[Basic compound]
Basic compound F-1: Compound having the structure shown below

〔particle〕
C-1: Organosilica sol MEK-ST-ZL (silica particles, average particle size: 70 nm to 100 nm, solid content 30% by mass, manufactured by Nissan Chemical Industries, Ltd.)

<Preparation of photosensitive transfer material>
The photosensitive resin composition was applied on a polyethylene terephthalate film having a thickness of 25 μm serving as a cover film using a slit nozzle so that the dry film thickness was 3.0 μm. After the application, the film was dried in a convection oven at 100 ° C. for 2 minutes to produce a film A having a photosensitive resin composition layer.
Moreover, E-MASK AW303D by Nitto Denko Corporation was prepared as the film B as a temporary support body with an adhesive layer containing a urethane type adhesive.
Finally, film A and film B were heat-laminated at 90 ° C. and 5 m / min so that the photosensitive layer of film A and the adhesive layer of film B were in contact with each other to produce a photosensitive transfer material.

<Production of resin pattern>
After peeling off the cover film from the produced photosensitive transfer material, the photosensitive resin composition layer is applied to a PET substrate with a copper layer under the lamination conditions of a linear pressure of 0.6 MPa and a linear velocity (laminate velocity) of 3.6 m / min. Laminated.
Thereafter, the temporary support with the adhesive layer is peeled off, and the photosensitive layer of the photosensitive transfer material and a mask having a line-and-space pattern (duty ratio 1: 1) made of glass with a line width of 3 to 20 μm are exposed. The contact was made while adjusting the position (alignment), and after exposure with an extra-high pressure mercury lamp through the above mask, the film was allowed to stand for 30 minutes and then developed. Development was carried out using a 1.0% sodium carbonate aqueous solution at 28 ° C. and shower development for 40 seconds to form a resin pattern.

<Preparation of wiring pattern>
The pattern-formed sample was etched at 23 ° C. for 30 seconds with a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Inc.), and a resist pattern was removed using a 4% sodium hydroxide solution to create a wiring pattern.

(Example 2)
A photosensitive transfer material was prepared in the same manner as in Example 1 except that the amount of particles C-1 added was 37.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 was 10% by mass). The resin pattern and the circuit wiring pattern were formed.

(Example 3)
A photosensitive transfer material was prepared in the same manner as in Example 1 except that the amount of particles C-1 added was 83.3 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 was 20% by mass). It produced and formed the resin pattern and the circuit wiring pattern.

(Example 4)
The photosensitive transfer material was prepared in the same manner as in Example 1 except that the addition amount of the particles C-1 was 222.3 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 was 40% by mass). The resin pattern and the circuit wiring pattern were formed.

(Example 5)
A photosensitive transfer material was prepared in the same manner as in Example 1 except that the amount of particles C-1 added was 500.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 was 60% by mass). It produced and formed the resin pattern and the circuit wiring pattern.

(Example 6)
The particle C-1 in the photosensitive resin composition 1 is changed to a particle C-2, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 40% by mass) A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particles C-2: Organo silica sol MEK-ST-40 (silica particles, average particle size: 10 nm to 15 nm, solid content 40% by mass, Nissan Chemical Industries, Ltd.)

(Example 7)
The particle C-1 in the photosensitive resin composition 1 is changed to the particle C-3, and the addition amount is 37.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 10% by mass). A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particles C-3: Organo silica sol MEK-ST-L (silica particles, average particle size: 40 nm to 50 nm, solid content 30% by mass, Nissan Chemical Industries, Ltd.)

(Example 8)
The particle C-1 in the photosensitive resin composition 1 is changed to the particle C-4, and the addition amount is 27.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 10% by mass). A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particle C-4: Organosilica sol MEK-AC-5140Z (silica particles, average particle size: 70 nm to 100 nm, solid content 40% by mass, manufactured by Nissan Chemical Industries, Ltd.)

(Example 9)
The particle C-1 in the photosensitive resin composition 1 is changed to a particle C-5, and the addition amount is 22.2 parts by mass (the content of particles in the total solid of the photosensitive resin composition 1 is 10% by mass) A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particle C-5: Organosilica sol MEK-EC-7150P (silica particles, average particle size: 50 nm to 60 nm, solid content 50 mass%, manufactured by Nissan Chemical Industries, Ltd.)

(Example 10)
The particle C-1 in the photosensitive resin composition 1 is changed to a particle C-6, and the addition amount is 55.5 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 10% by mass) A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particles C-6: Seahoster KE-E10 (amorphous silica, average particle size: 100 nm, solid content 20% by mass, manufactured by Nippon Shokubai Co., Ltd.)

(Example 11)
Change particle C-1 in photosensitive resin composition 1 to particle C-7, and add 55.5 parts by mass (the content of particles in the total solid of photosensitive resin composition 1 is 10% by mass) A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particles C-7: Seahoster KE-E30 (amorphous silica, average particle size: 300 nm, solid content 20% by mass, manufactured by Nippon Shokubai Co., Ltd.)

(Example 12)
The particle C-1 in the photosensitive resin composition 1 is changed to the particle C-8, and the addition amount is 74.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 10% by mass). A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particle C-8: Epostor MA1002 (acrylic crosslinked product, average particle diameter: 2000 nm, manufactured by Nippon Shokubai Co., Ltd.) was mixed with PGMEA so as to be 15% by mass, and particle C-8 was prepared using a paint shaker did.

(Example 13)
The particle C-1 in the photosensitive resin composition 1 is changed to the particle C-9, and the addition amount is 74.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 10% by mass). A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particle C-9: Eposer SS (melamine / formaldehyde condensate, average particle diameter: 100 nm, manufactured by Nippon Shokubai Co., Ltd.) is mixed with PGMEA to 15% by mass, and particle C-9 is mixed using a paint shaker Prepared.

(Example 14)
The particle C-1 in the photosensitive resin composition 1 is changed to the particle C-10, and the addition amount is 74.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 10% by mass). A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particle C-10: Eporator S (melamine / formaldehyde condensate, average particle size: 200 nm, manufactured by Nippon Shokubai Co., Ltd.) is mixed with PGMEA to 15% by mass, and particle C-10 is mixed using a paint shaker. Prepared.

(Example 15)
The particle C-1 in the photosensitive resin composition 1 is changed to the particle C-11, and the addition amount is 74.0 parts by mass (the content of the particles in the total solid of the photosensitive resin composition 1 is 10% by mass) A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particle C-11: Soken MP-1451 (non-crosslinked acrylic particle, average particle diameter: 150 nm, manufactured by Soken Chemical Co., Ltd.) is mixed with PGMEA so as to be 15% by mass, and particle C-11 is prepared using a paint shaker. Prepared.

(Example 16)
Change particle C-1 in photosensitive resin composition 1 to particle C-12, and add 74.0 parts by mass (the content of particles in the total solid content of photosensitive resin composition 1 is 10% by mass) A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particles C-12: Trepearl PAI (Polyamide imide resin, average particle diameter: 200 nm to 500 nm, Toray Industries, Inc.) is mixed with PGMEA to 15% by mass, and particles C-12 are prepared using a paint shaker. did.

(Example 17)
Change particle C-1 in photosensitive resin composition 1 to particle C-13, and add 74.0 parts by mass (the content of particles in the total solid content of photosensitive resin composition 1 is 10% by mass) A photosensitive transfer material was prepared in the same manner as in Example 1 except that a resin pattern and a circuit wiring pattern were formed.
Particles C-13: Alumina Spherical Particles AZ2-75 (Alumina particles, average particle size: 3000 nm, Nippon Steel Sumikin Micron Co., Ltd.) is mixed with PGMEA so as to be 15% by mass, and particles C-13 are obtained using a paint shaker. Was prepared.

(Example 18)
The photosensitive transfer was performed in the same manner as in Example 2 except that the temporary support E-MASK AW303D was changed to E-MASK RP207 (a temporary support with an adhesive layer containing an acrylic adhesive, manufactured by Nitto Denko Corporation). A material was prepared, and a resin pattern and a circuit wiring pattern were formed.

(Example 19)
A photosensitive transfer material is prepared in the same manner as in Example 2 except that temporary support E-MASK AW303D is changed to Panaprotect HP 25 (temporary support with an adhesive layer containing an acrylic adhesive, Panac Co., Ltd.). And formed a resin pattern and a circuit wiring pattern.

Example 20
A photosensitive transfer material is prepared in the same manner as in Example 2 except that temporary support E-MASK AW303D is changed to Panaprotect MK38S (temporary support with an adhesive layer containing an acrylic adhesive, Panac Co., Ltd.). And formed a resin pattern and a circuit wiring pattern.

(Example 21)
A photosensitive transfer material was prepared in the same manner as in Example 1 except that the photosensitive resin composition 1 was changed to the photosensitive resin composition 2, and a resin pattern and a wiring pattern were further prepared.

<Preparation of Photosensitive Resin Composition 2>
The following components were mixed and filtered with a polytetrafluoroethylene filter having a pore size of 5.0 μm to obtain a photosensitive resin composition.
PGMEA: 495.0 parts by mass Polymer A-2: 119.1 parts by mass Polymerizable compound D-1: 28.6 parts by mass Polymerizable compound D-2: 19.1 parts by mass Photopolymerization initiator B-CIM: 4.0 parts by mass Sensitizing dye PYR-1: 0.1 parts by mass Hydrogen donor LCV: 0.65 parts by mass Dye MKG: 0.03 parts by mass Particles C-1: 37.0 parts by mass

[Synthesis Example of Polymer A-2]
PGMEA (75.0 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. A solution in which MAA (20.0 parts by mass), BzMA (80.0 parts by mass), V-601 (4.1 parts by mass), and PGMEA (75.0 parts by mass) are added is a temperature of 90 ° C. ± 2 ° C. The solution was added dropwise over 2 hours into the three-necked flask solution maintained within the range. After completion of the dropwise addition, by stirring for 2 hours in a temperature range of 90 ° C. ± 2 ° C., a polymer A-2 (solid content concentration 40.0 mass%) was obtained.
Polymer A-2 is a binder polymer having an acid group.

  BzMA: benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Polymerizable compound]
Polymerizable compound D-1: FA-324M (manufactured by Hitachi Chemical Co., Ltd., product name): 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane Polymerizable compound D-2: FA-3200MY ( Hitachi Chemical Co., Ltd., product name): 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (ethylene oxide average 12 mol and propylene oxide average 4 mol adduct)

[Photopolymerization initiator]
Photopolymerization initiator B-CIM (product name, manufactured by Hampford): 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole dimer)

[Sensitizing dye]
Sensitizing dye PYR-1 (manufactured by Nippon Chemical Industrial Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline

[Hydrogen donor]
Hydrogen donor LCV (manufactured by Yamada Chemical Co., Ltd., product name): Leuco Crystal Violet

〔dye〕
Dye MKG (Osaka Organic Chemical Industry Co., Ltd. product name): Malachite green

(Example 22)
A photosensitive transfer material was prepared in the same manner as in Example 21 except that the amount of particles C-1 added was 83.3 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 2 was 20% by mass). It produced and formed the resin pattern and the circuit wiring pattern.

(Example 23)
A photosensitive transfer material was prepared in the same manner as in Example 21 except that the addition amount of the particles C-1 was 222.3 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 2 was 40% by mass). It produced and formed the resin pattern and the circuit wiring pattern.

(Example 24)
A photosensitive transfer material was prepared in the same manner as in Example 21 except that the amount of particles C-1 added was 500.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 2 was 60% by mass). It produced and formed the resin pattern and the circuit wiring pattern.

(Example 25)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-2, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 60% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 26)
The particle C-1 in the photosensitive resin composition 2 is changed to a particle C-3, and the addition amount is 83.3 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass) A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 27)
The particle C-1 in the photosensitive resin composition 2 is changed to a particle C-4, and the addition amount is 62.5 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass) A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 28)
The particle C-1 in the photosensitive resin composition 2 is changed to a particle C-5, and the addition amount is 50.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass) A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 29)
The particle C-1 in the photosensitive resin composition 2 is changed to a particle C-6, and the addition amount is 125.0 parts by mass (the content of the particles in the total solid content of the photosensitive resin composition 1 is 20% by mass) A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 30)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-7, and the addition amount is 125.0 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 31)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-8, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 32)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-9, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 33)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-10, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 34)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-11, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 35)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-12, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 36)
The particle C-1 in the photosensitive resin composition 2 is changed to the particle C-13, and the addition amount is 166.7 parts by mass (the content of particles in the total solid content of the photosensitive resin composition 1 is 20% by mass). A photosensitive transfer material was prepared in the same manner as in Example 21 except that a resin pattern and a circuit wiring pattern were formed.

(Example 37)
A photosensitive transfer material was produced in the same manner as in Example 21 except that the temporary support E-MASK AW303D was changed to E-MASK RP207, and a resin pattern and a circuit wiring pattern were formed.

(Example 38)
A photosensitive transfer material was prepared in the same manner as in Example 21 except that the temporary support E-MASK AW303D was changed to Panaprotect HP25, and a resin pattern and a circuit wiring pattern were formed.

(Example 39)
A photosensitive transfer material was produced in the same manner as in Example 21 except that the temporary support E-MASK AW303D was changed to Panaprotect MK38S, and a resin pattern and a circuit wiring pattern were formed.

(Comparative example 1)
A photosensitive transfer material was produced in the same manner as in Example 1 except that the particle C-1 was not added in the preparation of the photosensitive resin composition 1, and a resin pattern and a circuit wiring pattern were formed.

(Comparative example 2)
A photosensitive transfer material was produced in the same manner as in Example 21 except that the particle C-1 was not added in the preparation of the photosensitive resin composition 2, and a resin pattern and a circuit wiring pattern were formed.

(Comparative example 3)
A photosensitive transfer material was prepared in the same manner as in Example 2 except that a 25 μm-thick polyethylene terephthalate film not having an adhesive layer was used as a temporary support in place of E-MASK AW303D manufactured by Nitto Denko Corporation. , A resin pattern and a circuit wiring pattern were formed.

(Comparative example 4)
A photosensitive transfer material was prepared in the same manner as in Example 21 except that a 25 μm-thick polyethylene terephthalate film not having an adhesive layer was used as a temporary support in place of E-MASK AW303D manufactured by Nitto Denko Corporation. , A resin pattern and a circuit wiring pattern were formed.

(Evaluation)
<Evaluation of formation of unevenness>
The photosensitive transfer material prepared in each example or comparative example is laminated on a PET substrate with a copper layer under peeling conditions of linear pressure 0.6 MPa and linear velocity (laminating speed) 3.6 m / min after peeling the cover film. did. Thereafter, the temporary support and the adhesive layer were peeled off, and the formation of asperities on the surface of the photosensitive layer was confirmed by SEM. Those in which the irregularities were formed were regarded as "present", and those in which the irregularities were not formed or those in which the irregularities were crushed and pressed into the film were evaluated as "none".
The evaluation results are shown in Table 1 or Table 2.

<Evaluation of anti-mask slipperiness>
The photosensitive transfer material prepared in each example or comparative example is laminated on a PET substrate with a copper layer under the lamination conditions of linear pressure 0.6 MPa and linear velocity (lamination speed) 3.6 m / min after peeling the cover film. did.
Thereafter, the temporary support and the adhesive layer are peeled, and the photosensitive layer of the photosensitive transfer material is brought into contact with a glass mask having a line-and-space pattern (duty ratio 1: 1) having a line width of 3 μm to 20 μm. The static friction coefficient was calculated using a static friction meter Heidon 10 manufactured by Shinto Chemical Co., Ltd. The evaluation results are shown in Table 1 or Table 2. The evaluation result is preferably 3 to 5, more preferably 4 or 5, and still more preferably 5.
It is believed that the smaller the coefficient of static friction, the better the anti-mask slipperiness at the time of contact exposure, and the easier the alignment after the mask is brought into contact with the photosensitive layer.

〔Evaluation criteria〕
5: coefficient of static friction is less than 0.3 4: coefficient of static friction is not less than 0.3 but less than 0.5 3: coefficient of static friction is not less than 0.5 but less than 1.0 2: coefficient of static friction is not less than 1.0 but less than 1.6 1: Static friction coefficient is 1.6 or more

<Evaluation of linearity>
The produced photosensitive transfer material was peeled off the cover film, and then laminated on a PET substrate with a copper layer under the lamination conditions of linear pressure 0.6 MPa and linear velocity (lamination speed) 3.6 m / min.
Thereafter, the temporary support and the adhesive layer are peeled off, and the photosensitive layer of the photosensitive transfer material is brought into contact with a mask having a line-and-space pattern (duty ratio 1: 1) made of glass with a line width of 10 μm. After exposure with a ghi line (435 nm, 405 nm, 365 nm) with an extra-high pressure mercury lamp, development was carried out for 30 minutes with an exposure amount such that the line width after development of a 10 .mu.m line and space pattern becomes 10 .mu.m. A resin pattern was produced by performing development for 40 seconds by shower development using 1.0 mass% sodium carbonate aqueous solution of 28 ° C.
The wiring pattern is obtained by etching the sample on which the resin pattern is formed with a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.) at 23 ° C. for 30 seconds and stripping the resist with a 4 mass% sodium hydroxide solution. Was produced. 100 line widths of the wiring pattern were measured, LWR (standard deviation of line width) was calculated, and the linearity of the wiring was evaluated. The evaluation results are shown in Table 1 or Table 2. It is evaluated that it is excellent in the linearity of a wiring pattern, so that a numerical value is large among 1-5, and it is preferable.

〔Evaluation criteria〕
5: LWR less than 150 nm 4: LWR greater than or equal to 150 nm and less than 200 nm 3: LWR greater than or equal to 200 nm and less than 300 nm 2: LWR less than or equal to 300 nm and less than 500 nm 1: LWR less than or equal to 500 nm

<Evaluation of wiring>
The photosensitive transfer material prepared in each example or comparative example is laminated on a PET substrate with a copper layer under the lamination conditions of linear pressure 0.6 MPa and linear velocity (lamination speed) 3.6 m / min after peeling the cover film. did.
Thereafter, the temporary support and the adhesive layer are peeled off, the photosensitive layer of the photosensitive transfer material, a line-and-space pattern (duty ratio 1: 1) made of glass with a line width of 3 μm to 20 μm, and an alignment mark. The resist was brought into contact while adjusting the exposure position (alignment), exposed with an extra-high pressure mercury lamp through the mask, and allowed to stand for 30 minutes, followed by development. A resin pattern was produced by performing development for 40 seconds by shower development using 1.0 mass% sodium carbonate aqueous solution of 28 ° C.
Further, the alignment mark is formed by etching the patterned sample with a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.) at 23 ° C. for 30 seconds and stripping the resist with a 4 mass% sodium hydroxide solution. The wiring pattern which it has was produced.
The position of the alignment mark of the metal wiring pattern was confirmed, and those which could be manufactured as the target position were regarded as “good”, and those which had a deviation from the target position were regarded as “defective”. The evaluation results are shown in Table 1 or Table 2.
The “target position” means that the error from the target is within 50 μm.

In Table 1 or Table 2, the description of the content of particles indicates the content of particles with respect to the total mass of the photosensitive layer.
From the results described in Table 1, the photosensitive transfer material according to the embodiment of the present invention is excellent in anti-mask slipperiness at the time of contact exposure, and since the obtained wiring is formed at the target position, at the time of contact exposure It can be seen that the alignment of the is easy.
Further, in Comparative Example 1 or Comparative Example 2, the photosensitive layer does not contain particles, so that it is inferior in mask slipping property at the time of contact exposure. As a result, even in the evaluation of the obtained wiring, the metal wiring is the target position. It can be seen that they were not produced as they were.
In Comparative Example 3 or Comparative Example 4, a temporary support that does not have an adhesive layer is used. When such a temporary support is used, the temporary support and the photosensitive layer are not in close contact with each other. Since the transfer material can not be manufactured, it was impossible to evaluate the anti-mask slip, the linearity of the wiring, and the wiring.

(Example 101)
Indium tin oxide (ITO) is deposited by sputtering as a conductive layer of the second layer on a 100 μm-thick PET substrate by sputtering to a thickness of 150 nm, and copper is vacuum deposited thereon as a conductive layer of the first layer. A film was formed at a thickness of 200 nm to form a circuit formation substrate.
The photosensitive transfer material prepared in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.). Using a photomask provided with a pattern (hereinafter also referred to as “pattern A”) shown in FIG. 2 having a configuration in which the temporary support and the adhesive layer are peeled off and conductive layer pads are connected in one direction. Contact exposed.
In the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually illustrates the alignment alignment frame.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etchant (Kanto Chemical Co., Ltd. Cu-02), the ITO layer is etched using an ITO etchant (Kanto Chemical Co., Ltd. ITO-02), A substrate on which copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.

Next, pattern alignment was performed using a photomask provided with an opening of a pattern shown in FIG. 3 (hereinafter, also referred to as “pattern B”) in a state where alignment is aligned, and development and water washing were performed.
In the pattern B shown in FIG. 3, the gray portion G is a light shielding portion, and the dotted line portion DL virtually illustrates the alignment alignment frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive layer was peeled using a peeling solution (10 mass% aqueous sodium hydroxide solution) to obtain a wiring board.
Thus, a wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and it was a beautiful pattern.

  10: Temporary support, 14: Photosensitive layer, 16: Cover film, 18: Adhesive layer, 100: Photosensitive transfer material, SL: Solid line part, G: Gray part, DL: Dotted line part

Claims (9)

A photosensitive layer, an adhesive layer, and a temporary support on a cover film in this order,
The photosensitive layer comprises particles,
The photosensitive layer and the adhesive layer are in contact;
The photosensitive layer and the adhesive layer are peelable,
A photosensitive transfer material, wherein the surface of the photosensitive layer after peeling the photosensitive layer and the adhesive layer has irregularities formed by the particles.   The photosensitive transfer material according to claim 1, wherein the particles include at least one kind of particles selected from the group consisting of silica particles, alumina particles, and organic polymer particles.   The photosensitive transfer material according to claim 1, wherein the average particle diameter of the particles is 10 nm to 200 nm.   The photosensitive transfer material according to any one of claims 1 to 3, wherein the content of the particles with respect to the total mass of the photosensitive layer is 1% by mass to 80% by mass.   The photosensitive transfer material according to claim 1, wherein the photosensitive layer further contains a binder polymer having an acid group protected with an acid-decomposable group, and a photoacid generator. .   The photosensitive transfer material according to any one of claims 1 to 4, wherein the photosensitive layer further contains a binder polymer having an acid group, a polymerizable compound, and a photopolymerization initiator. Applying a photosensitive layer-forming composition containing at least particles on a cover film to form a photosensitive layer;
And affixing a temporary support having an adhesive layer so that the adhesive layer is in contact with the photosensitive layer. The process of peeling the said cover film in the photosensitive transfer material of any one of Claims 1-6,
A step of bringing the outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off into contact with a support having a conductive layer,
Peeling the temporary support, the adhesive layer, and the photosensitive layer;
Bringing an exposure mask into contact with the photosensitive layer and subjecting the photosensitive layer to pattern exposure through the exposure mask;
And developing the photosensitive layer to form a resin pattern in this order. The process of peeling the said cover film in the photosensitive transfer material of any one of Claims 1-6,
A step of bringing the outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off into contact with a support having a conductive layer,
Peeling the temporary support, the adhesive layer, and the photosensitive layer;
Bringing an exposure mask into contact with the photosensitive layer and subjecting the photosensitive layer to pattern exposure through the exposure mask;
Developing the photosensitive layer to form a resin pattern;
Etching the conductive layer using the formed resin pattern as a mask in this order.