WO2019102771A1

WO2019102771A1 - Photosensitive transfer material, method for producing resin pattern, and method for producing wiring line

Info

Publication number: WO2019102771A1
Application number: PCT/JP2018/039375
Authority: WO
Inventors: 一真両角; 藤本　進二; 漢那　慎一; 壮二石坂
Original assignee: 富士フイルム株式会社
Priority date: 2017-11-27
Filing date: 2018-10-23
Publication date: 2019-05-31
Also published as: TW201924935A; JPWO2019102771A1; JP6999693B2; CN111386498A; JP2022043153A

Abstract

A photosensitive transfer material which sequentially comprises a provisional supporting body, an intermediate layer and a photosensitive layer in this order, and wherein the intermediate layer contains a binder and particles that have an arithmetic mean particle diameter of 400 nm or less; and a method for producing a resin pattern and a method for producing a wiring line, each of which uses the above-described photosensitive transfer material.

Description

Photosensitive transfer material, resin pattern manufacturing method, and wiring manufacturing method

The present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, and a 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. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

As a conventional method, for example, in JP-A-2016-224161, a laminate having (a) a photosensitive layer and (b) a resin layer formed on a substrate is exposed, heat-treated, and developed. A method of forming a resist pattern is disclosed which includes the steps of
JP-A 2014-74764 discloses a photosensitive element comprising a support film and a photosensitive layer formed on the support film, wherein the support film is opposite to the surface in contact with the photosensitive layer. Disclosed is a photosensitive element having a self-healing layer on the surface, wherein the photosensitive layer comprises (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. It is done.

The problem to be solved by the embodiment of the present invention is to provide a photosensitive transfer material which is excellent in the adhesion between the intermediate layer and the photosensitive layer.
Another problem to be solved by another embodiment of the present invention is to provide a resin pattern manufacturing method and a wiring manufacturing method using the photosensitive transfer material.

Means for solving the above problems include the following aspects.
<1> A photosensitive transfer material comprising a temporary support, an intermediate layer, and a photosensitive layer in this order, wherein the intermediate layer contains a binder and particles having an arithmetic average particle diameter of 400 nm or less.
<2> The photosensitive transfer material according to <1>, wherein the volume fraction of the particles in the intermediate layer is 5% to 90% of the total volume of the intermediate layer.
<3> The photosensitive transfer material according to <1> or <2>, wherein an average film thickness of the intermediate layer is 0.3 μm to 10 μm.
<4> The particles of the above <1> to <3>, wherein the particles contained in the intermediate layer are oxide particles of at least one element selected from the group consisting of Si, Ti and Zr, or organic particles The photosensitive transfer material as described in any one.
<5> The photosensitive transfer material according to any one of the above <1> to <4>, wherein the photosensitive layer contains a binder and a photoacid generator.
<6> The photosensitive transfer material according to <5>, wherein the binder contained in the photosensitive layer contains a binder having an acid group protected by an acid-degradable group.
<7> The photosensitive transfer material according to any one of the above <1> to <4>, wherein the photosensitive layer contains a binder having an acid group, a polymerizable compound, and a photopolymerization initiator.
<8> The photosensitive transfer material according to any one of the above <1> to <7>, wherein the binder contained in the intermediate layer contains a modified cellulose resin.
<9> The photosensitive transfer material according to any one of the above <1> to <8>, wherein the intermediate layer has two or more layers.
<10> The photosensitive transfer material according to the above <9>, wherein particles having an arithmetic average particle diameter of 400 nm or less are contained only in the layer closest to the photosensitive layer among two or more layers in the intermediate layer.
<11> A step of laminating the outermost layer on the photosensitive layer side in the photosensitive transfer material according to any one of <1> to <10> to a support, a step of patternwise exposing the photosensitive layer, A method of producing a resin pattern comprising the step of developing the photosensitive layer which has been subjected to pattern exposure, and the step of peeling the temporary support after the step of bonding to the support and before the step of developing the photosensitive layer. .
<12> A step of bonding the outermost layer on the photosensitive layer side in the photosensitive transfer material according to any one of <1> to <10> to a support having a conductive layer on the surface, the photosensitive layer having a pattern The step of exposing, developing the pattern-exposed photosensitive layer to form a resin pattern, etching the conductive layer using the resin pattern as a mask, and peeling the resin pattern; A method for producing a wiring, comprising the step of peeling off the temporary support after the step of bonding to a body and before the step of developing the photosensitive layer.

According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material which is excellent in the adhesion between the intermediate layer and the photosensitive layer.
Further, according to another embodiment of the present invention, it is possible to provide a resin pattern manufacturing method and a wiring manufacturing method using the photosensitive transfer material.

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.
Further, in the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
Moreover, in this specification, "(meth) acryl" represents both or any of acrylic and methacryl, and "(meth) acrylate" represents both or any of acrylate and a methacrylate.
Furthermore, in the present specification, the amount of each component in the composition is the total of a plurality of corresponding substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term "process" is included in the term if the intended purpose of the process is achieved, even if it can not be clearly distinguished from other processes, as well as independent processes.
In the notation of groups (atomic groups) in the present specification, 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).
Moreover, the chemical structural formula in this specification may be described by the simplified structural formula which abbreviate | omitted the hydrogen atom.
In the present disclosure, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
Also, 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, and TSKgel G2000HxL (all are trade names manufactured by Tosoh Corporation) 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 temporary support, an intermediate layer, and a photosensitive layer in this order, and the intermediate layer contains a binder and particles having an arithmetic average particle diameter of 400 nm or less. .

There are various advantages in making the photosensitive transfer material into a layer structure of temporary support / interlayer / photosensitive layer (/ cover film). For example, when laminating a photosensitive layer on a substrate or the like and then performing pattern exposure, the temporary support can be peeled off and then the mask can be contact exposed (the photosensitive layer and the mask are not in contact) or the photosensitive layer. There is an advantage that a photosensitive layer having a uniform film thickness can be formed without being affected by irregularities on the surface of the temporary support or foreign substances at the time of formation.
With this configuration, when the temporary support is peeled off, it may be peeled off between the temporary support and the intermediate layer, or may be peeled off between the intermediate layer and the photosensitive layer, and the interface to be peeled is not stable. The inventors have found that there is a problem. That is, it is considered that the adhesion between the intermediate layer and the photosensitive layer may be insufficient.
In order to ensure sufficient interlayer adhesion between the intermediate layer and the photosensitive layer, the present inventors added a filler to the intermediate layer to increase the contact area with the photosensitive layer at the layer interface and to increase the adhesion by physical action. They found it. By doing this, it is possible to stably separate between the temporary support and the intermediate layer.
As a result of intensive studies, the present inventors have found that the adhesion between the intermediate layer and the photosensitive layer is excellent by using the photosensitive transfer material having the above configuration.
Although the mechanism of manifestation of the above-mentioned effects is unclear, as described above, the inclusion of particles having an arithmetic average particle diameter of 400 nm or less in the intermediate layer increases the contact area with the photosensitive layer at the layer interface, The present inventors estimate that the adhesion between the intermediate layer and the photosensitive layer is improved.
In addition, when the arithmetic average particle diameter of the particles is 400 nm or less, the contact area with the photosensitive layer at the layer interface is further increased, and the adhesion between the intermediate layer and the photosensitive layer is improved by the present inventors. Is estimating.

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, a temporary support 10, an intermediate layer 12, a photosensitive layer 14, and a cover film 16 are laminated in this order.
The intermediate layer 12 contains a binder and particles having an arithmetic average particle diameter of 400 nm or less.
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 intermediate layer and the photosensitive layer and can be peeled off from the intermediate layer.
The temporary support used in the present disclosure preferably has light transmittance from the viewpoint of being able to expose the photosensitive layer through the temporary support when the photosensitive layer is subjected to pattern exposure.
Having light transmission means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is a viewpoint of improving exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable. As a measuring method of the transmittance | permeability, the method of measuring using Otsuka Electronics Co., Ltd. product MCPD Series is mentioned.
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, 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 can be selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a wiring formation substrate, light transmittance required in the first exposure step, and the like. Just do it.

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

<Middle class>
The photosensitive transfer material according to the present disclosure contains a binder and particles having an arithmetic average particle diameter of 400 nm or less.

-binder-
The binder is preferably a water-soluble or alkali-soluble binder, and more preferably a water-soluble or alkali-soluble polymer.
In the present disclosure, “water-soluble” means that the solubility in water of pH 7.0 at 25 ° C. is 0.1% by mass or more, and “alkali-soluble” means that pH 8.5 at 25 ° C. It means that the solubility to 5 or more alkaline aqueous solution is 0.1 mass% or more.
The above-mentioned "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or both water-soluble and alkali-soluble.

As the binder, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p- or m- / p- mixed Any may be used) Novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having hydroxy group (for example, homopolymer or copolymer of hydroxyalkyl (meth) acrylate), Starches, glycogens, chitins, agaroses, carrageenans, pullulan, gum arabic, soy gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, Urethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol, and the like.

Among these, the binder is at least one resin selected from the group consisting of novolak resins, modified cellulose resins, and acrylic resins having a hydroxy group from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and patternability. It is preferable that the resin is at least one resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxy group, more preferably a modified cellulose resin.
Further, as the modified cellulose resin, a hydroxyalkylated cellulose is preferable from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer and the pattern forming property.
Preferred examples of the hydroxyalkylated cellulose include hydroxymethylcellulose, hydroxyethylcellulose, polyhydroxyethylated cellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, glyoxalized hydroxypropyl methylcellulose, hydroxypropyl methylcellulose phthalate and the like.
Among them, at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methylcellulose is preferable from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and patternability, and it is preferable to be hydroxypropyl methylcellulose. More preferable.
The binder is preferably at least one resin selected from the group consisting of polyvinyl alcohol and polyvinyl formal from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, and polyvinyl alcohol is more preferable. preferable.

The weight-average molecular weight of the binder is preferably 1,000 or more, from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, patternability, solubility in a developer after exposure, and transferability. It is preferably ̃100,000 and more preferably 10,000 to 50,000.

The intermediate layer may contain one kind of binder alone, or may contain two or more kinds of binders.
The content of the binder in the intermediate layer is 1 mass to the total mass of the intermediate layer from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer, the patternability, the solubility in a developer after exposure and the transferability. % Or more and 99% by mass or less is preferable, 1% by mass or more and 90% by mass or less is more preferable, 2% by mass or more and 80% by mass or less is more preferable, and 3% by mass or more and 70% by mass or less Is particularly preferred.

-Particles having an arithmetic mean particle size of 400 nm or less-
The intermediate layer contains particles having an arithmetic mean particle size of 400 nm or less.
The particles are preferably metal oxide particles or organic particles from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, and oxide particles of an element selected from the group consisting of Si, Ti and Zr Or, organic particles are more preferable.
Note that the metal of the metal oxide particles in the present disclosure 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, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, silica, titanium oxide, titanium complex oxide or zirconium oxide is more preferable, and silica, titanium oxide or zirconium oxide is particularly preferable.
As the organic particles, organic resin particles are preferably mentioned.
Examples of organic resin 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 Condensation polymers, rubber-based thermoplastic polymers such as butadiene-styrene copolymers, polymers obtained by polymerizing and crosslinking photopolymerizable or thermally polymerizable compounds such as epoxy compounds, Min compounds and the like.
Among these, acrylic resin particles are preferably mentioned as the organic particles, and polymethyl methacrylate particles are more preferably mentioned.
In addition, these particles can also be treated with an organic material or an inorganic material on the surface to impart dispersion stability. The particles are preferably particles having a hydrophilic surface. For example, the surface of the particles having a hydrophobic surface is subjected to a hydrophilization treatment, and the like.

The arithmetic mean particle diameter of the above particles is 400 nm or less, preferably 250 nm or less, more preferably 200 nm or less, and 150 nm or less from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer. More preferably, it is particularly preferably 10 nm to 150 nm.
The method of measuring the arithmetic mean particle size of particles in the present disclosure measures the particle size of 200 arbitrary particles by an electron microscope, and refers to the arithmetic mean. Also, when the shape of the particles is not spherical, the maximum diameter is taken as the diameter.

The volume fraction of the particles in the intermediate layer (the volume ratio of particles in the intermediate layer) is 5% to 90% of the total volume of the intermediate layer from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer 10% to 80% is more preferable, 15% to 70% is more preferable, and 20% to 60% is particularly preferable.
As described later, when the intermediate layer is formed into two layers, the volume fraction of the particles in all the intermediate layers (the volume ratio occupied by the particles in the intermediate layer) is from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer. Preferably 2% to 90%, more preferably 3% to 80%, still more preferably 5% to 20%, and still more preferably 10% to 20% of the total volume of the intermediate layer. Being particularly preferred.

-Other additives-
The intermediate layer in the present disclosure can contain, if necessary, known additives in addition to the binder and the particles.
As other additives, other additives used for the photosensitive layer described later are preferably mentioned.

-Composition of the middle layer-
The intermediate layer may have two or more layers, and when the intermediate layer is formed of two or more layers, adhesion between the intermediate layer and the temporary support, and the intermediate layer From the viewpoint of adhesion to each of the photosensitive layers, it is preferably formed of 2 to 5 layers, more preferably formed of 2 or 3 layers, and formed of 2 layers Is particularly preferred.
When the intermediate layer has two or more layers, it is preferable to contain a water-soluble or alkali-soluble binder in each layer, and the same type of binder may be used in each layer, and different binders may be used. Good.
When the intermediate layer has two or more layers, particles having an arithmetic average particle diameter of 400 nm or less may be contained in a plurality of layers, but from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, It is preferable to be contained in the layer closest to the photosensitive layer.
In addition, from the viewpoint of adhesion between the temporary support and the intermediate layer, particles having an arithmetic average particle diameter of 400 nm or less are contained in the layer closest to the temporary support among two or more layers in the intermediate layer. Preferably not. That is, the particles having an arithmetic average particle diameter of 400 nm or less are more preferably contained only in the layer closest to the photosensitive layer among the two or more layers in the intermediate layer.
For example, in the photosensitive transfer material, when the intermediate layer and the photosensitive layer are in contact with each other, “the layer closest to the photosensitive layer among the two or more layers in the intermediate layer” is “the layer in the intermediate layer It corresponds to "the layer in contact with the photosensitive layer" among the layers above.

-Average film thickness of middle layer-
The average film thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and further preferably 0.3 μm to 2 μm, from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and pattern formability. Is particularly preferred.
The measuring method of the average film thickness of each layer in this indication does not have a restriction | limiting in particular, A well-known method can be used. Moreover, it is preferable to measure and calculate an average value 10 points or more.
Specifically, for example, surface shape measurement, optical microscope observation of a cross section, electron microscope observation and the like can be mentioned. Further, for surface profile measurement, Dektak series manufactured by Bruker can be suitably used. In addition, a scanning electron microscope (SEM) can be suitably used for cross-sectional observation.
The thickness of the intermediate layer is preferably smaller than the thickness of the photosensitive layer.

When the intermediate layer has two or more layers, the average film thickness of each layer is not particularly limited as long as it is within the above range, but of the two or more layers in the intermediate layer, the average of the layers closest to the photosensitive layer The film thickness is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2.0 μm from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and pattern formability. .

-Method of forming the intermediate layer-
The formation method of the intermediate layer is not particularly limited, but the respective components and a solvent (preferably, an aqueous solvent) are mixed in a predetermined ratio and in an arbitrary method, stirred and dissolved to form the intermediate layer A composition for forming an intermediate layer can be prepared. 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 diameter of 5 μm or the like.
Examples of the aqueous solvent include water and water-soluble solvents such as alcohols.

The intermediate layer can be easily formed on the temporary support by applying the composition for forming an intermediate layer to the temporary support 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.
In addition, after forming the below-mentioned other layers (for example, thermoplastic resin layer etc.) on a temporary support body, an intermediate | middle layer can also be apply | coated.

<Photosensitive layer>
The photosensitive transfer material according to the present disclosure has a temporary support, an intermediate layer, and a photosensitive layer in this order.
In addition, the photosensitive layer in the present disclosure may be a positive photosensitive layer or may be negative photosensitive.
When it is a positive photosensitive layer, the photosensitive layer is preferably a chemically amplified positive photosensitive layer.
A photoacid generator such as an onium salt or an oxime sulfonate compound, which will be described later, is a protected acid in a binder having an acid degradable protected acid group in which an acid generated in response to actinic radiation (actinic ray) is generated. Since it acts as a catalyst for group deprotection, an 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, to a power of 10 High sensitivity is obtained as a result of so-called chemical amplification.
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 the 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 and a photoacid generator from the viewpoint of pattern formability. In addition, the binder preferably contains a binder having an acid-degradable group-protected acid group from the viewpoint of pattern formability, and a polymer having a structural unit having an acid-degradable protected acid group It is more preferable to contain
When the photosensitive layer is a negative photosensitive layer, the photosensitive layer preferably contains a binder having an acid group, a polymerizable compound, and a photopolymerization initiator from the viewpoint of pattern formation.

-Polymer component including a polymer having a structural unit having an acid-degradable protected acid group-
The photosensitive layer contains a polymer (also referred to as a “specific polymer”) having a structural unit (also referred to as “structural unit A”) having an acid-degradable protected acid group.
In addition to the polymer having the structural unit A, the 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-degradable protected acid group in the specific polymer is subjected to a deprotecting reaction by the action of a catalytic amount of an acidic substance generated by exposure to light, thereby becoming an acid group. This acid group enables a curing reaction.
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-degradable protected acid 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.
In addition, the photosensitive layer may further contain a polymer other than these. 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 a resin of addition polymerization type, 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 contains a polymer having a structural unit A1 represented by the following formula A1 as the structural unit A as a polymer component from the viewpoint of suppressing deformation of a pattern shape, solubility in a developer and transferability. It is preferable that the polymer component contains 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, As the structural unit A, 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.degree. C. or less More preferable.
The specific polymer contained in the photosensitive layer may be only one type, or two or more types.

<< Constituent Unit A >>
The polymer component includes a polymer having at least a constituent unit A having an acid-degradable protected acid 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 and 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. Moreover, as the acid-degradable protected acid group, a group which is relatively easy to be decomposed by an acid (for example, an ester group protected by a group represented by the formula A1, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) And the like (acetal functional groups such as, etc.) and groups which are relatively difficult to be decomposed by acid (for example, tertiary alkyl groups such as tert-butyl ester group, tertiary alkyl carbonate groups such as tert-butyl carbonate group) it can.
Among these, as the above-mentioned acid-decomposable group, a group having a structure protected in the form of acetal is preferable.

<< Constituent Unit A >>
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 the 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. Each of R ³¹ and R ³² is 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.
In addition, the alkyl group and the aryl group in R ³¹ to 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 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 of being able to lower the Tg of the specific polymer.
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 confirm by intensity ratio of peak intensity.

Among the structural units A1 represented by the formula A1, structural units represented by the following formula A2 are more preferable from the viewpoint of further enhancing the sensitivity at the time of 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.

The structural unit A is preferably a structural unit represented by the following formula A3 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, 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 R ^B1 or R ^B2 and R ^B3 may combine to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, and X ^B is a single bond or a divalent linking group. R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In the 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. Each of R ^B1 and R ^B2 is 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, and is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
In addition, the alkyl group and the 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. The carbon number of the alkylene group is preferably 1 to 10, and more preferably 1 to 4. When X ^B contains —C (-O) O—, an embodiment in which the carbon atom contained in —C (= O) O— and 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 having 1 to 4 carbon atoms or a hydrogen atom, and 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 in the para position.
In formula A3, R ^B12 represents a substituent, preferably an alkyl group or a halogen atom. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In formula A3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

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, the content (content ratio: mass ratio) of the constituent unit in which R ^B4 in the formula A3 is a hydrogen atom in the constituent unit A is calculated according to a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can confirm by intensity ratio of peak intensity.

Among the structural units represented by 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 represent 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. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In formula A4, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

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.

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 to the total mass of the specific polymer. More preferably, it is 70% by 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.
Further, 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. The pKa of the acid group is preferably -5 or more.

A specific polymer contains a specific polymer by containing the structural unit A and the structural unit B which has an acidic group which is not protected by a protecting group as a copolymerization component, and setting a glass transition temperature to 90 degrees C or less. The positive photosensitive layer has better transferability and removability from the temporary support while maintaining good resolution and sensitivity during pattern formation.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group (phenolic hydroxy group), and a sulfonylimide group. Among them, at least one acid group selected from the group consisting of a carboxylic acid group (carboxy 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 of a structural unit (structural unit B) having an acid group, based on the total mass of the specific polymer, and includes 0.5% by mass to 15% by mass Is more preferable, and 1% by mass to 10% by mass is more preferable. Within the above range, pattern formability becomes better.
The content (content ratio: mass ratio) of the structural unit B in the specific polymer can be confirmed by the intensity ratio of peak intensities calculated from ¹³ C-NMR measurement by a conventional method.

<< Other composition unit >>
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 compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having aliphatic cyclic skeleton, other unsaturated Saturated compounds can be mentioned.
Various properties of the specific polymer can be adjusted by adjusting at least one of the type 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, 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) Examples thereof include structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be mentioned.

Further, 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 properties of the transfer material to be obtained. 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 in the adhesive viewpoint, for example. Among them, (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples thereof 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 More preferred is a polymer containing the structural unit B derived from and a structural unit (c) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate.
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.
Further, the lower limit value of the above Tg is not particularly limited, but is preferably −20 ° C. or more, more preferably −10 ° C. or more. When the Tg of the specific polymer is −20 ° C. or higher, good pattern formability is maintained, and, for example, when a cover film is used, the decrease in peelability at the time of peeling the cover film 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 specification 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 the glass transition temperature is determined, the temperature is maintained at about 50 ° C. lower than the expected polymer Tg until the device is stabilized, and then the heating rate: 20 ° C./min, about 30 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 .
The weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, and more preferably 3,000 to 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)-8220 GPC (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 standard curve is the "standard sample TSK standard, polystyrene" manufactured by Tosoh Corp .: "F-40", "F-20", "F-4", "F-1", "A-5000", " It can be prepared using any of the seven samples of A-2500 "and" A-1000 ".

The ratio (dispersion degree) of the number average molecular weight to 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 include 70% by mass to 98% by mass.
In addition, the photosensitive layer contains the specific polymer in 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 exhibiting good adhesion to the substrate. Is preferable, and it is more preferable to include 70% by mass to 98% by mass.

<< Other polymer >>
The photosensitive layer contains, as a polymer component, a polymer which does not contain the structural unit (a) represented by the formula A in addition to the specific polymer as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired 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 (all manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 678 , Joncryl 67, and Joncryl 586 (above, manufactured by BASF Corp.) can also be used.

-Photo acid generator-
The photosensitive layer 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 light 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 specific examples of trichloromethyl-s-triazines and diazomethane derivatives, compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be exemplified.

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

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.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. 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-oxo norbornyl group, etc. And preferably a bicycloalkyl group or the like, or a halogen atom.
The aryl group of R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. 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 paragraphs 0078 to 0111 of JP-A-2014-85643.

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

As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 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, based on the total mass of the photosensitive layer, from the viewpoint of sensitivity and resolution. It is more preferable that the content be 5% by mass.

-Polymerizable compound-
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.

The photosensitive layer is preferably a bifunctional ethylenic unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or more ethylenic one from the viewpoint of further improving the wet heat resistance of the cured film after salting. It is particularly preferable to contain an unsaturated compound (preferably, a trifunctional or higher functional (meth) acrylate compound).

There is no restriction | limiting in particular as a bifunctional ethylenic unsaturated compound, It can select suitably from well-known compounds.
Examples of difunctional ethylenic unsaturated compounds include tricyclodecane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate etc. are mentioned.
More specifically, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, as a difunctional ethylenically unsaturated compound) Shin-Nakamura Chemical Co., Ltd. product, 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd. product), 1,6-hexanediol diacrylate (A-HD-N, Shin Nakamura Chemical Industry Co., Ltd. product etc. are mentioned.

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 compounds of (meth) acrylate compounds (Nippon Kayaku Co., Ltd. KAYARAD RP-1040, Shin-Nakamura Chemical Co. Ltd. ATM-35E, A-9300, Daicel Ornex Co., Ltd. EBECRYL (registered trademark) 135 Etc.), ethoxylated glycerin triacrylate (eg, 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 urethane (meth) acrylate compounds having three or more functional groups include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co. And the like.

Moreover, it is preferable that an ethylenically unsaturated compound contains an ethylenically unsaturated compound which has an acidic radical from a viewpoint of the developability improvement and the wet heat tolerance improvement after salt water provision of a cured film.
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.
As the ethylenically unsaturated compound having an acid group, for example, a 3- to 4-functional ethylenically unsaturated compound having an acid group (a compound in which a carboxy group is 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 acid groups (in which a carboxy group is introduced to the dipentaerythritol penta and hexaacrylate (DPHA) skeleton (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. Thereby, the wet heat resistance after salty application of a cured film increases.
The bifunctional or more ethylenically unsaturated compound containing a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
Examples of the bifunctional or higher ethylenic unsaturated compound containing a carboxy group include, for example, Allonix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Allonix M-520 (manufactured by Toagosei Co., Ltd.), or And Alonix 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 No. 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 preferably, 20% by mass to 50% by mass is particularly preferable.

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% by mass to 90% by mass is preferable, 20% by mass to 85% by mass is more preferable, and 30% by mass to 80% by mass is more preferable with respect to the ethylenically unsaturated compound of
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. % By mass is more preferable, and 20% by mass to 70% by mass is even more preferable.
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. It 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 more ethylenically unsaturated compound, the content of the bifunctional or more ethylenically unsaturated compound is the same as the ethylenically unsaturated compound contained in the photosensitive layer. The content is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, with respect to the total content of

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. The content of the ethylenically unsaturated compound is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and still more preferably 1% by mass to 10% by mass, with respect to the photosensitive layer.

-Binder having an acid group-
The photosensitive layer preferably contains a binder having an acid group.
As a binder 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 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 containing an acid value of 60 mg KOH / g or more Particularly preferred is an acrylic resin.
It is presumed that the binder having an acid group can thermally crosslink with a compound capable of reacting with an acid by heating to increase the three-dimensional crosslink density by having the acid value. In addition, it is presumed that the carboxy group of the carboxy group-containing acrylic resin is anilized and hydrophobized to contribute to the improvement of the wet heat resistance.

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 carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, paragraphs 0033 to 0052 of JP-A-2010-237589 Among the polymers described, carboxy group-containing acrylic resins having an acid value of 60 mg KOH / g or more can be preferably used as the specific polymer A in the present disclosure.
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.

The preferred 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, with respect to 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 as a means for introducing the reactive group into the specific polymer A, a hydroxyl group, a carboxy group, a primary or secondary amino group, an acetoacetyl group, a sulfonic acid And the like, for example, a method of reacting an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a 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 having an acid group used in the present disclosure is preferably 60 mg KOH / g to 200 mg KOH / g, more preferably 60 mg KOH / g to 150 mg KOH / g, and more preferably 60 mg KOH, from the viewpoint of alkali developability. It is further preferable that the amount is in the range of / g to 110 mg KOH / g.
In the present specification, 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 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.

Moreover, the binder which has the said acid group can be suitably selected and used for any film formation resin other than the said specific polymer A according to the objective. For example, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, etc. can be mentioned preferably.

The binder 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 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. Is more preferably 30% by mass to 70% by mass.

-Photopolymerization initiator-
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 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-aminoalkylphenone”) 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") Also referred to as

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. .

Further, as the photopolymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-014783 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) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF AG) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2- Droxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) 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, BASF) (Product name: Lunar 6, D) SH manufactured by Japan Co., Ltd.), 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 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, KP (made by Shin-Etsu Chemical Co., Ltd.), Polyflow (made by Kyoeisha Chemical Co., Ltd.), F-top (made by JEMCO), Megafac (made by DIC), Florard (Sumitomo 3M) under the following trade names Each series may be mentioned, such as (manufactured by Co., Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning).
Moreover, the weight average as polystyrene conversion measured by the gel permeation chromatography at the time of using tetrahydrofuran (THF) as a solvent, containing the structural unit A and the structural unit B represented by following formula I-1 as surfactant is used 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), each of R ⁴⁰¹ and R ⁴⁰³ independently represents 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 L represents an alkyl group having 3 to 6 carbon atoms, p and q each represent a polymerization percentage, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18 and s represents an integer of 1 to 10, and * represents a binding site to another structure Represent.

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in the formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and in view of compatibility and wettability to the coated surface, an alkyl group having 1 to 3 carbon atoms is preferable, and the carbon number is 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 paragraph 0060 to paragraph 0071 of JP2009-237362A 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, and more preferably 0.01% by mass or less with respect to the total mass of the photosensitive layer. More preferably, it is 3% by mass.

[Polymerization inhibitor]
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 them, phenothiazine, phenoxazine or 4-methoxyphenol can be suitably 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 preferably 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.
Moreover, in order to form the said photosensitive layer easily, the photosensitive resin composition which forms the said photosensitive layer makes a solvent contain once, adjusts the viscosity of the photosensitive resin composition, and the photosensitive resin composition containing a solvent is included. Can be applied and dried to suitably form the photosensitive layer.
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. Further, specific examples of the solvent also include the solvents described in paragraphs [0174] to [0178] of JP-A-2011-221494, the contents of which are incorporated in the present specification.

In addition to the solvents described above, 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, 1 if necessary. 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.
As solvents having a boiling point of 130 ° C. or more and less than 160 ° C., 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.), Propylene glycol methyl-n-propyl ether (bp 131 ° C.) can be exemplified.
As solvents having a boiling point of 160 ° C. or higher, 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.

When the photosensitive resin composition is applied, the content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is 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 may contain a plasticizer for the purpose of improving the plasticity.
It is preferable that the said plasticizer has a smaller weight average molecular weight than a specific polymer.
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 formulae, R is an alkyl group having 2 to 8 carbon atoms, n is an integer of 1 to 50, and * represents a bonding site to another atom.

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

As said plasticizer, although the compound which has the following structure is mentioned, for example, it is not limited to these.

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]
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 paragraph 0139 to paragraph 0141 of WO 2015/093271.

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.

[Basic compound]
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.
Examples of the heterocyclic amine include 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] -7-Undesen etc. are mentioned.
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 compounds]
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.

The addition amount of the heterocyclic compound in the photosensitive layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive layer, when the heterocyclic compound is added. % 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, commercially available products described in paragraph 0189 of JP-A-2011-221494, such as JER 828, JER 1007, JER 157 S70 (manufactured by Mitsubishi Chemical Corporation), JER 157 S 65 (manufactured by Mitsubishi Chemical Holdings), and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, made 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-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 (manufactured by Nagase Chemtech Inc.), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Celoxide 2021 P, 2081, 2000, 3000, EHPE 3150, Epolide GT 400, Celliners B 0134, B 0177 (manufactured by Daicel Co., Ltd.) 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 alonoxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX 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, it is preferable from the viewpoint of etching resistance and line width stability that the heterocyclic compound is a compound having an epoxy group.

[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-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxy Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more 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-A-2014-85643, the contents of which are incorporated herein.

-Average film thickness of photosensitive layer-
The average film thickness of the photosensitive layer is preferably 1.0 μm or more, more preferably 2.0 μm or more, and still more preferably 5.0 μm or more, from the viewpoint of transferability (lamination property). 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 photosensitive resin composition for forming a photosensitive layer can be prepared by mixing each component and a solvent in any proportion and in any method and stirring and dissolving. 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.

A photosensitive transfer material according to the present disclosure having a photosensitive layer on a temporary support can be obtained by applying the photosensitive resin composition onto the intermediate layer 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.
In addition, after forming the other layer mentioned later on an intermediate | middle layer, a photosensitive layer can also be apply | coated.

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

-Thermoplastic resin layer, cover film etc.-
The photosensitive transfer material according to the present disclosure preferably further includes a thermoplastic resin layer between the temporary support and the intermediate layer from the viewpoint of transferability.
The photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive layer.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-85643, and preferred embodiments of the other layers are described in paragraphs 0194 to 0-196 of JP-A-2014-85643, respectively. The contents of this publication are incorporated herein.
Among them, from the viewpoint of transferability, the thermoplastic resin layer preferably contains at least one thermoplastic resin selected from the group consisting of an acrylic resin and a styrene / acrylic copolymer.

When the photosensitive transfer material according to the present disclosure has another layer such as a thermoplastic resin layer, it is produced according to the method for producing a photosensitive transfer material described in paragraph 0094 to paragraph 0098 of JP-A-2006-259138. can do.
For example, in the case of producing a photosensitive transfer material according to the present disclosure having a thermoplastic resin layer, a solution in which a thermoplastic organic polymer and an additive are dissolved on a temporary support (for thermoplastic resin layer Coating liquid) is applied and dried to form a thermoplastic resin layer, and then a resin and an additive are added to a solvent which does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer (intermediate liquid (intermediate) Layer composition) is applied and dried to laminate the intermediate layer. The photosensitive transfer material according to the present disclosure is preferably applied by further applying a photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer onto the formed intermediate layer, and drying and laminating a photosensitive layer. Can be produced.

-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 a contrast enhancement layer, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to 0055 of JP-A-6-332167, a photopolymer handbook, a photopolymer conference, an industry survey 1989), Photopolymer Technology, Yamaoka, Nagamatsu ed., Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

(Resin pattern manufacturing method and wiring manufacturing method)
The resin pattern production method according to the present disclosure is not particularly limited as long as it is a resin pattern production method using the photosensitive transfer material according to the present disclosure, but the photosensitive transfer material according to the present disclosure is nearest to the photosensitive layer side. The process of bonding the outer layer to the support, the process of exposing the photosensitive layer to a pattern, and the process of developing the photosensitive layer subjected to the pattern exposure, and developing the photosensitive layer after the process of bonding to the support Preferably, the method further comprises the step of peeling off the temporary support.
Further, the wiring manufacturing method according to the present disclosure is not particularly limited as long as it is a wiring manufacturing method using the photosensitive transfer material according to the present disclosure, but the most on the photosensitive layer side in the photosensitive transfer material according to the present disclosure. A step of bonding the outer layer to a support having a conductive layer on the surface, a step of pattern exposing the photosensitive layer, a step of developing the photosensitive layer subjected to the pattern exposure to form a resin pattern, the conductive using the resin pattern as a mask The process of etching a layer and the process of peeling the said resin pattern are included, The process of peeling the said temporary support after the process of bonding together to the said support and before the process of developing the said photosensitive layer Is preferred.
The “outside layer on the photosensitive layer side” in the photosensitive transfer material according to the present disclosure means a temporary support, an intermediate layer, and a photosensitive transfer material according to the present disclosure having the photosensitive layer in this order. Needless to say, it 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 a conductive layer in the said surface is also called a "board | substrate."

Conventionally, the photosensitive resin composition is divided into a negative type in which a portion irradiated with an actinic ray remains as an image and a positive type in which a portion not irradiated with an actinic ray is left as an image. 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. In addition, since the technique of exposing the remaining photosensitive layer again to produce different patterns can not be realized without the photosensitive layer, the resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure Preferably, the mode in which is carried out two or more times is mentioned.

<Lamination process>
The resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure is a support having the outermost layer on the photosensitive layer side in the photosensitive transfer material according to the present disclosure, or a support having a conductive layer on the surface. It is preferable that the process (lamination process) of bonding together is included.
In the bonding step, the photosensitive transfer material is preferably brought into contact with a support or a base material having a conductive layer on the surface thereof for bonding.
Further, in the bonding step, it is preferable that the conductive layer be pressure-bonded so that the outermost layer on the photosensitive layer side is in contact. 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 restriction | limiting in particular as a method to crimp the said base material and the said photosensitive transfer material, A well-known transfer method and the lamination method can be used.
Specifically, for example, it is preferable to overlap the photosensitive layer side of the photosensitive transfer material on the conductive layer, and to apply pressure by a roll or the like or to apply pressure and heat. 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 are appropriately set according to 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. can do. 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)]
It is preferable that a support body is a glass base material or a film base material, and, as for a substrate by which a plurality of conductive layers were laminated on a support body, it is more preferred that it is a film base material. When the wiring manufacturing method which concerns on this indication is wiring for touch panels, it is especially preferable that a support body 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 base material, materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate having no optical distortion and a substrate having high transparency, and for specific materials, 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 resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure, it is preferable that at least one of the plurality of conductive layers includes a metal oxide.
As a conductive layer, it is preferable that it is an electrode pattern corresponded to the sensor of the visual recognition part used for an electrostatic capacitance type touch panel, or wiring of a periphery extraction part.

[Wiring forming substrate]
The 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.

<Exposure process>
The resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure preferably includes the step of exposing the photosensitive layer to a pattern (exposure step) after the bonding step.
In the exposure step, it is preferable to irradiate an actinic ray through a support provided with a coating or a mask having a predetermined pattern on a substrate. 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.
In the present disclosure, the detailed arrangement and specific size of the pattern 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.
The exposure in the exposure step may be exposure through a mask or digital exposure using a laser or the like, but is preferably exposure through an exposure mask.
The resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure includes the step of bringing the photosensitive transfer material into contact with the exposure mask between the bonding step and the exposure step. Is preferred. It is excellent by the resolution of the pattern obtained as it is the said aspect.

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 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.

Even if the pattern exposure is performed after peeling off the temporary support from the intermediate layer and the photosensitive layer, exposure is performed via the temporary support before peeling off the temporary support, and then the temporary support is peeled off. May be The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Development process>
The resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure preferably includes the step (developing step) of developing the photosensitive layer after the exposing step to form a pattern.
In addition, in the development step, the intermediate layer of the exposed portion is also removed together with the exposed photosensitive layer.
Furthermore, in the development step, the intermediate layer in the unexposed area may also be removed in the form of being dissolved or dispersed in the developer.
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 exposed portion of the photosensitive layer can be removed, and, for example, a known developer such as a developer described in JP-A-5-72724 can be used. The developing solution is preferably a developing solution in which the exposed portion of the photosensitive layer has a dissolution type developing behavior. The developer is preferably an alkaline aqueous solution, and more preferably an alkaline aqueous solution containing, for example, a compound having a pKa of 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, to describe shower development, exposed portions can be removed by spraying a developer onto the photosensitive layer and the intermediate 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 temperature of the developing solution is preferably 20 ° C to 40 ° C.
Moreover, the effect of suppressing the deformation of the pattern shape in the present disclosure is more exhibited when the time from exposure to development is longer. It may be developed immediately after exposure, but in the aspect in which development is carried out after lapse of time from exposure to development of preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 6 hours or more from exposure. The effect of suppressing the deformation of the pattern shape in the present disclosure is further exerted.
In addition, the resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure includes known steps 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 to 121.6 kPa, and more preferably performed under an environment of 50.66 kPa or more. On the other hand, it is more preferable to carry out under an environment of 111.46 kPa or less, and it is particularly preferable to carry out 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.

Although there are no particular limitations on the transport speed of the support at each step in the resin pattern production method according to the present disclosure or the wiring production method according to the present disclosure, it is 0.5 m / min to 10 m except during exposure. / Min is preferable, and 2.0 m / min to 8.0 m / min is more preferable except at the time of exposure.

<Peeling process>
The method for producing a resin pattern according to the present disclosure or the method for producing a wiring according to the present disclosure includes the step of peeling the temporary support after the step of bonding to the support and before the step of developing the photosensitive layer. It is preferable to include a (peeling step).
The resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure uses the photosensitive transfer material having the above-mentioned intermediate layer, so that it is at any timing after laminating the photosensitive transfer material and before development. Even if the temporary support is peeled off, since the adhesion between the intermediate layer and the photosensitive layer is excellent, the occurrence of defects such as partial peeling of the intermediate layer can be suppressed, and pattern formation can be favorably performed.
Further, in the resin pattern manufacturing method according to the present disclosure or the wiring manufacturing method according to the present disclosure, from the viewpoint of pattern formability and resolution, after the step of bonding the support to the support, the step of pattern exposing the photosensitive layer It is more preferable to include the step of exfoliating the above-mentioned temporary support before. Furthermore, in the above aspect, when pattern exposure is performed by bringing a mask into contact, the photosensitive layer and the mask do not come in direct contact with each other, so the pattern formability and resolution are superior.
The method of peeling off the temporary support in the peeling step is not particularly limited, and may be peeled by a known method.

<Etching process>
It is preferable that the wiring manufacturing method which concerns on this indication includes the process (etching process) which carries out the etching process of the said conductive layer in the area | region where the said pattern is not arrange | positioned.
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.
For the etching of the conductive layer, etching can be applied by a known method such as a method described in paragraph 0048 to paragraph 0054 of JP-A-2010-152155 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 the contamination of the process line, a step of washing the support having the etched conductive layer (washing step), if necessary, and a support having the etched conductive layer You may perform the process (drying process) to dry. For the cleaning step, for example, the substrate may be cleaned with pure water at normal temperature (10 ° C. to 35 ° C.) for 10 seconds to 300 seconds. For the drying step, for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm ² to 5 kg / cm ² ) may be appropriately adjusted to perform drying.

<Etching resist peeling process>
It is preferable that the wiring manufacturing method 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 for peeling using a peeling solution, for example, the substrate having the above-mentioned photosensitive layer or the like is preferably added to the peeling solution during stirring at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. A method of soaking for a minute may be mentioned.
As the peeling solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or a quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And stripping solutions dissolved in these mixed solutions. A peeling solution may be used, and peeling may be performed by a spray method, a shower method, a paddle method, or the like.

In addition, in the wiring manufacturing method according to the present disclosure, the exposure step, the developing step, and the etching step may be repeated twice or more as necessary.
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 wiring manufacturing method according to the present disclosure may include other arbitrary steps. For example, although the following processes are mentioned, it is not limited to these processes.

<Step of reducing visible light reflectance>
The wiring manufacturing method according to the present disclosure can include 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 provided on the support.
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>
In the wiring manufacturing method according to the present disclosure, a step of forming an insulating film on the support having the conductive layer, for example, on the formed wiring (the conductive layer etched), and a new conductive layer on the insulating film It is also preferable to include the forming step.
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.

In the wiring manufacturing method according to the present disclosure, the 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.
The wiring substrate obtained by the wiring manufacturing method according to the present disclosure may have a wiring of only one layer or a wiring of two or more layers on the substrate.

In the wiring manufacturing method according to the present disclosure, the support may have a plurality of conductive layers on both surfaces respectively, and circuits may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the support. preferable. 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 wiring manufacturing method 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 wiring manufacturing method 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 wiring manufacturing method concerning 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 wiring manufacturing method 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 wiring manufacturing method 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 wiring manufacturing method 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, and those described in FIG. 1 and FIG. 5 of Japanese Patent Application Laid-Open No. 2012-89102, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (e.g. 2 of 2013-54727, other configurations (for example, the one described in FIG. 6 of JP-A-2013-164871), various out-cell types (so-called GG, G1 · G2, GFF, 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 configurations 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, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed 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 Composition 1 for Forming Intermediate Layer>
Composition 1 for forming an intermediate layer was produced according to the following formulation.
Distilled water: 13.4 parts Methanol: 75.6 parts Hydroxypropyl methylcellulose (trade name: TC-5, manufactured by Shin-Etsu Chemical Co., Ltd.):
4.1 parts · Snowtex O (silica particles, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm): 68.5 parts

<Synthesis of MATHF Copolymer>
Methacrylic acid (86 g, 1 mole) was allowed to cool to 15 ° C. and camphor sulfonic acid (4.6 g, 0.02 mole) was added. To the solution was added dropwise 2,3-dihydrofuran (71 g, 1 mole, 1.0 equivalent). After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) is added, extraction is performed with ethyl acetate (500 mL), drying is performed with magnesium sulfate, insolubles are filtered and concentrated under reduced pressure at 40 ° C. or less. Distillation under reduced pressure gave 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg fraction as a colorless oil (yield: 80 mol%).
Using this, the following MATHF copolymers were synthesized by the method described in paragraphs 0248 to 0249 of JP 2013-61616A. The weight average molecular weight of the obtained MATHF copolymer measured by gel permeation chromatography (GPC) was 14,000. The structure of the MATHF copolymer was as shown below (the numerical values in the structural formula are molar ratios).

<Preparation of Photosensitive Resin Composition 1>
Each component was mixed so that it might become the following composition, and the photosensitive resin composition 1 was produced.
MATHF copolymer: 93.9 parts Photoacid generator (following PAG-1): 5.0 parts Surfactant (following surfactant 1): 0.1 parts Additive (following additive 1) ): 1.0 part, PGMEA: 900 parts

PAG-1: Compound A-1 of the following structure
Surfactant 1: F-554, a perfluoroalkyl group-containing nonionic surfactant (manufactured by DIC Corporation)
Additive 1: (N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea, abbreviated as CHMETU)

<Preparation of photosensitive transfer material>
Composition 1 for forming an intermediate layer was slit coated on a 50 μm thick polyethylene terephthalate (PET) film (provisional support 1) so as to have a dry film thickness of 2.0 μm, and dried in a 100 ° C. convection oven for 2 minutes I did. Next, photosensitive resin composition 1 was applied onto this intermediate layer using a slit nozzle so that the dry film thickness would be 3.0 μm. Thereafter, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (manufactured by Tredegar, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist (photosensitive transfer material) of Example 1.

(Examples 2 to 11 and 14 to 17)
Example 2 to Example 2 in the same manner as Example 1 except that the composition for forming an intermediate layer having the composition described in Table 1 was used, and the intermediate layer was formed to have the volume fraction and the film thickness described in Table 1. 11 and 14 to 17 photosensitive transfer materials were prepared, respectively.

(Example 12)
A photosensitive transfer material of Example 12 was obtained in the same manner as Example 1, except that the following photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

<Preparation of Photosensitive Resin Composition 2>
Each component was mixed so that it might become the following composition, and the photosensitive resin composition 2 was produced.

-composition-
Novolak resin (metacresol: paracresol = 30: 70 (mass ratio), molecular weight 5, 500): 79.9 parts Photosensitive agent: Naphthoquinone diazide (described below) described on page 4 of JP-A-4-22955 And NQD.) Compound (1): 20 parts, surfactant (the above surfactant 1): 0.1 parts, PGMEA: 900 parts

(Example 13)
A photosensitive transfer material of Example 13 was obtained in the same manner as Example 1, except that the following photosensitive resin composition 3 was used instead of the photosensitive resin composition 1.

<Preparation of Photosensitive Resin Composition 3>
A negative photosensitive resin composition 3 was produced according to the following formulation.
Acrylic acid-methyl methacrylate copolymer (Mw 20,000, acid value 130 mg KOH / g): 30 parts Propylene glycol monomethyl ether: 100 parts Irgacure 907 (manufactured by BASF): 4.0 parts Trimethylpropane triacrylate: 15.0 copies

(Comparative example 1)
A photosensitive transfer material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the following laminated temporary support was used instead of the temporary support 1 and the intermediate layer was not formed.
Laminated temporary support: Toray Industries Co., Ltd., a laminated support of polyethylene terephthalate (PET), and the layer on the photosensitive layer side contains SiO ₂ particles (average particle diameter: 500 nm).

(Comparative example 2)
A photosensitive transfer material of Comparative Example 2 was obtained in the same manner as Example 1, except that the intermediate layer contained no particles.

(Evaluation)
<Evaluation of adhesion between interlayer and photosensitive layer>
Copper was deposited as a conductive layer to a film thickness of 200 nm by a vacuum evaporation method on a PET substrate having a film thickness of 100 μm, to obtain a circuit formation substrate.
The protective film is peeled off from the photosensitive transfer material of Example 1, and the photosensitive transfer material obtained on the copper layer is laminated at 100 ° C., a speed of 1 m / min, a linear pressure of 0.6 MPa, and temporarily supported. The body was peeled off to prepare a laminate in which a photosensitive layer was laminated on a copper layer.
Printerac C (manufactured by Nitto Denko Corp.) cut into 4.5 cm × 15 cm was stuck on the laminate, and cut into 4.5 cm × 9 cm so that the width of the tape and the support matched. The resultant was subjected to 180 ° peeling at a peeling speed of 100 mm / min using a Tensilon universal tester made by A & D Co., and the adhesion between the intermediate layer and the photosensitive layer was measured.
The adhesion at that time was evaluated according to the following evaluation criteria. The larger the value, the better, and 5 to 3 is a practical range.
〔Evaluation criteria〕
5: Measurement upper limit (22 gf / cm (0.22 N / cm)) or more 4: 5.0 gf / cm (0.098 N / cm) or more and less than 22.0 gf / cm 3: 2.0 gf / cm (0.049 N / cm) or more and less than 10.0 gf / cm 2: less than 2.0 gf / cm 1: Since the interlayer was also exfoliated at the time of exfoliation of the support

It is understood from Table 1 that the photosensitive transfer material of the example is excellent in the adhesion between the intermediate layer and the photosensitive layer as compared with the photosensitive transfer material of the comparative example.

In addition, the average particle diameter of the particle | grains described in Table 1 is an arithmetic mean particle diameter, and is measured by the measuring method mentioned above.
A to C described in the “Resist” column in Table 1 indicate that the photosensitive layer in the photosensitive transfer material is a chemically amplified positive resist layer in the case of A, and in the case of B, the photosensitive transfer material In the case of C, it represents that the photosensitive layer in the photosensitive transfer material is a negative resist layer.
In addition, the details of the particles described in Table 1 other than those described above are as follows.
SiO ₂ (average particle diameter 50 nm): silica particles, Nissan Chemical Industries Ltd. Snowtex XL, arithmetic average particle diameter 50 nm
SiO ₂ (average particle size 100 nm): silica particles, Snowtex MP-1040 manufactured by Nissan Chemical Industries, Ltd., arithmetic average particle size 100 nm
SiO ₂ (average particle size 200 nm): silica particles, Snowtex MP-2040 manufactured by Nissan Chemical Industries, Ltd., arithmetic average particle size 200 nm
SiO ₂ (average particle size 300 nm): silica particles, Snowtex MP-3040 manufactured by Nissan Chemical Industries, Ltd., arithmetic average particle size 300 nm
TiO ₂ (average particle size 20 nm): titanium oxide particles, SST-21 manufactured by Ishihara Sangyo Co., Ltd., arithmetic average particle size 20 nm
ZrO ₂ (average particle size 42 nm): Zirconium oxide particles, Nanouse ZR-20AS manufactured by Nissan Chemical Industries, Ltd., arithmetic average particle size 42 nm
PMMA (average particle size 40 nm): Polymethyl methacrylate particles, EPOLER MX030W manufactured by Nippon Shokubai Co., Ltd., arithmetic average particle size 40 nm
PVA: polyvinyl alcohol, Kuraray Co., Ltd. Kuraray Poval PVA 205

(Example 18)
<Preparation of Composition 18 for Forming Intermediate Layer A and Composition 18 for Forming Intermediate Layer B>
Composition 18 for forming intermediate layer A (hereinafter referred to as “interlayer of two layers”) by the same method as in Example 1 so as to obtain the composition described in Table 2 and the volume fraction described in Table 2 The layer provided on the temporary support side is also referred to as an intermediate layer A), and the composition 18 for forming an intermediate layer B (hereinafter, the layer provided on the photosensitive layer side among the two intermediate layers) is referred to as an intermediate layer B. Also referred to are each prepared.

<Preparation of photosensitive transfer material>
Composition 18 for forming intermediate layer A was slit coated on a 50 μm thick polyethylene terephthalate (PET) film (provisional support 1) so as to have a dry film thickness of 2.0 μm, and 2 in a 100 ° C. convection oven. It was allowed to dry for a minute to form an intermediate layer A. Next, the composition 18 for forming an intermediate layer B was slit-coated so as to have a dry film thickness of 2.0 μm and dried in a 100 ° C. convection oven for 2 minutes to form an intermediate layer B. Next, photosensitive resin composition 1 was applied onto this intermediate layer using a slit nozzle so that the dry film thickness would be 3.0 μm. Thereafter, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (manufactured by Tredegar, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist (photosensitive transfer material) of Example 18.
The adhesion evaluation was performed in the same manner as in Example 1 using the obtained photosensitive transfer material of Example 18. The evaluation results are shown in Table 2.

(Examples 19 to 25)
Using the composition for forming the intermediate layer A and the composition for forming the intermediate layer B having the composition of the intermediate layer A and the intermediate layer B described in Table 2, it is carried out so as to have the volume fraction and the film thickness described in Table 2. The photosensitive transfer materials of Examples 19 to 25 were produced in the same manner as in Example 18 except that the intermediate layer A and the intermediate layer B were formed in the same manner as in Example 18, and the adhesion was evaluated. The evaluation results are shown in Table 2.

(Example 26)
A photosensitive transfer material of Example 26 was obtained in the same manner as in Example 23, except that the following photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

(Example 27)
A photosensitive transfer material of Example 27 was obtained in the same manner as in Example 23, except that the following photosensitive resin composition 3 was used instead of the photosensitive resin composition 1.

Details of the binders and particles described in Table 2 are as follows.
HMPC: hydroxypropyl methylcellulose (trade name: TC-5, manufactured by Shin-Etsu Chemical Co., Ltd.)
PVA: Polyvinyl alcohol (trade name: Kurare Hoval PVA 205, manufactured by Kuraray Co., Ltd.)
HPC: Hydroxypropyl Cellulose (trade name: HPC-SSL, manufactured by Nippon Soda Co., Ltd.)
Acrylic resin: methacrylic acid / benzyl methacrylate copolymer (Mw: 11,000, composition ratio (molar ratio): 30/70)
SiO ₂ (average particle diameter 50 nm): silica particles, Nissan Chemical Industries Ltd. Snowtex XL, arithmetic average particle diameter 50 nm

(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 to a thickness of 150 nm by sputtering, and copper is deposited thereon by a vacuum evaporation method to a thickness of 200 nm as a conductive layer of the first layer. The film formation was performed 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.). The contact pattern was exposed using a photomask provided with a pattern (hereinafter also referred to as “pattern A”) shown in FIG. 2 having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support.
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, the copper layer is etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched using an ITO etching liquid (ITO-02 manufactured by Kanto Chemical Co., Ltd.) The board | substrate with which copper (solid line part SL) and ITO (gray part G) were both drawn by 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, 12: intermediate layer, 14: photosensitive layer, 16: cover film, 100: photosensitive transfer material, SL: solid line portion, G: gray portion, DL: dotted portion

Claims

Having a temporary support, an intermediate layer, and a photosensitive layer in this order,
A photosensitive transfer material, wherein the intermediate layer contains a binder and particles having an arithmetic average particle diameter of 400 nm or less.
The photosensitive transfer material according to claim 1, wherein the volume fraction of the particles in the intermediate layer is 5% to 90% with respect to the total volume of the intermediate layer.
The photosensitive transfer material according to claim 1 or 2, wherein an average film thickness of the intermediate layer is 0.3 μm to 10 μm.
The oxide particles of at least one element selected from the group consisting of Si, Ti, and Zr, or organic particles, is contained in the intermediate layer. Photosensitive transfer material described in the above.
The photosensitive transfer material according to any one of claims 1 to 4, wherein the photosensitive layer contains a binder and a photoacid generator.
The photosensitive transfer material according to claim 5, wherein the binder contained in the photosensitive layer contains a binder having an acid-degradable group-protected acid group.
The photosensitive transfer material according to any one of claims 1 to 4, wherein the photosensitive layer contains a binder having an acid group, a polymerizable compound, and a photopolymerization initiator.
The photosensitive transfer material according to any one of claims 1 to 7, wherein the binder contained in the intermediate layer contains a modified cellulose resin.
The photosensitive transfer material according to any one of claims 1 to 8, wherein the intermediate layer has two or more layers.
The photosensitive transfer material according to claim 9, wherein among the two or more layers in the intermediate layer, particles having an arithmetic average particle diameter of 400 nm or less are contained only in the layer closest to the photosensitive layer.
A step of laminating the outermost layer on the photosensitive layer side in the photosensitive transfer material according to any one of claims 1 to 10 to a support,
Exposing the photosensitive layer to a pattern;
Developing the pattern-exposed photosensitive layer;
A method for producing a resin pattern, comprising the step of peeling off the temporary support after the step of bonding to the support and before the step of developing the photosensitive layer.
A step of bonding the outermost layer on the photosensitive layer side of the photosensitive transfer material according to any one of claims 1 to 10 to a support having a conductive layer on the surface,
Pattern exposing the photosensitive layer;
Developing the photosensitive layer subjected to pattern exposure to form a resin pattern;
Etching the conductive layer using the resin pattern as a mask;
Including the step of peeling the resin pattern,
A process for producing a wiring, comprising the step of peeling off the temporary support after the step of bonding to the support and before the step of developing the photosensitive layer.