TW201924935A - Photosensitive transfer material, method for manufacturing resin pattern, and method for manufacturing circuit - Google Patents

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 invention relates to a photosensitive transfer material, a resin pattern production method, and a wiring manufacturing method.

In a display device (organic electroluminescence (EL) display device, liquid crystal display device, etc.) including a touch panel such as a capacitive input device, an electrode pattern corresponding to a visible portion, a peripheral wiring portion, and a take-out wiring portion The conductive layer pattern of the wiring or the like is provided inside the touch panel.
In the formation of a patterned layer, since the number of steps for obtaining a desired pattern shape is small, the following method is widely used for a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material. The layer is developed after exposure through a mask having a desired pattern.

As a conventional method, for example, a step of exposing a layered body on which a (a) photosensitive layer and a (b) resin layer are formed and heat-treated on a substrate is disclosed in Japanese Laid-Open Patent Publication No. 2016-224161. A method of forming a resist pattern.
Further, Japanese Laid-Open Patent Publication No. 2014-074764 discloses a photosensitive element comprising a support film and a photosensitive layer formed on the support film, wherein the support film has self-healing on a side opposite to the surface in contact with the photosensitive layer. In the layer, the photosensitive layer contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator.

An object of the present invention is to provide a photosensitive transfer material which is excellent in adhesion between an intermediate layer and a photosensitive layer.
Further, another object of the present invention is to provide a resin pattern producing method and a wiring manufacturing method using the above-described photosensitive transfer material.

The 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 mean 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% with respect to the total volume of the intermediate layer.
<3> The photosensitive transfer material according to <1>, wherein the intermediate layer has an average film thickness of 0.3 μm to 10 μm.
The photosensitive transfer material according to any one of the above aspects, wherein the particles contained in the intermediate layer are at least one selected from the group consisting of Si, Ti, and Zr. An oxide particle or an organic particle of an element.
The photosensitive transfer material according to any one of <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-decomposable group.
The photosensitive transfer material according to any one of <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 the above aspects, wherein the binder contained in the intermediate layer contains a modified cellulose resin.
The photosensitive transfer material according to any one of <1> to <8> wherein the intermediate layer has two or more layers.
<10> The photosensitive transfer material according to <9>, wherein among the two or more layers in the intermediate layer, only the layer closest to the photosensitive layer contains particles having an arithmetic mean particle diameter of 400 nm or less.
<11> A resin pattern manufacturing method comprising:
The step of attaching the outermost layer on the photosensitive layer side of the photosensitive transfer material according to any one of <1> to <10> to a support; the step of patterning the photosensitive layer; and The step of developing the pattern-exposed photosensitive layer includes 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.
<12> A wiring manufacturing method, comprising: bonding the outermost layer on the photosensitive layer side of the photosensitive transfer material according to any one of <1> to <10> to a support having a conductive layer on the surface a step of patterning the photosensitive layer; a step of developing the patterned photosensitive layer to form a resin pattern; a step of etching the conductive layer by using the resin pattern as a mask; and stripping The step of the resin pattern includes 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.
[Effect of the invention]

According to an embodiment of the present invention, it is possible to provide a photosensitive transfer material which is excellent in adhesion between an intermediate layer and a photosensitive layer.
Moreover, 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.

Hereinafter, the content of the present invention will be described. Further, the description will be made with reference to the drawings, but the symbols may be omitted.
In addition, the numerical range represented by "-" in this specification is the range which the numerical value of the [----
In the present specification, "(meth)acrylic acid" means two or any of acrylic acid and methacrylic acid, and "(meth)acrylate" means either or both of an acrylate and a methacrylate.
In addition, the amount of each component in the composition in the present specification means a plurality of substances present in the composition, unless otherwise specified, in the case where a plurality of substances corresponding to the respective components are present in the composition. Total measurement.
In this specification, the term "step" includes not only independent steps, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended purpose of the steps is achieved.
In the label of the group (atomic group) in the present specification, it is not described that the substituted or unsubstituted label includes a group having a substituent and a substituent. For example, "alkyl" means not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, the chemical structural formulae in the present specification may be described by a simple structural formula in which a hydrogen atom is omitted.
In the present invention, the meaning of "% by mass" is the same as the meaning of "% by weight", and the meaning of "parts by mass" is the same as the meaning of "parts by weight".
Further, in the present invention, a combination of two or more preferred embodiments is a more preferable aspect.
In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are those using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both product names manufactured by TOSOH CORPORATION) unless otherwise specified. A column gel permeation chromatography (GPC) analyzer was used to detect the molecular weight converted by using polystyrene as a standard substance by a solvent of THF (tetrahydrofuran) or a differential refractometer.

(photosensitive transfer material)
The photosensitive transfer material of the present invention 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 mean particle diameter of 400 nm or less.

The layer structure having a photosensitive support material as a temporary support/intermediate layer/photosensitive layer (/cover film) has various advantages. For example, there is an advantage that, when pattern exposure is performed after laminating a photosensitive layer on a substrate or the like, after the temporary support is peeled off, the mask can be exposed to contact (the photosensitive layer and the mask are not in contact with each other), or when the photosensitive layer is formed. A photosensitive layer having a uniform film thickness can be formed by the unevenness of the surface of the temporary support and foreign matter.
The present inventors have found that when this structure is used, when the temporary support is peeled off, peeling occurs between the temporary support and the intermediate layer, peeling occurs between the intermediate layer and the photosensitive layer, and peeling occurs. The problem of unstable cross section. That is, it is considered that the adhesion between the intermediate layer and the photosensitive layer may be insufficient.
The inventors have found that in order to sufficiently ensure the interlayer adhesion between the intermediate layer and the photosensitive layer, a filler is added to the intermediate layer to increase the contact area with the photosensitive layer at the layer interface, and the adhesion is enhanced by physical action. Thereby, it is possible to stably peel off between the temporary support and the intermediate layer.
As a result of intensive studies, the present inventors have found that the photosensitive layer having the above-described structure is excellent in adhesion between the intermediate layer and the photosensitive layer.
Although the detailed mechanism of the above effects is not clear, as described above, the inventors speculated that by the intermediate layer containing particles having an arithmetic mean particle diameter of 400 nm or less, the contact area with the photosensitive layer at the layer interface is increased, and the middle is increased. The adhesion between the layer and the photosensitive layer.
Further, the inventors presumed that the arithmetic mean particle diameter of the particles was 400 nm or less, and the contact area with the photosensitive layer at the layer interface was further increased, and the adhesion between the intermediate layer and the photosensitive layer was improved.

Hereinafter, the photosensitive transfer material of the present invention will be described in detail.

Fig. 1 is a view schematically showing an example of a layer structure of a photosensitive transfer material of the present invention. The photosensitive transfer material 100 shown in FIG. 1 sequentially laminates the temporary support 10, the intermediate layer 12, the photosensitive layer 14, and the cover film 16.
The intermediate layer 12 contains a binder and particles having an arithmetic mean particle diameter of 400 nm or less.
Hereinafter, the constituent materials and the like of the photosensitive transfer material of the present invention will be described.

<temporary support>
The temporary support system supports the intermediate layer and the photosensitive layer and is capable of being peeled off from the intermediate layer.
The temporary support used in the present invention has a light transmissive property from the viewpoint of being able to expose the photosensitive layer via the temporary support when the photosensitive layer is subjected to pattern exposure.
The light transmittance means that the transmittance of the main wavelength of the light for pattern exposure is 50% or more, and from the viewpoint of improving the exposure sensitivity, the transmittance of the dominant wavelength of the light for pattern exposure is preferably 60% or more. More than 70% is better. As a method of measuring the transmittance, a method of measurement using an MCPD Series manufactured by Otsuka Electronics Co., Ltd. is mentioned.
A glass substrate, a resin film, paper, etc. are mentioned as a temporary support, and a resin film is especially preferable from a viewpoint of intensity|strength, and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, the biaxially oriented polyethylene terephthalate film is particularly preferred.

The thickness of the temporary support is not particularly limited, and is preferably in the range of 5 μm to 200 μm, and is preferably in the range of 10 μm to 150 μm from the viewpoint of ease of handling and versatility.
The thickness of the temporary support may be selected depending on the material from the viewpoints of the strength of the support, the flexibility required for bonding the wiring forming substrate, and the light transmittance required in the first exposure step.

A preferred aspect of the temporary support is described in paragraphs 0017 to 0018 of JP-A-2014-085643, the contents of which are incorporated herein.

<intermediate layer>
The photosensitive transfer material of the present invention contains a binder and particles having an arithmetic mean diameter of 400 nm or less.

-Binder -
The binder is preferably a water-soluble or alkali-soluble binder, and a water-soluble or alkali-soluble polymer is more preferred.
Further, in the present invention, "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 the solubility in an aqueous alkali solution having a pH of 8.5 or more at 25 ° C is 0.1. More than % by mass.
Moreover, the above "water-soluble or alkali-soluble" means any of water-soluble or alkali-soluble, and may be water-soluble and alkali-soluble.

Examples of the binder include a phenol formaldehyde resin, a m-cresol formaldehyde resin, a p-cresol formaldehyde resin, a meta/p-mixed cresol formaldehyde resin, and a phenol/cresol (which may be an inter-, a- or an inter/pair mixture). Any of a mixture of a novolak resin such as a formaldehyde resin, a gallic phenol acetone resin, a polyhydroxystyrene resin, a modified cellulose resin, an acrylic resin having a hydroxyl group (for example, homopolymerization of a hydroxyalkyl (meth)acrylate) Or copolymer), starch, hepatic sugar, chitin, agarose, carrageenan, pullulan, gum arabic, soy gum, polyamide resin, epoxy resin, polyacetal Resin, acrylic resin, polystyrene resin, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol, etc. .

In the above, the binder is at least selected from the group consisting of a novolak resin, a modified cellulose resin, and an acrylic resin having a hydroxyl group from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and pattern formation properties. One type of resin is preferable, and at least one type of resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxyl group is more preferable, and a modified cellulose resin is further preferable.
Further, as the modified cellulose resin, hydroxyalkylated cellulose is preferred from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and pattern formability.
As the hydroxyalkylated cellulose, preferred are hydroxymethylcellulose, hydroxyethylcellulose, polyhydroxyethylated cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and ethylene. Aldehyde hydroxypropyl methylcellulose, hydroxypropyl methylcellulose phthalate, and the like.
In view of the adhesion between the intermediate layer and the photosensitive layer and the pattern formation property, at least one resin selected from the group consisting of hydroxypropylcellulose and hydroxypropylmethylcellulose is preferred, and the hydroxyl group is preferred. More preferably, propylmethylcellulose is preferred.
Further, as the binder, at least one resin selected from the group consisting of polyvinyl alcohol and polyvinyl formal is preferable from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, and polyvinyl alcohol is more preferable. good.

The weight average molecular weight of the binder is preferably 1,000 or more, and preferably 2,000 to 100,000, from the viewpoints of adhesion between the intermediate layer and the photosensitive layer, pattern formation property, solubility in the developer after exposure, and transferability. 10,000 to 50,000 is better.

The intermediate layer may contain one type of binder alone or two or more types.
From the viewpoint of the adhesion between the intermediate layer and the photosensitive layer, the pattern formation property, the solubility in the developer after exposure, and the transferability, the content of the binder in the intermediate layer is 1 mass with respect to the total mass of the intermediate layer. More preferably, it is more preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 90% by mass or less, further preferably 2% by mass or more and 80% by mass or less, and more preferably 3% by mass or more and 70% by mass or less. .

- Particles with an arithmetic mean particle size below 400 nm -
The intermediate layer contains particles having an arithmetic mean particle diameter of 400 nm or less.
As the particles, metal oxide particles or organic particles are preferable from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, and oxide particles or organic particles of an element selected from the group consisting of Si, Ti, and Zr are Better.
Further, the metal of the metal oxide particles in the present invention further contains a semimetal such as B, Si, Ge, As, Sb or Te.
The metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B. As the oxide particles of atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc., cerium oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin oxide or More preferably, cerium/tin oxide is used, and cerium oxide, titanium oxide, titanium composite oxide or zirconia is further preferred, and cerium oxide, titanium oxide or zirconium oxide is particularly preferred.
As the organic particles, organic resin particles are preferably exemplified.
Examples of the organic resin particles include homopolymers and copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylate, and methacrylate, and nitrocellulose, methyl cellulose, and ethyl cellulose. Cellulose-based polymer such as cellulose acetate, polyethylene, polypropylene, polystyrene, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinyl butyral, polyethylene a copolymer of a vinyl polymer such as an alcohol and a vinyl compound; a condensed polymer such as polyester, polyurethane or polyamide; a rubber-based thermoplastic polymer such as a butadiene-styrene copolymer; and an epoxy compound; A polymerizable or thermally polymerizable compound is polymerized, a polymer obtained by crosslinking, a melamine compound, or the like.
Among these, as the organic particles, acrylic resin particles are preferred, and polymethyl methacrylate particles are more preferred.
Further, the particles can also be treated with an organic material or an inorganic material to impart dispersion stability. It is preferred that the surface of the particle system is hydrophilic. For example, hydrophilization treatment may be performed on the surface of the particles whose surface is hydrophobic.

The arithmetic mean particle diameter of the particles is 400 nm or less. From the viewpoint of the adhesion between the intermediate layer and the photosensitive layer, 250 nm or less is preferable, 200 nm or less is more preferable, and 150 nm or less is further preferable, and 10 nm is preferable. 150 nm is especially good.
The method of measuring the arithmetic mean particle diameter of the particles in the present invention means measuring the particle diameter of 200 arbitrary particles by an electron microscope, and the arithmetic mean thereof. Also, when the shape of the particles is not spherical, the largest diameter is taken as the diameter.

From the viewpoint of the adhesion between the intermediate layer and the photosensitive layer, the volume fraction of the particles in the intermediate layer (the volume ratio of the particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer. Preferably, 10% to 80% is more preferably, 15% to 70% is further preferred, and 20% to 60% is particularly preferred.
As will be described later, in the case where the intermediate layer is two layers, the volume fraction of the above-mentioned particles in all the intermediate layers with respect to the total volume of the intermediate layer from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer (intermediate layer) The proportion of the particles in the film is preferably 2% to 90%, more preferably 3% to 80%, further preferably 5% to 20%, and particularly preferably 10% to 20%.

-Other additives -
In addition to the binder and the particles, the intermediate layer in the present invention may contain a known additive as needed.
As other additives, other additives used in the photosensitive layer described later are preferably mentioned.

- Structure 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, the adhesion between the intermediate layer and the temporary support and the adhesion between the intermediate layer and the photosensitive layer may be From the viewpoint of the viewpoint, it is preferable to form from 2 to 5 layers, more preferably 2 or 3 layers, and particularly preferably 2 layers.
In the case where the intermediate layer has two or more layers, it is preferred to contain a water-soluble or alkali-soluble binder in each layer, and the same kind of binder may be used in each layer, or different bonding may be used. Agent.
When the intermediate layer has two or more layers, the particles having an arithmetic mean particle diameter of 400 nm or less may be contained in a plurality of layers, and are included in the closest viewpoint from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. A layer of the photosensitive layer is preferred.
Further, from the viewpoint of the adhesion between the temporary support and the intermediate layer, the particles having an arithmetic mean particle diameter of 400 nm or less are included in the layer of the two or more layers in the intermediate layer which is closest to the temporary support. good. That is, it is more preferable that the particles having an arithmetic mean particle diameter of 400 nm or less are contained only in the layer closest to the photosensitive layer among the two or more layers among the intermediate layers.
Further, for example, in the photosensitive transfer material, when the intermediate layer is in contact with the photosensitive layer, "the layer closest to the photosensitive layer among the two or more layers in the intermediate layer" corresponds to "two or more of the intermediate layers" The layer in the layer that is in contact with the photosensitive layer."

- average film thickness of the intermediate layer -
The average thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and 0.3 μm to 2 μm, from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and pattern formation properties. good.
The method for measuring the average film thickness of each layer in the present invention is not particularly limited, and a known method can be used. Further, it is preferable that the average value is 10 points or more.
Specific examples thereof include surface shape measurement, optical microscopy of a cross section, and observation by an electron microscope. Further, in the measurement of the surface shape, the Dektak series manufactured by Bruker Corporation can be suitably used. Further, a scanning electron microscope (SEM) can be suitably used in the cross-sectional observation.
Further, the thickness of the intermediate layer is preferably thinner than the thickness of the photosensitive layer.

In the case where 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, and the intermediate portion is considered from the viewpoint of adhesion between the intermediate layer and the photosensitive layer and pattern formability. Among the two or more layers in the layer, the average film thickness of the layer closest to the photosensitive layer 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.

- Method of forming the intermediate layer -
The method for forming the intermediate layer is not particularly limited, and an intermediate layer forming composition for mixing the respective components and a solvent (preferably an aqueous solvent) in a specific ratio and by any method and stirring and dissolving them to form an intermediate layer can be prepared. Things. For example, it is also possible to prepare a composition by mixing each component as a solution previously dissolved in a solvent and mixing the obtained solution in a specific ratio. After the composition prepared as above is filtered by a filter having a pore size of 5 μm or the like, it can also be used.
Examples of the aqueous solvent include water-soluble solvents such as water and alcohol.

The intermediate layer forming composition is applied onto the temporary support and dried, whereby the intermediate layer can be easily formed on the temporary support.
The coating method is not particularly limited, and it can be applied by a known method such as slit coating, spin coating, curtain coating, or inkjet coating.
Further, after forming another layer (for example, a thermoplastic resin layer or the like) to be described later on the temporary support, the intermediate layer can be applied.

<Photosensitive layer>
The photosensitive transfer material of the present invention has a temporary support, an intermediate layer, and a photosensitive layer in this order.
Further, the photosensitive layer in the present invention may be a positive photosensitive layer or a negative photosensitive property.
In the case of a positive photosensitive layer, the photosensitive layer is preferably a chemically amplified positive photosensitive layer.
The photoacid generator such as the onium salt and the sulfonate compound described later is protected by an acid generated by inductively active radiation (actinic ray) as a catalyst for an acid group having an acid group which is protected by acid decomposition. Since the deprotection of the acid group functions, the acid generated by the action of one photon contributes to a plurality of deprotection reactions, and the quantum yield exceeds 1, for example, a value as large as a number of 10, as a so-called As a result of the chemical increase, high sensitivity can be obtained.
On the other hand, in the case where a bismuth compound (NQD) is used as a photoacid generator for inducing active radiation, a carboxyl group is formed by a chain photochemical reaction, but the quantum yield must be 1 or less, and does not conform to Chemical amplification type.

In the case where the photosensitive layer is a positive photosensitive layer, it is preferable that the photosensitive layer contains a binder and a photoacid generator from the viewpoint of pattern formability. Moreover, it is preferable that the binder contains a binder having an acid group protected by an acid-decomposable group, and a polymer containing a constituent unit having an acid group which is protected by acid decomposition is more preferable from the viewpoint of pattern formability. good.
In the case where the photosensitive layer is a negative photosensitive layer, it is preferable that the photosensitive layer contains an acid group-containing binder, a polymerizable compound, and a photopolymerization initiator from the viewpoint of pattern formation properties.

- a polymer component comprising a polymer having a constituent unit having an acid group which is protected by acid decomposition -
The photosensitive layer contains a polymer (also referred to as "specific polymer") containing a constituent unit (also referred to as "constituted unit A") having an acid group protected by acid decomposition.
Further, the photosensitive layer may contain other polymers in addition to the polymer constituting the unit A. In the present invention, the polymer having the constituent unit A and other polymers are collectively referred to as "polymer component".
The specific polymer is subjected to a deprotection reaction to form an acid group by the action of an acidic substance which is caused by an amount of a catalyst generated by exposure, and which has an acid group which is protected by acid decomposition in a specific polymer. By the acid group, a hardening reaction can be performed.
Hereinafter, a preferred aspect of the constituent unit A will be described.

The photosensitive layer may further contain a polymer other than a polymer having a constituent unit containing an acid group decomposed by acid decomposition.
Further, it is preferable that all of the polymers contained in the polymer component are at least a polymer having a constituent unit containing an acid group described later.
Further, the photosensitive layer may further contain a polymer other than the above. The above polymer component in the present invention is intended to include other polymers which are added as needed unless otherwise specified. Further, the compound corresponding to the crosslinking agent and the dispersing agent described later is a compound which is not contained in the polymer component even if it is a polymer compound.

A specific polymer-based addition polymerization type resin is preferable, and a polymer having a constituent unit derived from (meth)acrylic acid or an ester thereof is more preferable. Further, in addition to the constituent unit other than the constituent unit derived from (meth)acrylic acid or an ester thereof, for example, a constituent unit derived from styrene or a constituent unit derived from a vinyl compound may be used.

The photosensitive layer contains, as the polymer component, a polymer having the constituent unit A1 represented by the following formula A1 as the constituent unit A, from the viewpoint of suppressing the deformation of the pattern shape, the solubility in the developer, and the transfer property. In addition, it is preferable that the photosensitive resin composition contains a specific polymer having the structural unit A1 represented by the following formula A and having a glass transition temperature of 90 ° C or less as a polymer component, and the above-mentioned photosensitive property. Further, the resin composition is further preferably a polymer component having a constituent unit A1 represented by the following formula A1 and a constituent unit B having an acid group described later and having a glass transition temperature of 90 ° C or less as a polymer component. .
The specific polymer contained in the photosensitive layer may be one type or two or more types.

<<Composition unit A>>
The polymer component contains a polymer having at least a constituent unit A containing an acid group protected by acid decomposition. The polymer component includes a polymer having the constituent unit A, whereby a chemically amplified positive photosensitive layer having extremely high sensitivity can be used.
The "acid group protected by acid decomposition" in the present invention can be used as an acid group or an acid-decomposable group, and is not particularly limited. As a specific acid group, a carboxyl group and a phenolic hydroxyl group are preferable. Further, as the acid group which is protected by acid decomposition, a group which is relatively easily decomposed by an acid (for example, an ester group protected by a group represented by the formula A1, a tetrahydropyranyl ester group or a tetrahydrofuran ester group) can be used. An aldehyde functional group) or a group which is relatively hard to be decomposed by an acid (for example, a tertiary alkyl group such as a tertiary alkyl group such as a third butyl ester group or a third alkyl carbonate group such as a third butyl carbonate group).
Among these, as the acid-decomposable group, a group having a structure protected by an acetal form is preferred.

<<Composition unit A>>
From the viewpoint of sensitivity and resolution, the constituent unit A having an acid group protected by the acid-decomposable group is preferably a constituent unit A1 represented by the following formula A1.

[Chemical 1]

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

In the case of the R ³¹ or R ³² -alkyl group in the formula A1, an alkyl group having 1 to 10 carbon atoms is preferred. In the case of R ³¹ or R ³² -based aryl, phenyl is preferred. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A1, R ³³ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred.
Further, the alkyl group and the aryl group in R ³¹ to R ³³ may have a substituent.
In the formula A1, R ³¹ or R ³² may be bonded to R ³³ to form a cyclic ether, and R ³¹ or R ³² may be bonded to R ³³ to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferred, and 5 is more preferred.
In the formula A1, X ⁰ represents a single bond or an extended aryl group, and a single bond is preferred. The extended aryl group may have a substituent.
The constituent unit A1 represented by the above formula A1 is a constituent unit having a carboxyl group protected by an acid-decomposable group. Since the specific polymer contains the structural unit A1 represented by the formula A1, the sensitivity at the time of pattern formation is excellent, and the resolution is further excellent.

In the formula A1, R ³⁴ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint of further lowering the Tg of the specific polymer.
More specifically, it is preferable that the constituent unit of the R ³⁴ -based hydrogen atom in the formula A is 20% by mass or more based on the total amount of the constituent units A1 contained in the specific polymer.
In addition, in the structural unit A1, the content (content ratio: mass ratio) of the constituent unit of the R ³⁴ hydrogen atom in the formula A1 can be measured by ¹³ C-nuclear magnetic resonance spectroscopy (NMR) and the peak value calculated by a usual method. The intensity ratio of the strength is confirmed.

In the structural unit A1 represented by the formula A1, the constituent unit represented by the following formula A2 is more preferable from the viewpoint of further improving the sensitivity at the time of pattern formation.

[Chemical 2]

In the 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 the formula A2, a R ³⁴ -based hydrogen atom is preferred.
In the formula A2, a hydrogen atom of R ³⁵ to R ⁴¹ is preferred.

A preferred specific example of the structural unit A1 having a carboxyl group protected by an acid-decomposable group represented by the formula A1 can be exemplified as the following constituent unit. Further, R ³⁴ represents a hydrogen atom or a methyl group.

[Chemical 3]

In addition, as the constituent unit A, a constituent unit represented by the following formula A3 is preferable from the viewpoint of suppressing deformation of the pattern shape.

[Chemical 4]

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

In the formula A3, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ^B1 or R ^B2 is an aryl group, a phenyl group is preferred. It is preferred that R ^B1 and R ^B2 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A3, R ^B3 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred.
Further, the alkyl group and the aryl group in R ^B1 to R ^B3 may have a substituent.
In the formula A3, R ^B1 or R ^B2 and R ^B3 may be bonded to form a cyclic ether, and R ^B1 or R ^B2 may be bonded to R ^B3 to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferred, and 5 is more preferred.
In the formula A3, X ^B represents a single bond or a divalent linking group, a single bond or an alkyl group, -C(=O)O-, -C(=O)NR ^N -, -O- or these combinations are Preferably, a single button is preferred. The alkylene group may be linear, may have a branched chain, may have a cyclic structure, or may have a substituent. The carbon number of the alkylene group is preferably from 1 to 10, more preferably from 1 to 4. When X ^B contains -C(=O)O-, it is preferred that the carbon atom contained in -C(=O)O- is directly bonded to the carbon atom bonded to R ^B4 . When X ^B contains -C(=O)NR ^N -, it is preferred that the carbon atom contained in -C(=O)NR ^N - is directly bonded to the carbon atom bonded to R ^B4 . R ^N represents an alkyl group or a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydrogen atom is preferred, and a hydrogen atom is more preferred.
In the formula A3, a group containing R ^B1 to R ^B3 and X ^B are preferably bonded to each other in the para position.
In the formula A3, R ^B12 represents a substituent, and an alkyl group or a halogen atom is preferred. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
In the formula A3, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

In the formula A3, R ^B4 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint of being able to further lower the Tg of the specific polymer.
More specifically, it is preferable that the constituent unit of the R ^B4 -based hydrogen atom in the formula A3 is 20% by mass or more based on the total content of the constituent unit A contained in the specific polymer.
Further, in the structural unit A, the content (content ratio: mass ratio) of the constituent unit of the R ^B4 -based hydrogen atom in the formula A3 can be determined by ¹³ C-nuclear magnetic resonance spectroscopy (NMR) and the peak value calculated by a usual method. The intensity ratio of the strength is confirmed.

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

[Chemical 5]

In the formula A4, R ^B4 represents a hydrogen atom or a methyl group, and 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 represents an integer of 0 to 4.
In the formula A4, a R ^B4 -based hydrogen atom is preferred.
In the formula A4, a hydrogen atom of R ^B5 to R ^B11 is preferred.
In the formula A4, R ^B12 represents a substituent, and an alkyl group or a halogen atom is preferred. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
In the formula A4, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

As a preferable specific example of the structural unit A4 represented by Formula A4, the following structural unit can be exemplified. Further, R ^B4 represents a hydrogen atom or a methyl group.

[Chemical 6]

The constituent unit A included in the specific polymer may be one type or two or more types.
The content of the constituent unit A in the specific polymer is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, even more preferably 30% by mass to 70% by mass, based on the total mass of the specific polymer. .
The content (content ratio: mass ratio) of the constituent unit A in the specific polymer can be confirmed by the intensity ratio of the peak intensity measured by ¹³ C-NMR and calculated by a usual method.
Further, after all the polymer components are decomposed into constituent units (monomer units), the ratio of the constituent unit A is preferably 5% by mass to 80% by mass based on the total mass of the polymer component, and 10% by mass to 80% by mass. More preferably, 30% by mass to 70% by mass is particularly preferred.

<<constitution unit B>>
It is preferred that the above specific polymer contains the constituent unit B having an acid group.
The constituent unit B is a protecting group, and is, for example, an acid group protected by an acid-decomposable group, that is, a constituent unit containing an acid group having no protecting group. When the specific polymer contains the constituent unit B, the sensitivity at the time of pattern formation is good, and it is easily dissolved in the alkaline developing solution in the development step after the pattern exposure, and the development time can be shortened.
The acid group in the present specification means a proton dissociative group having a pKa of 12 or less. The acid group is usually incorporated into the polymer using a monomer capable of forming an acid group as a constituent unit (constituting unit B) containing an acid group. From the viewpoint of improving the sensitivity, the acid group has a pKa of 10 or less, more preferably 6 or less. Further, the acid group has a pKa system of -5 or more.

The specific polymer contains the constituent unit B which constitutes the unit A and the acid group which is not protected by the protective group as a copolymerization component, and by setting the glass transition temperature to 90 ° C or lower, the positive photosensitive layer containing the specific polymer will be transferred. The printability and the peeling property from the temporary support are maintained at a good level, and the resolution and sensitivity at the time of pattern formation are further improved.

The acid group may, for example, be a carboxyl group, a sulfonylamino group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group (phenolic hydroxyl group) or a sulfonyl iminoimine 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 preferred.
The introduction of a constituent unit having an acid group into a specific polymer can be carried out by copolymerizing a monomer having an acid group.
The constituent unit containing the acid group as the constituent unit B is a constituent unit derived from a structural unit derived from styrene or a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth)acrylic acid. Better.

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

The constituent unit B contained in the specific polymer may be one type or two or more types.
It is preferable that the specific polymer contains 0.1% by mass to 20% by mass of the constituent unit having an acid group (constituting unit B), and more preferably 0.5% by mass to 15% by mass, based on the total mass of the specific polymer. The mass % to 10% by mass is further preferably. When it is in the above range, the pattern formability is further improved.
The content (content ratio: mass ratio) of the constituent unit B in the specific polymer can be confirmed by measuring the intensity ratio of the peak intensity calculated by the usual method from ¹³ C-NMR.

<<Other components>>
The specific polymer may include other constituent units (hereinafter, sometimes referred to as constituent unit C) in addition to the constituent unit A and the constituent unit B described above, insofar as the effect of the photosensitive transfer material of the present invention is not impaired. .).
The monomer forming the constituent unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, and aryl (meth)acrylates. , unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated Dicarboxylic anhydride, a group having an aliphatic cyclic skeleton, and other unsaturated compounds.
By using the constituent unit C, at least one of the type and the content can be adjusted, whereby various characteristics of the specific polymer can be adjusted. In particular, by appropriately using the constituent unit C, the Tg of the specific polymer can be easily adjusted to 90 ° C or lower.
The specific polymer may contain only one type of constituent unit C, or may contain two or more types.

Specifically, the constituent unit C can be exemplified by styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, ethoxylated styrene, methoxystyrene, and ethoxybenzene. Ethylene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylate Isopropyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobutyl (meth)acrylate, acrylonitrile or polyethylene glycol A constituent unit formed by acetonitrile acetate mono(meth)acrylate or the like. Further, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be cited.

Further, as the constituent unit C, from the viewpoint of improving the electrical characteristics of the obtained transfer material, a constituent unit having an aromatic ring or a constituent unit having an aliphatic cyclic skeleton is preferable. Specific examples of the monomer forming the constituent unit include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, and dicyclopentanyl (meth)acrylate. Cyclohexyl (meth)acrylate, isoindole (meth) acrylate, benzyl (meth) acrylate, and the like. Among them, as the constituent unit C, a constituent unit derived from cyclohexyl (meth)acrylate is preferred.

Further, as the monomer forming the constituent unit C, for example, an alkyl (meth)acrylate is preferable from the viewpoint of adhesion. Among them, from the viewpoint of adhesion, an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. ester.

The content of the constituent unit C is preferably 70% by mass or less based on the total mass of the specific polymer, more preferably 60% by mass or less, and still more preferably 50% by mass or less. The lower limit value may be 0% by mass, preferably 1% by mass or more, more preferably 5% by mass or more. When it is in the above range, the resolution and the adhesion are further improved.

From the viewpoint of optimizing the solubility with respect to the developer and the physical properties of the photosensitive layer, it is preferred that the specific polymer contains a constituent unit of the ester having the acid group in the above-mentioned structural unit B as the constituent unit C.
Among them, the specific polymer includes a constituent unit having a carboxylic acid group as the constituent unit B, and further includes a constituent unit C having a carboxylate group as a copolymerization synthesis, and for example, includes a constituent unit B derived from (meth)acrylic acid. Further, a polymer of the structural unit (c) derived from cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or n-butyl (meth)acrylate is more preferable.
Hereinafter, preferred examples of the specific polymer in the present invention are given, but the present invention is not limited to the following examples. In addition, the ratio of the structural unit and the weight average molecular weight in the following exemplified compounds can be appropriately selected in order to obtain preferable physical properties.

[Chemistry 7]

<<The glass transition temperature of the polymer: Tg>>
The specific polymer glass transition temperature (Tg) in the present invention is preferably 90 ° C or lower. The Tg is 90 ° C or less, whereby the photosensitive layer has high adhesion and is more excellent in transferability.
The Tg is preferably 60 ° C or lower, and more preferably 40 ° C or lower.
Further, the lower limit of the Tg is not particularly limited, but is preferably -20 ° C or higher, more preferably -10 ° C or higher. When the Tg of the specific polymer is -20 ° C or higher, good pattern formation property is maintained, and when a cover film is used, for example, the peeling property at the time of peeling off the cover film is suppressed.
Further, from the viewpoint of transferability, the glass transition temperature (Tg) of the entire polymer component in the present invention is preferably 90 ° C or less, more preferably 60 ° C or less, and still more preferably 40 ° C or less.

The glass transition temperature of the polymer can be determined using a differential scanning calorimeter (DSC).
The specific measurement method is carried out in the order of the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature in the present specification uses an extrapolated glass transition start temperature (hereinafter, sometimes referred to as Tig).
The method for measuring the glass transition temperature will be more specifically described.
When the glass transition temperature is determined, the device is held at a temperature lower than the Tg of the expected polymer by about 50 ° C until stable, and then heated at a heating rate of 20 ° C / min to a temperature higher than the temperature at which the glass transition is completed. Temperature of 30 ° C and depict DTA curve or DSC curve.
The extrapolation glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line extending along the high temperature side of the reference line on the low temperature side in the DTA curve or the DSC curve, and a stepwise change portion in the glass transition. The gradient of the curve becomes the temperature at the intersection of the tangent to the largest point.

As a method of adjusting the Tg of the polymer to a preferred range as described above, for example, it is possible to control the Tg of the homopolymer of each constituent unit of the target polymer and the FOX formula by the mass ratio of each constituent unit. The Tg of the specific polymer as the target.
About FOX,
The Tg of the homopolymer of the first constituent unit contained in the polymer is Tg1, the mass fraction in the copolymer of the first constituent unit is W1, and the Tg of the homopolymer of the second constituent unit is set. When Tg2 and the mass fraction in the copolymer of the second structural unit are W2, Tg0(K) of the copolymer including the first structural unit and the second structural unit can be estimated by the following formula.
FOX type: 1/Tg0=(W1/Tg1)+(W2/Tg2)
By using the FOX formula described above, the type and mass fraction of each constituent unit contained in the copolymer can be adjusted to obtain a copolymer having a desired Tg.
Further, the Tg of the polymer can also be adjusted by adjusting the weight average molecular weight of the polymer.

<<Molecular weight of polymer: Mw>>
The molecular weight of the specific polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. 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 lower) can be achieved when bonding to the substrate.
Further, the weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
Further, the weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device, and the contents and measurement techniques of the device are well known to those skilled in the art. .
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark)-8220GPC (manufactured by TOSOH CORPORATION) is used as the measuring device, and each TSKgel (registered trademark) Super is used in series. HZM-M (4.6 mmID × 15 cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6 mmID × 15 cm, manufactured by TOSOH CORPORATION), Super HZ3000 (4.6 mmID × 15 cm, manufactured by TOSOH CORPORATION), Super HZ2000 (4.6 mmID × 15) The column of cm and TOSOH CORPORATION can be used as an eluent, and THF (tetrahydrofuran) can be used.
In addition, as a measurement condition, the sample concentration was 0.2% by mass, the flow rate was 0.35 ml/min, the sample injection amount was 10 μl, and the measurement temperature was 40° C. RI) detector to carry out.
The calibration curve can utilize "standard sample TSK standard, polystyrene" by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A Manufactured from any of the 7 samples of -2500" and "A-1000".

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

<<Manufacturing method of specific polymer>>
The production method (synthesis method) of the specific polymer is not particularly limited. However, as an example, the polymerizable monomer for forming the structural unit A1 represented by Formula A is used to form an acid group. The polymerizable monomer constituting the unit B and, if necessary, an organic solvent containing a polymerizable monomer for forming another constituent unit C, can be synthesized by polymerization using a polymerization initiator. Moreover, it can also be synthesized by a so-called polymer reaction.

The photosensitive layer in the present invention preferably contains the polymer component in a ratio of 50% by mass to 99.9% by mass based on the total solid content of the photosensitive layer in view of the adhesion of the substrate to the photosensitive layer. The ratio of the mass% to 98% by mass is more preferably the above polymer component.
Further, from the viewpoint of exhibiting good adhesion to the substrate, the photosensitive layer preferably contains the specific polymer in a ratio of 50% by mass to 99.9% by mass based on the total solid content of the photosensitive layer, and is preferably 70% by mass. The ratio of % to 98% by mass is more preferably the above specific polymer.

<<Other polymers>>
In the photosensitive layer, the polymer component may contain a constituent unit (a) not represented by Formula A, in addition to the specific polymer, insofar as the effect of the photosensitive transfer material of the present invention is not impaired. Polymer (sometimes referred to as "other polymers"). 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, and still more preferably 20% by mass or less.

The photosensitive layer may contain only one type of other polymer, or may contain two or more types, in addition to a specific polymer.
As the other polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, Sartomer Company, Inc.), ARUFON can also be used. UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (above, manufactured by TOAGOSEI CO., LTD.) and Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (above, BASF company).

- Photoacid generator -
The photosensitive layer contains a photoacid generator.
The photoacid generator used in the present invention is a compound capable of generating an acid by irradiation of radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present invention is preferably a compound having a wavelength of 300 nm or more, preferably an actinic ray having a wavelength of 300 nm to 450 nm, which generates an acid, and the chemical structure thereof is not limited. In addition, a photoacid generator that does not directly induce an actinic ray having a wavelength of 300 nm or more can be used as a compound which generates an acid by using an actinic ray having a wavelength of 300 nm or more and a sensitizer. The sensitizer is preferably used after combination.
The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, and more preferably a photoacid generator which produces an acid having a pKa of 3 or less, and has a pKa of 2 or less. The acid photoacid generator is particularly preferred. The lower limit of pKa is not particularly limited, and for example, it is preferably -10.0 or more.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
In addition, as the photo-acid generator, a compound containing at least one selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound to be described later is preferable, and includes ruthenium. The sulfonate compound is more preferred.

Examples of the nonionic photoacid generator include a trichloromethyl-s-triazine, a diazomethane compound, a quinone imide sulfonate compound, and an anthracene sulfonate compound. Among these, a photoacid generator-based sulfonate compound is preferable from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used alone or in combination of two or more. Specific examples of the trichloromethyl-s-triterpenoids and the diazomethane derivatives are exemplified by the compounds described in paragraphs 0003 to 088 of JP-A-2011-221494.

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

[化8]

In the formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site with other atoms or other groups.

The compound having the oxime sulfonate structure represented by the formula (B1) may be substituted for all the groups, and the alkyl group in R ²¹ may be linear or branched, and may have a ring structure. Hereinafter, the permissible substituents will be described.
As the alkyl group of R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferred. The alkyl group of R ²¹ may be bridged by an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including 7,7-dimethyl-2-oxonorbornyl group). An alicyclic group, preferably a bicycloalkyl group, or the like, or a halogen atom.
As the aryl group of R ^{21 ,} an aryl group having 6 to 18 carbon atoms is preferred, and a phenyl group or a naphthyl group is more preferred. 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 an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-085643.

Examples of the ionic photoacid generator include an onium salt compound such as a diarylsulfonium salt and a triarylsulfonium salt, and a quaternary ammonium salt. Among these, an onium salt compound is preferred, and a triarylsulfonium salt and a diarylsulfonium salt are particularly preferred.

As the ionic photoacid generator, an ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-085643 can be preferably used.

The photoacid generator may be used singly or in combination of two or more.
The content of the photoacid generator in the photosensitive layer is preferably 0.1% by mass to 10% by mass, and preferably 0.5% by mass to 5% by mass, based on the total mass of the photosensitive layer, from the viewpoint of sensitivity and resolution. good.

- Polymeric compound -
It is preferred that the photosensitive layer contains a polymerizable compound.
As the polymerizable compound, an ethylenically unsaturated compound is preferred.
The ethylenically unsaturated compound contributes to the photosensitivity (that is, photocurability) of the photosensitive layer and the strength of the cured film.
Further, the ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.

It is preferred that the photosensitive layer contains a bifunctional or higher ethylenically unsaturated compound as the ethylenically unsaturated compound.
Here, the bifunctional or higher ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group, a (meth) acrylonitrile group is more preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferred.

The photosensitive layer contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher ethyl group from the viewpoint of further improving the wet heat resistance after the brine to be applied to the cured film. An unsaturated compound (preferably a trifunctional or higher (meth) acrylate compound) is particularly preferred.

The bifunctional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and 1,9-nonanediol di(a). Acrylate, 1,6-hexanediol di(meth)acrylate, and the like.
As a bifunctional ethylenically unsaturated compound, a tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol Methacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1, 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) or the like can be mentioned.

The trifunctional or higher ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.
Examples of the trifunctional or higher ethylenically unsaturated compound include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate and neopentyl alcohol (tri/tetra) (meth) acrylate. , trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, iso-cyanuric acid (meth) acrylate, triglyceride (meth) acrylate skeleton (meth) acrylate compound and the like.

Among them, "(three/four/five/six) (meth) acrylate" contains tris(meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (methyl) The concept of acrylate, "(tri/tetra) (meth) acrylate" is a concept comprising tris(meth) acrylate and tetra (meth) acrylate.

Further, as the ethylenically unsaturated compound, a caprolactone-modified compound of a (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20, manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. . A-9300-1CL, etc., alkylene oxide modified compound of (meth) acrylate compound (KAYARAD RP-1040, manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. ATM-35E, A-9300, EBECRYL (registered trademark) 135, manufactured by DAICEL-ALLNEX LTD., ethoxyglycerin triacrylate (A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd., etc.) Wait.

The ethylenically unsaturated compound may also be an amine ester (meth) acrylate compound (preferably a trifunctional or higher amine ester (meth) acrylate compound).
Examples of the trifunctional or higher amine ester (meth) acrylate compound include 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO, LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA. -1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.) or the like.

Moreover, it is preferable that the ethylenically unsaturated compound contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability and improving wet heat resistance after application of the cured film brine.
Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group, and a carboxyl group is preferred.
Examples of the ethylenically unsaturated compound having an acid group include a 3- to 4-functional ethylenically unsaturated compound (neopentitol tetraacrylate and neopentyltetraol tetraacrylate (PETA) having a carboxyl group introduced into an acid group. Skeleton (acid value = 80 mgKOH/g to 120 mgKOH/g)), introducing a carboxyl group into a 5- to 6-functional ethylenically unsaturated compound having an acid group (dipentaerythritol pentaacrylate and dipentaerythritol) A hexaacrylate (DPHA) skeleton (acid value = 25 mgKOH/g to 70 mgKOH/g)).
The trifunctional or higher ethylenically unsaturated compound having such an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group as needed.

The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxyl group and a carboxylic acid anhydride. Thereby, the wet heat resistance after the hardened film brine is applied is improved.
The bifunctional or higher ethylenically unsaturated compound having a carboxyl group is not particularly limited, and can be appropriately selected from known compounds.
For example, ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) can be preferably used as the ethylenically unsaturated compound having a carboxyl group-containing bifunctional or higher functional group. ) or ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

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

The weight average molecular weight (Mw) of the polymerizable compound used in the present invention is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200.
Further, in the polymerizable compound used in the photosensitive layer, the content of the polymerizable compound having a molecular weight of 300 or less is preferably 30% by mass or less based on 30% by mass or less of all the ethylenically unsaturated compound contained in the photosensitive layer. The mass% or less is more preferably 20% by mass or less.

One type of the polymerizable compound may be used alone or two or more types may be used in combination.
The content of the polymerizable compound in the photosensitive layer is preferably from 1% by mass to 70% by mass, more preferably from 10% by mass to 70% by mass, and particularly preferably from 20% by mass to 60% by mass based on the total mass of the photosensitive layer. More preferably, 20% by mass to 50% by mass is particularly preferable.

Further, when the photosensitive layer contains a bifunctional ethylenically unsaturated compound and a trifunctional or higher ethylenically unsaturated compound, a bifunctional ethylenically unsaturated compound is added to all of the ethylenically unsaturated compounds contained in the photosensitive layer. The content is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, still more preferably 30% by mass to 80% by mass.
In this case, the content of the trifunctional or higher ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, and preferably 15% by mass based on the total amount of the ethylenically unsaturated compound contained in the photosensitive layer. More preferably, 80% by mass is more preferably 20% by mass to 70% by mass.
In this case, the content of the bifunctional or higher ethylenically unsaturated compound is 40% by mass or more and less than 100 based on the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher ethylenically unsaturated compound. The mass % is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.

Further, when the photosensitive layer contains a bifunctional or higher ethylenically unsaturated compound, the photosensitive layer may further contain a monofunctional ethylenically unsaturated compound.
In the case where the photosensitive layer contains a bifunctional or more ethylenically unsaturated compound, among the ethylenically unsaturated compounds contained in the photosensitive layer, a bifunctional or higher ethylenically unsaturated compound-based main component is preferable.
Specifically, when the photosensitive layer contains a bifunctional or higher ethylenically unsaturated compound, the content of the bifunctional or higher ethylenically unsaturated compound is 60 based on the total content of the ethylenically unsaturated compound contained in the photosensitive layer. The mass % to 100% by mass is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass.

Further, when the photosensitive layer contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or more ethylenically unsaturated compound having a carboxyl group or a carboxylic anhydride thereof), it has an acid group-containing ethyl group with respect to the photosensitive layer. The content of the unsaturated compound is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 20% by mass, even more preferably from 1% by mass to 10% by mass.

- adhesive with acid group -
It is preferred that the photosensitive layer contains a binder having an acid group.
As the binder having an acid group, an alkali-soluble resin is preferred.
Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group.
Among them, as the acid group, a carboxyl group is preferred.
The acid value of the binder having the acid group is not particularly limited, and from the viewpoint of alkali developability, an alkali-soluble resin having an acid value of 60 mgKOH/g or more is preferable, and a carboxyl group having an acid value of 60 mgKOH/g or more is preferable. The acrylic resin is particularly good.
The binder having an acid group has the above acid value, whereby it is presumed that it is thermally crosslinked with a compound which can be reacted by heating with an acid, and the three-dimensional crosslinking density can be improved. Further, it is presumed that the carboxyl group of the carboxyl group-containing acrylic resin is anhydrous and hydrophobized, thereby contributing to improvement in wet heat resistance.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more (hereinafter sometimes referred to as a specific polymer A) is not particularly limited as long as the acid value is satisfied, and a known resin can be appropriately selected.
For example, as the specific polymer A in the present invention, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more in the polymer described in paragraph 0025 of JP-A-2011-095716 can be preferably used. An alkali-soluble resin, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of JP-A-2010-237589.
Here, the (meth)acrylic resin means a resin containing at least one of a constituent unit derived from (meth)acrylic acid and a constituent unit derived from (meth)acrylic acid ester.
The total ratio of the constituent unit derived from (meth)acrylic acid and the constituent unit derived from (meth)acrylic acid in the (meth)acrylic resin is preferably 30 mol% or more, and more preferably 50 mol% or more. good.

The copolymerization ratio of the monomer having a carboxyl group in the specific polymer A is preferably from 5% by mass to 50% by mass, more preferably from 10% by mass to 40% by mass, even more preferably 100% by mass based on the polymer. 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, an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl anthracene compound, an aldehyde compound, a hydroxyl group may be mentioned. The base compound, the carboxylic anhydride, and the like are reacted with a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an etidinyl group, a sulfonic acid or the like.
As the specific polymer A, the compound A shown below is preferred. Further, the content ratio of the structural unit shown below can be appropriately changed depending on the purpose.

[Chemistry 9]

From the viewpoint of alkali developability, the acid value of the acid group-containing binder used in the present invention is preferably 60 mgKOH/g to 200 mgKOH/g, and more preferably 60 mgKOH/g to 150 mgKOH/g. Further, 60 mgKOH/g to 110 mgKOH/g is further preferred.
In the present specification, the acid value is a value measured in accordance with the method described in JIS K0070 (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.

Further, in addition to the specific polymer A described above, the binder having the acid group described above can be appropriately selected and used depending on the purpose. For example, a polyhydroxystyrene resin, a polyimide resin, a polybenzoxazole resin, a polyoxyalkylene resin, or the like can be preferably used.

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

-Photopolymerization initiator -
It is preferred that the photosensitive layer contains a photopolymerization initiator. The photopolymerization initiator receives actinic rays such as ultraviolet rays and visible rays to initiate polymerization of an ethylenically unsaturated compound.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
As a photopolymerization initiator, a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as "an oxime photopolymerization initiator"), a photopolymer having an α-aminoalkylphenone structure An initiator (hereinafter also referred to as "α-aminoalkylphenone photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as " a ?-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having a mercaptophosphine oxide structure (hereinafter also referred to as "mercaptophosphine oxide-based photopolymerization initiator"), A photopolymerization initiator of N-phenylglycine (hereinafter also referred to as "N-phenylglycine acid photopolymerization initiator").

The photopolymerization initiator comprises a photopolymerization initiator selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, an α-hydroxyalkylphenone polymerization initiator, and N-phenylglycine. At least one of the group consisting of a photopolymerization initiator is preferably selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, and N-phenylglycine. At least one of the groups consisting of photopolymerization initiators is more preferred.

In addition, as the photopolymerization initiator, for example, a polymerization initiator described in paragraphs 0031 to 0044 of JP-A-2011-095716 and paragraphs 0064 to 0081 of JP-A-2015-014783 can be used.

As a commercial product of a photopolymerization initiator, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzamide) (product name: IRGACURE ( Registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzhydrazide)-9H-indazol-3-yl]ethanone-1-(O-B醯基肟) (product name: IRGACURE OXE-02, manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4 - Oral phenyl) phenyl]-1-butanone (product name: IRGACURE 379EG, manufactured by BASF Corporation), 2-methyl-1-(4-methylthiophenyl)-2-indolyl propane 1-ketone (product name: IRGACURE 907, manufactured by BASF Corporation), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)diphenylethylenedione]phenyl} -2-methylpropan-1-one (product name: IRGACURE 127, manufactured by BASF Corporation), 2-diphenylethylenedione-2-dimethylamino-1-(4-normanolinylphenyl) - Butanone-1 (product name: IRGACURE 369, manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: IRGACURE 1173, manufactured by BASF Corporation), 1-hydroxyl Cyclohexyl phenyl ketone (product name: IRGACURE 184, manufactured by BASF Corporation), 2, 2 -Dimethoxy-1,2-diphenylethane-1-one (product name: IRGACURE 651, manufactured by BASF Corporation), an oxime ester type (product name: Lunar 6, manufactured by DKSH Japan), 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, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more based on the total mass of the photosensitive layer. good.
Further, the content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less based on the total mass of the photosensitive layer.

-Other additives -
In addition to the above components, the photosensitive layer in the present invention may further contain a known additive.

[Surfactant]
From the viewpoint of film thickness uniformity, it is preferred that the photosensitive layer contains a surfactant. As the surfactant, any of an anionic, cationic, nonionic (Nonionic) or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and polyoxyn oxide systems. Fluorine surfactant. In the following product names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by JEMCO CORPORATION), and MEGAFACE (DIC Corporation Co., Ltd.), FLUORAD (manufactured by Sumitomo 3M Limited), ASAHI GUARD, SURFLON (manufactured by ASAHI GLASS CO., LTD.), POLYFOX (manufactured by OMNOVA Solutions Inc.), and SH-8400 (manufactured by Dow Corning Toray Co., Ltd.) ) and other series.
Further, the surfactant A includes the constituent unit A and the constituent unit B represented by the following formula I-1, and a preferred example thereof is gel permeation chromatography using tetrahydrofuran (THF) as a solvent. The polystyrene-equivalent weight average molecular weight (Mw) measured by the method is a copolymer of 1,000 or more and 10,000 or less.

[化10]

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

L is preferably a branched alkyl group represented by the following formula (I-2). R ⁴⁰⁵ in the formula (I-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and an alkyl group having 1 or more and 3 or less carbon atoms from the viewpoint of compatibility and wettability with respect to the surface to be coated. Preferably, an alkyl group having 2 or 3 carbon atoms is more preferred. The sum of p and q (p+q) is preferably p+q=100, that is, 100% by mass.

[11]

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

In addition, the surfactant described in paragraphs 0060 to 0071 of JP-A-4502784 and JP-A-2009-237362 can also be used.

The surfactant may be used singly or in combination of two or more.
The amount of the surfactant to be added is preferably 10% by mass or less based on the total mass of the photosensitive layer, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 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, a morphine, a morphine or a 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 based on the total mass of the photosensitive layer, and more preferably 0.01% by mass to 1% by mass, and 0.01% by mass. From % to 0.8% by mass is further preferred.

[solvent]
The above photosensitive layer may contain a solvent.
In addition, in order to facilitate the formation of the photosensitive layer, the photosensitive resin composition forming the photosensitive layer temporarily contains a solvent to adjust the viscosity of the photosensitive resin composition, and the photosensitive resin composition containing the solvent is applied and dried. The above photosensitive layer is preferably formed.
As the solvent used in the present invention, a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, and propylene glycol. Alkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl groups Ether acetates, esters, ketones, guanamines and lactones. Moreover, as a specific example of the solvent, the solvent described in paragraphs 0174 to 0178 of JP-A-2011-221494 can be cited, and the contents are incorporated in the present specification.

Further, according to requirements, benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone can be added to the solvent described. , caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or A solvent such as propylene carbonate.
The solvent may be used alone or in combination of two or more.
The solvent which can be used in the present invention can be used singly or in combination of two. When two or more types of solvents are used, for example, a combination of a propylene glycol monoalkyl ether acetate and a dialkyl ether, a diacetate and a diethylene glycol dialkyl ether, or an ester and a butyl group. The use of a glycol alkyl ether acetate is preferred.

Further, as the solvent, 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 is preferred.
Examples of the solvent having a boiling point of 130 ° C or more and less than 160 ° C include propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monoethyl ether acetate (boiling point: 158 ° C), and propylene glycol methyl-n-butyl ether (boiling point 155). °C) and propylene glycol methyl-n-propyl ether (boiling point 131 ° C).
The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ethyl ether (boiling point: 176 ° C), and 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-butanediol II Acetate (boiling point 232 ° C).

The content of the solvent when the photosensitive resin composition is applied is preferably from 50 parts by mass to 1,900 parts by mass, more preferably from 100 parts by mass to 900 parts by mass, per 100 parts by mass of the total solid content of the photosensitive resin composition. .
In addition, the content of the solvent in the photosensitive layer is preferably 2% by mass or less based on the total mass of the photosensitive resin layer, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less.

[Plasticizer]
The photosensitive layer may contain a plasticizer for the purpose of improving plasticity.
The weight average molecular weight of the above plasticizer is preferably less than the weight average molecular weight of the 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 compatible with a specific polymer and exhibits plasticity. However, from the viewpoint of imparting plasticity, it is preferred that the plasticizer has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer has the following structure.

[化12]

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

Further, for example, even a compound having an alkyleneoxy group having the above structure (referred to as "compound X"), a compound X is specifically mixed with a chemically amplified positive photosensitive resin composition formed without the compound X. When the plasticity of the chemically amplified positive photosensitive resin composition obtained by the polymer and the photoacid generator is not improved, the plasticizer which is the present invention is not satisfied. For example, the arbitrarily added surfactant is not generally used in an amount that imparts plasticity to the photosensitive resin composition, and therefore does not conform to the plasticizer as the present specification.

The plasticizing agent may, for example, be a compound having the following structure, but is not limited thereto.

[Chemistry 13]

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

[sensitizer]
The photosensitive layer can further comprise a sensitizer.
The sensitizer absorbs actinic rays and becomes an electronically excited state. The sensitizer that is in an electronically excited state contacts the photoacid generator to generate electron transfer, energy transfer, and heat generation. Thereby, the photoacid generator causes a chemical change to decompose, thereby generating an acid.
The exposure sensitivity can be improved by including a sensitizer.

As a sensitizer, a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a basic styrene derivative, and a stilbene benzene derivative Preferably, the anthracene derivative is more preferred.
As an anthracene derivative, anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromo Preferably, hydrazine, 9-chloropurine, 9,10-dibromofluorene, 2-ethylhydrazine or 9,10-dimethoxyfluorene is preferred.

Examples of the sensitizer include the compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/093271.

The content of the sensitizer is preferably from 0% by mass to 10% by mass based on the total mass of the photosensitive layer, and more preferably from 0.1% by mass to 10% by mass.

[alkaline compound]
It is preferred that the photosensitive layer further contains a basic compound.
The basic compound can be arbitrarily selected from the basic compounds used in the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of such compounds include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-221494, the contents of which are incorporated herein by reference.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and trisole. - n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.
Examples of the aromatic amine 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, and N-. Methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, smoke Alkali, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, anthraquinone, pyrrolidine, piperidine, piperazine, oroproline, 4-methyl mouth Lin, 1,5-dioxabicyclo[4.3.0]-5-pinene and 1,8-dioxabicyclo[5.3.0]-7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, ammonium tetramethylbenzoate, tetra-n-butylammonium acetate, and tetra-n-butylbenzoic acid ammonium.

These 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 based on the total mass of the photosensitive layer, and more preferably 0.005% by mass to 3% by mass.

[Heterocyclic compound]
The photosensitive layer in the present invention can contain a heterocyclic compound.
The heterocyclic compound in the present invention is not particularly limited. For example, a compound having an epoxy group or an oxetanyl group in the molecule, a heterocyclic compound containing an alkoxymethyl group, various other cyclic ethers, and a cyclic ester (lactone) may be added. A nitrogen-containing monomer such as an oxygen monomer, a cyclic amine or an oxazoline, or a heterocyclic monomer having d electrons such as hydrazine, sulfur or phosphorus.

When the heterocyclic compound is added, the amount of the heterocyclic compound in the photosensitive layer is preferably 0.01% by mass to 50% by mass, and preferably 0.1% by mass to 10% by mass based on the total mass of the photosensitive layer. More preferably, 1% by mass to 5% by mass is further more preferable. When it is in the above range, it is preferable from the viewpoint of adhesion and etching resistance. The heterocyclic compound can be used alone or in combination of two or more.

Specific examples of the compound having an epoxy group in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type epoxy resin. Aliphatic epoxy resin, etc.

A compound having an epoxy group in the molecule can be obtained as a commercially available product. For example, commercially available products such as JER 828, JER 1007, JER 157 S70 (manufactured by Mitsubishi Chemical Corporation), JER 157 S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like in paragraph 0189 of JP-A-2011-221494 can be cited.
As other commercial products, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD -1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA CORPORATION), 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-212L, 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 Chemtex Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) CELLOXIDE 2021P , 2081, 2000, 3000, EHPE 3150, EPOLEAD GT400, SERUBINASU B0134, B0177 (manufactured by Daicel Corporation), and the like.
The compound having an epoxy group in the molecule may be used alone or in combination of two or more.

Among the compounds having an epoxy group in the molecule, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and an aliphatic epoxy resin can be more preferably used. A good example is an aliphatic epoxy resin.

Specific examples of the compound having an oxetanyl group in the molecule can be used Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX ( Above, manufactured by TOAGOSEI CO., LTD.).

Further, the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

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

[Alkoxydecane compound]
The photosensitive layer may contain an alkoxydecane compound. As the alkoxydecane compound, a trialkoxydecane compound is preferably exemplified.
Examples of the alkoxydecane compound include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-. Glycidoxypropyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ- Chloropropyltrialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. Among these, γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane is more preferable, γ-glycidoxypropyltrialkoxydecane Further preferably, 3-glycidoxypropyltrimethoxydecane is particularly preferred. These can be used singly or in combination of two or more.

[Other ingredients]
In the photosensitive layer of the present invention, metal oxide particles, an antioxidant, a dispersant, an acid multiplier, a development accelerator, a conductive fiber, a colorant, a thermal radical polymerization initiator, a thermal acid generator, and ultraviolet rays can be added. A known additive such as an absorbent, a tackifier, a crosslinking agent, and an organic or inorganic inhibitor.
The preferred aspect of the other components is described in paragraphs 0015 to 0184 of JP-A-2014-085643, the contents of which are incorporated herein.

- average film thickness of the photosensitive layer -
The average thickness of the photosensitive layer is preferably 1.0 μm or more, more preferably 2.0 μm or more, and even more preferably 5.0 μm or more, from the viewpoint of transferability (layering property). Further, from the viewpoint of production suitability, the average thickness of the photosensitive layer is preferably 20 μm or less, and more preferably 15 μm or less.

- Method of forming photosensitive layer -
The components and the solvent are mixed at an arbitrary ratio and by any method, and stirred and dissolved, whereby a photosensitive resin composition for forming a photosensitive layer can be prepared. For example, it is also possible to prepare a composition by mixing each component as a solution previously dissolved in a solvent and mixing the obtained solution in a specific ratio. After the composition prepared as above is filtered by a filter having a pore size of 0.2 μm or the like, it can also be used.

The photosensitive resin composition is applied onto an intermediate layer and dried, whereby a photosensitive transfer material of the present invention having a photosensitive layer on a temporary support can be obtained.
The coating method is not particularly limited, and it can be applied by a known method such as slit coating, spin coating, curtain coating, or inkjet coating.
Further, it is also possible to apply a photosensitive layer after forming another layer described later on the intermediate layer.

<other layer>
The photosensitive transfer material of the present invention may have a layer other than the temporary support, the intermediate layer, and the photosensitive layer (hereinafter sometimes referred to as "other layer"). As another layer, a contrast enhancement layer, a cover film, a thermoplastic resin layer, etc. are mentioned.

- thermoplastic resin layer, cover film, etc. -
From the viewpoint of transferability, the photosensitive transfer material of the present invention preferably has a thermoplastic resin layer between the temporary support and the intermediate layer.
Further, the photosensitive transfer material of the present invention may further have a cover film for the purpose of protecting the photosensitive layer.
In the preferred embodiment of the thermoplastic resin layer, there is a description of paragraphs 0189 to 0193 of JP-A-2014-085643, and a preferred aspect of the other layer is 0194 of JP-A-2014-085643. Paragraphs ~ 0196, the contents of this bulletin are incorporated in this specification.
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 of the present invention has another layer such as a thermoplastic resin layer, it can be produced in accordance with the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138.
For example, when a photosensitive transfer material of the present invention having a thermoplastic resin layer is produced, a solution (a coating liquid for a thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved is applied onto a temporary support, and After the thermoplastic resin layer is dried, a preparation liquid (intermediate layer composition) prepared by adding a resin and an additive to a solvent in which the thermoplastic resin layer is not dissolved is applied onto the obtained thermoplastic resin layer, and dried to laminate an intermediate layer. Further, a photosensitive resin composition prepared by using a solvent which does not dissolve the intermediate layer is applied to the formed intermediate layer, and dried to laminate a photosensitive layer, whereby the photosensitive transfer material of the present invention can be preferably produced. .

- Contrast enhancement layer -
The photosensitive transfer material of the present invention can have a contrast enhancement layer in addition to the above-mentioned photosensitive layer.
Contrast Enhancement Layer (CEL) contains a material that absorbs relatively large relative to the exposure wavelength before exposure but absorbs gradually with exposure, that is, a material having a high light transmittance (referred to as a photodecolorizing pigment component). Layer. As the photodecolorizing dye component, a diazonium salt, a phosphonium salt, an aryl nitroso salt or the like is known. As the film forming component, a phenol resin or the like can be used.
In addition, as the contrast-enhanced layer, it is possible to use the paragraphs 0004 to 0051 of JP-A-6-097065, paragraphs 0012 to 0055 of JP-A-6-332167, the photosensitive resin manual, and the photosensitive resin exchange meeting. The materials described in the Industrial Investigation Society (1989), Photosensitive Resin, Technology, Yamagata, and Yongsong, NIKKAN KOGYO SHIMBUN, LTD. (1988).

(Resin pattern manufacturing method and wiring manufacturing method)
The method for producing a resin pattern of the present invention is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material of the present invention, and the method includes the side of the photosensitive layer in the photosensitive transfer material of the present invention. a step of bonding the outermost layer to the support; a step of patterning the photosensitive layer; and a step of developing the photosensitive layer exposed by the pattern, after the step of bonding to the support and It is preferred to include a step of peeling off the temporary support before the step of developing the photosensitive layer.
Further, the wiring manufacturing method of the present invention is not particularly limited as long as it is a wiring manufacturing method using the photosensitive transfer material of the present invention, and the method includes the photosensitive layer side in the photosensitive transfer material of the present invention. a step of bonding the outermost layer to the support having the conductive layer on the surface; a step of patterning the photosensitive layer; and developing the patterned photosensitive layer to form a resin pattern; and using the resin pattern as a step of masking and etching the conductive layer; and a step of peeling off the resin pattern, the step of peeling off the temporary support before the step of bonding to the support and before developing the photosensitive layer good.
In the photosensitive transfer material of the present invention, the "outermost layer on the photosensitive layer side" is the outermost layer on the photosensitive layer side of the photosensitive transfer material of the present invention having a temporary support, an intermediate layer, and a photosensitive layer in this order. .
Further, the support is also referred to as a "substrate", and a support having a conductive layer on the surface is also referred to as a "substrate".

Conventionally, the photosensitive resin composition is classified into a negative type which is left as an image by irradiation with a portion of the actinic ray, and a positive type which remains as an image of a portion which is not irradiated with the actinic ray, depending on the difference in the photosensitive system. In the positive type, by irradiating an actinic ray, for example, a sensitizer which generates an acid by irradiation with an actinic ray is used to improve the solubility of the exposed portion, and thus the exposed portion and the unexposed portion are not hardened during pattern exposure. When the pattern shape is poor, the substrate can be reused (rework) by full exposure or the like. Therefore, a positive type is preferable from the viewpoint of excellent secondary workability. Further, only the photosensitive resin layer can realize a technique of re-exposing the remaining photosensitive layer to produce different patterns. Therefore, in the resin pattern producing method of the present invention or the wiring manufacturing method of the present invention, the exposure is performed twice or more.

<Fitting step>
The resin pattern producing method of the present invention or the wiring manufacturing method of the present invention comprises the step of bonding the outermost layer on the photosensitive layer side of the photosensitive transfer material of the present invention to a support or a support having a conductive layer on the surface thereof. (Adhesion step) is preferred.
In the above bonding step, it is preferred to bond the photosensitive transfer material to the support or the substrate having the conductive layer on the surface in contact with each other.
Further, in the bonding step, it is preferable that the conductive layer and the outermost layer on the side of the photosensitive layer are pressure-contacted in contact with each other. According to the above aspect, the photosensitive layer forming the exposed and developed pattern can be preferably used as an etching resist for etching the conductive layer.
The method of pressure-bonding the above-mentioned base material to the above-mentioned photosensitive transfer material is not particularly limited, and a known transfer method and lamination method can be used.
Specifically, for example, it is preferred that the photosensitive layer side of the photosensitive transfer material is superposed on the conductive layer and pressurized by a roll or the like or by pressurization and heating. A known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further improving productivity can be used for the lamination.
The pressure and pressure in the bonding step are not particularly limited, and can be appropriately set depending on the material of the surface of the bonded support, such as the material of the conductive layer and the photosensitive layer, the transport speed, and the crimping machine to be used. . Further, in the case where the coating layer 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 base material is a resin film, the roll-to-roll pressure bonding may be performed.

[support (substrate)]
Regarding the substrate on which a plurality of conductive layers are laminated on the support, a support system glass substrate or a film substrate is preferable, and a film substrate is more preferable. In the case where the wiring manufacturing method of the present invention is a wiring for a touch panel, the sheet-like resin composition of the support system is particularly preferable.
Further, 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 light-transmitting substrate such as a glass substrate, and tempered glass such as GORILLA glass of Corning Incorporated may be used. Further, as the transparent substrate, materials used in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492 can be preferably used.
When a film substrate is used as the substrate, a substrate having no optical strain and a substrate having high transparency are more preferable, and a specific material may be polyethylene terephthalate (PET) or poly. Ethylene naphthalate, polycarbonate, triethyl fluorenyl cellulose, cycloolefin polymer.

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

In the method for producing a resin pattern of the present invention or the method for producing a wiring of the present invention, it is preferred that at least one of the plurality of conductive layers contains a metal oxide.
As the conductive layer, it is preferable to correspond to the electrode pattern of the sensor for the visual recognition portion of the capacitive touch panel or the wiring of the edge take-out portion.

[Substrate for wiring formation]
The substrate for wiring formation used in the present invention is preferably a substrate having a conductive layer on the surface of the substrate. Wiring is formed by patterning a conductive layer. In this embodiment, it is preferred to provide a plurality of conductive layers such as a metal oxide and a metal on a film substrate such as PET.

<Exposure step>
The resin pattern producing method of the present invention or the wiring manufacturing method of the present invention preferably comprises a step of exposing the photosensitive layer to a pattern (exposure step) after the bonding step.
In the above exposure step, it is preferred that the actinic beam or the substrate provided with the coating film is irradiated with actinic rays through a mask having a specific pattern. In this step, the photoacid generator decomposes and produces an acid. The acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to form an acid group such as a carboxyl group or a phenolic hydroxyl group.
In the present invention, the detailed arrangement of the patterns and the specific dimensions are not particularly limited. From the viewpoint of improving the display quality of a display device (for example, a touch panel) having an input device and minimizing the area occupied by the taken-out wiring, at least a part of the pattern (particularly, the electrode pattern of the touch panel and the portion where the wiring is taken out) is 100 μm. The following thin line is preferable, and a thin line of 70 μm or less is more preferable, and the input device has the circuit board manufactured in the present invention.
Further, the exposure in the above-described exposure step may be exposure via a mask, or may be digital exposure using a laser or the like, and exposure by an exposure mask is preferred.
The resin pattern producing method of the present invention or the wiring manufacturing method of the present invention preferably comprises a step of bringing the photosensitive transfer material into contact with the exposure mask between the bonding step and the exposure step. In the above aspect, the resolution of the obtained pattern is more excellent.

Examples of the actinic ray include visible light, ultraviolet light, and electron beam, and visible light or ultraviolet light is preferred, and ultraviolet light is particularly preferred.
As the exposure light source based on the actinic ray, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a light-emitting diode (LED) light source, an excimer laser generating device, or the like can be used, and g-ray (436) can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as nm), i-ray (365 nm), and h-ray (405 nm). Further, the irradiation light can be adjusted via a long-wavelength cut filter, a short-wavelength cut filter, or a spectroscopic filter such as a belt pass filter as needed.
As the exposure device, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity method, a contact, a microlens array, and a laser exposure can be used.
The exposure amount may be appropriately selected depending on the photosensitive layer to be used, preferably 5 mJ/cm ² to 200 mJ/cm ^{2 , more} preferably 10 mJ/cm ² to 100 mJ/cm ² .
Further, for the purpose of improving the rectangularity and linearity of the pattern after the exposure, it is also preferable to carry out heat treatment before development. By the step called so-called PEB (Post Exposure Bake), the roughness of the pattern edge of the standing wave generated in the photosensitive layer at the time of exposure can be reduced.

Further, the pattern exposure may be performed after the temporary support is peeled off from the intermediate layer and the photosensitive layer, or may be exposed through the temporary support before the temporary support is peeled off, and then the temporary support is peeled off. In addition, the pattern exposure may be exposure via a mask, or may be digital exposure using a laser or the like.

<Development step>
The method for producing a resin pattern of the present invention or the method for producing a wiring of the present invention includes a step of developing a pattern by developing the photosensitive layer after the step of exposing (developing step).
Further, in the developing step, the exposed intermediate portion is also removed together with the exposed photosensitive layer.
Further, in the developing step, the intermediate layer of the unexposed portion may be removed in the form of being dissolved or dispersed in the developer.
The development of the exposed photosensitive layer in the above development step can be carried out using a developer.
The developer is not particularly limited as long as the exposed portion of the photosensitive layer can be removed. For example, a known developer such as a developer described in JP-A-2005-072724 can be used. Further, it is preferable that the developer is a developer which can perform a dissolution type development operation on the exposed portion of the photosensitive layer. As the developer, an aqueous alkali solution is preferred, and for example, an alkaline aqueous solution containing a compound having a pKa = 7 to 13 at a concentration of from 0.05 mol/L (liter) to 5 mol/L is more preferable. The developer may further contain an organic solvent having a miscibility with water, a surfactant, and the like. The developer which can be preferably used in the present invention is, for example, a developer described in paragraph 0194 of International Publication No. 2015/093271.

The development method is not particularly limited, and may be any of spin coating immersion development, shower development, shower and spin development, immersion development, and the like. Here, in the case of the shower development, the exposed portion can be removed by blowing a developer onto the exposed photosensitive layer and the intermediate layer by showering. Further, it is preferable to remove the development residue while wiping off the cleaning agent or the like by spraying with a brush or the like. The liquid temperature of the developer is preferably from 20 ° C to 40 ° C.
Moreover, the effect of suppressing the deformation of the pattern shape in the present invention is further exhibited in the case where the time from exposure to development is long. The development may be carried out immediately after the exposure, but the time from the exposure to the development is preferably from 0.5 hours or longer, more preferably 1 hour or longer, and even more preferably after 6 hours or more. Further, the effect of suppressing the deformation of the pattern shape in the present invention can be further exerted.
Moreover, the resin pattern manufacturing method of the present invention or the wiring manufacturing method of the present invention may include a known step such as a step of washing by water or the like, a step of drying a support having the obtained pattern, and the like.

Further, it is also possible to have a baking step after heat-treating the pattern obtained by development.
The post-baking heating is preferably carried out in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferably carried out in an environment of 111.46 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
The post-baking temperature is preferably from 80 ° C to 250 ° C, more preferably from 110 ° C to 170 ° C, and particularly preferably from 130 ° C to 150 ° C.
The post-baking time is preferably from 1 minute to 30 minutes, more preferably from 2 minutes to 10 minutes, and particularly preferably from 2 minutes to 4 minutes.
Post-baking can also be carried out in an air environment or in a nitrogen-substituted environment.

The conveying speed of the support at each step in the resin pattern producing method of the present invention or the wiring manufacturing method of the present invention is not particularly limited, and is preferably 0.5 m/min to 10 m/min except for exposure. Other than exposure, 2.0 m/min to 8.0 m/min is more preferable.

<Peeling step>
The resin pattern manufacturing method of the present invention or the wiring manufacturing method of the present invention, after the step of bonding to the support and before the step of developing the photosensitive layer, includes a step of peeling off the temporary support (peeling step) It is better.
Since the resin pattern manufacturing method of the present invention or the wiring manufacturing method of the present invention uses the photosensitive transfer material having the above intermediate layer, even if the temporary support is peeled off after bonding the photosensitive transfer material and before development, the intermediate layer Since the adhesion to the photosensitive layer is also excellent, it is possible to suppress the occurrence of defects such as partial peeling of the intermediate layer, and to perform pattern formation favorably.
Moreover, the resin pattern manufacturing method of the present invention or the wiring manufacturing method of the present invention includes, after the step of bonding to the support and the step of patterning the photosensitive layer, from the viewpoint of pattern formation property and resolution. The step of peeling off the above temporary support is more preferable. Further, in the above-described aspect, when the pattern is exposed by contact with the mask, the photosensitive layer and the mask are not in direct contact with each other, and thus the pattern formation property and the resolution are more excellent.
The method of peeling off the temporary support in the above-mentioned peeling step is not particularly limited, and peeling may be performed by a known method.

<etching step>
The wiring manufacturing method of the present invention preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not disposed.
In the etching step, the pattern formed from the photosensitive layer by the developing step is used as an etching resist, and the etching treatment of the conductive layer is performed.
The etching of the above-mentioned conductive layer can be applied by a known method such as a method described in paragraphs 0048 to 0054 of the Japanese Patent Laid-Open Publication No. 2010-152155, or a conventional method such as plasma etching.
For example, as a method of etching, a wet etching method which is usually immersed in an etching liquid can be mentioned. The etching liquid used for the wet etching may appropriately select an etching liquid of an acidic type or an alkaline type depending on the object to be etched.
Examples of the acidic type etching liquid include an aqueous solution of an acidic component such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid or phosphoric acid, an acidic component, and a mixture of salts such as ferric chloride, ammonium fluoride or potassium permanganate. Aqueous solution, etc. As the acidic component, a component in which a plurality of acidic components are combined can be used.
As the alkaline etchant, an aqueous solution, an alkaline component, and a high manganese of a single basic component such as a salt of an organic amine such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine or tetramethylammonium hydroxide can be exemplified. A mixed aqueous solution of a salt such as potassium acid. As the alkaline component, a component in which a plurality of basic components are combined can be used.

The temperature of the etching solution is not particularly limited, and is preferably 45 ° C or lower. The pattern used as the etching mask (etching pattern) in the present invention is particularly excellent in resistance to an acidic and alkaline etching liquid in a temperature region of 45 ° C or lower. Therefore, the peeling of the above-described pattern in the etching step is prevented, and the portion where the above pattern is not present is selectively etched.

After the etching step, in order to prevent contamination of the production line, a step of cleaning the support having the etched conductive layer (cleaning step) and a step of drying the support having the etched conductive layer (drying step) may be performed as needed . For the washing step, for example, the substrate is washed with pure water at normal temperature (10 ° C to 35 ° C) for 10 seconds to 300 seconds. Regarding the drying step, for example, it is sufficient to use a blast and appropriately adjust the blast pressure (about 0.1 kg/cm ² to 5 kg/cm ² ) to perform drying.

<etching resist stripping step>
The wiring manufacturing method of the present invention preferably includes a step of etching the photosensitive layer (etching resist stripping step) using a stripping liquid after the etching step.
After the etching step is completed, the photosensitive layer forming the pattern remains. If the photosensitive layer is not required, all of the remaining photosensitive layers may be removed.
The method of performing the peeling by the peeling liquid is, for example, a peeling liquid in which the base material having the photosensitive layer or the like is stirred, preferably at 30 ° C to 80 ° C, more preferably 50 ° C to 80 ° C. Immerse for 5 minutes to 30 minutes.
Examples of the peeling liquid include an inorganic alkaline component such as sodium hydroxide or potassium hydroxide or an organic alkaline component such as a tertiary amine or a fourth-order ammonium salt dissolved in water, dimethyl sulfoxide or N-methylpyrrolidone. Or the stripping solution of the mixed solution. It is also possible to use a peeling liquid and perform peeling by a spray method, a shower method, a spin coating method, or the like.

Moreover, the wiring manufacturing method of the present invention can repeat the exposure step, the development step, and the etching step twice or more as needed.
As an example of the exposure step, the development step, and the other steps in the present invention, the method described in paragraphs 0035 to 0051 of JP-A-2006-023696 can be preferably used in the present invention.

The resin pattern producing method of the present invention or the wiring manufacturing method of the present invention may include any other steps. For example, the following steps can be cited, and are not limited to the steps.

<Steps to reduce visible light reflectance>
The wiring manufacturing method of the present invention can include a step of performing a treatment for reducing the visible light reflectance of a surface of the conductive layer, for example, a part or all of the conductive layer on the support.
As a process of reducing the reflectance of visible light, an oxidation process etc. are mentioned. For example, copper is oxidized and copper oxide is used for blackening, whereby the visible light reflectance can be lowered.
A preferred aspect of the process for reducing the reflectance of visible light is disclosed in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0044, 0048, and 0058 of JP-A-2013-206315. The contents of this bulletin are described in the paragraph.

<Step of forming an insulating film on a support having the above-mentioned conductive layer etched and forming a new conductive layer on the insulating film>
The wiring manufacturing method of the present invention includes the steps of forming an insulating film on the support having the conductive layer, for example, the formed wiring (the etched conductive layer), and forming a new conductive layer on the insulating film. Preferably.
The step of forming the insulating film is not particularly limited, and a method of forming a known permanent film can be mentioned. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive layer on the insulating film is not particularly limited. A new conductive layer that forms a desired pattern by photolithography may also be used using a photosensitive photosensitive material.

Further, in the wiring manufacturing method of the present invention, the etching resist may be formed by the same method as described above, and the new conductive layer may be etched, or may be etched by a known method.
The wiring board obtained by the wiring manufacturing method of the present invention may have only one wiring on the substrate, or may have two or more wirings.

Further, in the wiring manufacturing method of the present invention, each of the two surfaces of the support has a plurality of conductive layers, and it is also preferable to form circuits on the conductive layers formed on both surfaces of the support sequentially or simultaneously. With such a structure, it is possible to form a wiring in which a first conductive pattern (first wiring) is formed on one surface of the support and a second conductive pattern (second wiring) is formed on the other surface, preferably a touch panel. Use wiring.

(wiring and wiring board)
The wiring of the present invention is a wiring manufactured by the wiring manufacturing method of the present invention. Moreover, as the wiring, a circuit wiring can be preferably exemplified.
The wiring board of the present invention is a substrate having wiring manufactured by the wiring manufacturing method of the present invention.
The use of the wiring board of the present invention is not limited, and for example, a wiring board for a touch panel is preferable.

(input device and display device)
As an apparatus which has the wiring manufactured by the wiring manufacturing method of this invention, an input device is mentioned.
The input device of the present invention may be any input device having at least wiring manufactured by the wiring manufacturing method of the present invention, and a capacitive touch panel is preferable.
The display device of the present invention is preferably provided with the input device of the present invention. The display device of the present invention is preferably an image display device such as an organic EL display device or a liquid crystal display device.

(touch panel and touch panel display device)
The touch panel of the present invention is a touch panel having at least wiring manufactured by the wiring manufacturing method of the present invention. Moreover, it is preferable that the touch panel of the present invention has at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device of the present invention is a touch panel display device having at least wiring manufactured by the wiring manufacturing method of the present invention, and a touch panel display device having the touch panel of the present invention is preferable.
The touch panel of the present invention and the touch panel display device of the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance method is preferred.

As the touch panel type, a so-called in-line type (for example, those shown in FIG. 5, FIG. 6, FIG. 7, and FIG. 8 of JP-A-2012-517051) and a so-called external type (for example, In the case of FIG. 19 of the Japanese Patent Publication No. 2013-168125, the one shown in FIG. 1 and FIG. 5 of JP-A-2012-089102, the OGS (One Glass Solution) type, and the TOL (Touch-on-Lens). Other types (for example, those shown in FIG. 2 of JP-A-2013-054727) and other structures (for example, those shown in FIG. 6 of JP-A-2013-164871) and various external types (so-called GG, G1)・G2, GFF, GF2, GF1, G1F, etc.).

As the touch panel of the present invention and the touch panel display device of the present invention, "the latest touch panel technology" (released on July 6, 2009, Techno Times Co., Ltd.), Sangu Yuji, "touch" can be applied. "Technology and Development of Control Panel" (December 2004, CMC Publishing), FPD International 2009 Forum T-11 lecture materials, Cypress Semiconductor Corporation Application Guide AN2292, etc.
[Examples]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the embodiments of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. In addition, “parts” and “%” are quality standards unless otherwise specified.

(Example 1)
<Preparation of Composition 1 for Intermediate Layer Formation>
The intermediate layer forming composition 1 was produced by the following formulation.
- distilled water: 13.4 parts, methanol: 75.6 parts, hydroxypropyl methylcellulose (product name: TC-5, manufactured by Shin-Etsu Chemical Co., Ltd.): 4.1 parts SNOWTEX O (cerium oxide particles, Nissan) Chemical Industries, LTD., average particle size 12 nm): 68.5 parts

<Synthesis of MATHF Copolymer>
Methacrylic acid (86 g, 1 mol) was cooled to 15 °C and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution was added 2,3-dihydroxyfuran (71 g, 1 mol, 1.0 eq.). After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, and extracted with ethyl acetate (500 mL). After drying over magnesium sulfate, the insolubles were filtered, and concentrated under reduced pressure at 40 ° C or less. The yellow oil was distilled under reduced pressure to give a crude oil (yield: 80 mol%) of THF (tetrahydrofuran-2-yl) (MATHF), which had a boiling point (bp.) of 54 to 56 ° C / 3.5 mmHg.
Using the oil, the following MATHF copolymer was synthesized by the method described in paragraphs 0248 to 0249 of JP-A-2013-061616. The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained MATHF copolymer was 14,000. The structure of the MATHF copolymer is shown below (the value in the structural formula is the molar ratio).

[Chemistry 14]

<Production of Photosensitive Resin Composition 1>
The photosensitive resin composition 1 was produced by mixing the components in such a manner as to have the following composition.
・MATHF copolymer: 93.9 parts ・Photoacid generator (PAG-1 below): 5.0 parts ・Interactive surfactant (the following surfactant 1): 0.1 parts ・Additives (Additive 1 below): 1.0 parts ・PGMEA :900 copies

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

[化15]

<Production of photosensitive transfer material>
The intermediate layer-forming composition 1 was formed on a polyethylene terephthalate (PET) film (temporary support 1) having a thickness of 50 μm so as to have a dry film thickness of 2.0 μm, and dried in a convection oven at 100 ° C. It took 2 minutes. Next, the photosensitive resin composition 1 was applied onto the intermediate layer so that the dried film thickness was 3.0 μm using a slit nozzle. Then, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a dry film resist was produced by pressure-bonding a polyethylene film (manufactured by Tredegar Corporation, OSM-N) as a protective film. The obtained dry film resist was used as the dry film resist (photosensitive transfer material) of Example 1.

(Examples 2 to 11 and Examples 14 to 17)
The intermediate layer-forming composition having the composition shown in Table 1 was produced in the same manner as in Example 1 except that the intermediate layer was formed so as to have the volume fraction and the film thickness shown in Table 1. The photosensitive transfer materials of Examples 2 to 11 and Examples 14 to 17 were used.

(Embodiment 12)
The photosensitive transfer material of Example 12 was obtained in the same manner as in Example 1 except that the photosensitive resin composition 2 described below was used instead of the photosensitive resin composition 1.

<Production of Photosensitive Resin Composition 2>
The photosensitive resin composition 2 was produced by mixing each component so that it might become the following composition.

-composition-
・Vinyl varnish resin (m-cresol: p-cresol = 30:70 (mass ratio), molecular weight: 5,500): 79.9 parts, sensitizer: The diazonium-resistant sputum described on page 4 of JP-A-4-022955 (hereinafter, also referred to as NQD.) Compound (1): 20 parts, surfactant (the above surfactant 1): 0.1 part, PGMEA: 900 parts

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

<Production of Photosensitive Resin Composition 3>
A negative photosensitive resin composition 3 was produced from the following formulation.
・Acrylic-methyl methacrylate copolymer (Mw20,000, acid value: 130 mgKOH/g): 30 parts, propylene glycol monomethyl ether: 100 parts, IRGACURE 907 (manufactured by BASF): 4.0 parts, trimethylpropane three Acrylate: 15.0 parts

(Comparative Example 1)
The photosensitive transfer material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the laminated temporary support was used instead of the temporary support 1 and the intermediate layer was not formed.
Laminated temporary support: The layered support of polyethylene terephthalate (PET) manufactured by TORAY INDUSTRIES, INC., and the layer on the side of the photosensitive layer contain SiO ₂ particles (having an average particle diameter of 500 nm).

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

(Evaluation)
<Evaluation of adhesion between intermediate layer and photosensitive layer>
A circuit-formed substrate was produced by forming a film of copper on a PET substrate having a film thickness of 100 μm on a PET substrate having a film thickness of 200 nm by a vacuum deposition method.
The protective film was peeled off from the photosensitive transfer material of Example 1, and the photosensitive transfer material obtained by laminating the copper layer at 100 ° C, a speed of 1 m/min, and a linear pressure of 0.6 MPa was peeled off and temporarily supported. The body is formed into a laminate in which a photosensitive layer is laminated on a copper layer.
A printing nail C (manufactured by Nitto Denko Corporation) cut into 4.5 cm × 15 cm was attached to the laminate, and the tape was cut into 4.5 cm × 9 cm so as to match the width of the support. Using a TENSILON universal testing machine manufactured by A&D Company, Limited, 180° peeling was performed by a peeling speed of 100 mm/min, and the adhesion between the intermediate layer and the photosensitive layer was measured.
The adhesion at this time was evaluated according to the following evaluation criteria. The larger the value, the more preferable, and the range of 5 to 3 is practical.
[evaluation benchmark]
5: upper limit of measurement (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: When the support is peeled off, the intermediate layer is also peeled off, so it cannot be evaluated.

[Table 1]

As is clear from Table 1, the adhesion between the intermediate layer of the photosensitive transfer material of the example and the photosensitive layer was superior to that of the photosensitive transfer material of the comparative example.

Further, the average particle diameter of the particles described in Table 1 is an arithmetic mean particle diameter, which is measured by the above-described measurement method.
In the case of A in the "resist" column described in Table 1, in the case of A, the photosensitive layer in the photosensitive transfer material is a chemically amplified positive resist layer, and in the case of B, The photosensitive layer in the photosensitive transfer material is a positive resist layer containing NQD, and in the case of C, 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 the above are as follows.
SiO ₂ (average particle diameter: 50 nm): cerium oxide particles, SNOWTEX XL manufactured by Nissan Chemical Industries, LTD., arithmetic mean particle diameter 50 nm
SiO ₂ (average particle diameter: 100 nm): cerium oxide particles, SNOWTEX MP-1040 manufactured by Nissan Chemical Industries, LTD., arithmetic mean particle diameter 100 nm
SiO ₂ (average particle diameter: 200 nm): cerium oxide particles, SNOWTEX MP-2040 manufactured by Nissan Chemical Industries, LTD., arithmetic mean particle diameter 200 nm
SiO ₂ (average particle diameter: 300 nm): cerium oxide particles, SNOWTEX MP-3040 manufactured by Nissan Chemical Industries, LTD., arithmetic mean particle diameter 300 nm
TiO ₂ (average particle size 20 nm): titanium oxide particles, STS-21 manufactured by ISHIHARA SANGYO KAISHA, LTD., arithmetic mean particle size 20 nm
ZrO ₂ (average particle diameter: 42 nm): zirconia particles, NanoUse ZR-20AS manufactured by Nissan Chemical Industries, LTD., arithmetic mean particle diameter 42 nm
PMMA (average particle size 40 nm): polymethyl methacrylate particles, EOSTAR MX030W manufactured by NIPPON SHOKUBAI CO., LTD., arithmetic mean particle size 40 nm
PVA: polyvinyl alcohol, Kuraray POVAL PVA205 manufactured by Kuraray Co., Ltd.

(Embodiment 18)
<Preparation of Composition 18 for Forming Intermediate Layer A and Composition 18 for Forming Intermediate Layer B>
In the same manner as in Example 1, the intermediate layer A-forming composition 18 was prepared in the same manner as in Example 1 in the composition shown in Table 2 and the volume fraction described in Table 2 (hereinafter, also in the middle of the two layers) The layer disposed on the temporary support side in the layer is referred to as the intermediate layer A.) and the intermediate layer B forming composition 18 (hereinafter, the layer disposed on the side of the photosensitive layer in the intermediate layer of the two layers is also referred to as an intermediate layer B.).

<Production of photosensitive transfer material>
The intermediate layer A-forming composition 18 was slit-coated on a polyethylene terephthalate (PET) film (temporary support 1) having a thickness of 50 μm so that the dry film thickness was 2.0 μm, at 100 ° C. It was allowed to dry in a convection oven for 2 minutes to form an intermediate layer A. Then, the intermediate layer B-forming composition 18 was slit-coated so that the dry film thickness became 2.0 μm, and dried in a convection oven at 100° C. for 2 minutes to form the intermediate layer B. Next, the photosensitive resin composition 1 was applied to the intermediate layer so that the dried film thickness was 3.0 μm using a slit nozzle. Thereafter, the film was dried in a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (OSM-N, manufactured by Tredegar Corporation) 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.
Using the obtained photosensitive transfer material of Example 18, adhesion evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Examples 19 to 25)
The composition for forming the intermediate layer A and the composition for forming the intermediate layer B which are the compositions of the intermediate layer A and the intermediate layer B described in Table 2 are used 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 photosensitive resin composition 2 described below was used instead of the photosensitive resin composition 1.

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

[Table 2]

The details of the binder and particles described in Table 2 are as follows.
HMPC: hydroxypropylmethylcellulose (product name: TC-5, manufactured by Shin-Etsu Chemical Co., Ltd.)
PVA: polyvinyl alcohol (product name: KURARAY POVAL PVA205, manufactured by Kuraray Co., Ltd.)
HPC: hydroxypropyl cellulose (product name: HPC-SSL, NIPPON SODA CO., LTD.)
Acrylic resin: methacrylic acid / benzyl methacrylate copolymer (Mw: 11,000, composition ratio (Morby): 30/70)
SiO ₂ (average particle diameter: 50 nm): cerium oxide particles, SNOWTEX XL manufactured by Nissan Chemical Industries, LTD., arithmetic mean particle diameter 50 nm

(Example 101)
Indium tin oxide (ITO) was formed as a second conductive layer on a 100 μm thick PET substrate by sputtering at a thickness of 150 nm, and copper was formed thereon by vacuum evaporation at a thickness of 200 nm. As the first conductive layer, a circuit-formed substrate was prepared.
The photosensitive transfer material produced in Example 1 (linear pressure 0.8 MPa, linear velocity 3.0 m/min, roll temperature 90 ° C) was laminated on the copper layer. The contact pattern exposure is performed by using a mask provided with a pattern (hereinafter, also referred to as "pattern A") having a structure in which a conductive layer pad is connected in one direction, without peeling off the temporary support.
Further, in the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are shielding portions, and the broken line portion DL virtually indicates the aligned frame.
Thereafter, the temporary support was peeled off, developed, and washed with water to obtain a pattern A. Then, after etching the copper layer using a copper etching solution (Cu-02 manufactured by KANTO CHEMICAL CO., INC.), the ITO layer was etched using an ITO etching solution (ITO-02 manufactured by KANTO CHEMICAL CO., INC.), thereby obtaining copper. (solid line portion SL) A substrate drawn by pattern A together with ITO (grey portion G).

Next, in the state of being aligned, pattern exposure was performed using the mask of the opening pattern shown in FIG. 3 (hereinafter, also referred to as "pattern B"), and development and water washing were performed.
Further, in the pattern B shown in FIG. 3, the ash portion G is a blocking portion, and the broken line portion DL virtually indicates an aligned frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive layer was peeled off using a peeling liquid (10% by mass aqueous sodium hydroxide solution) to obtain a wiring board.
Thereby, a wiring board was obtained. The result of observation by a microscope is a clear pattern without peeling or defects.

10‧‧‧ temporary support

12‧‧‧Intermediate

14‧‧‧Photosensitive layer

16‧‧‧ Cover film

100‧‧‧Photosensitive transfer material

SL‧‧‧solid line

G‧‧‧ Gray Department

DL‧‧‧dotted section

Fig. 1 is a schematic view showing an example of a layer structure of a photosensitive transfer material of the present invention.

Fig. 2 is a schematic view showing a pattern A.

Fig. 3 is a schematic view showing a pattern B.

Claims (12)

A photosensitive transfer material which in turn has a temporary support, an intermediate layer and a photosensitive layer, The intermediate layer contains a binder and particles having an arithmetic mean 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 The intermediate layer has an average film thickness of 0.3 μm to 10 μm. The photosensitive transfer material according to claim 1 or 2, wherein The particles contained in the intermediate layer are selected from oxide particles or organic particles of at least one element selected from the group consisting of Si, Ti, and Zr. The photosensitive transfer material according to claim 1 or 2, 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 group protected by an acid-decomposable group. The photosensitive transfer material according to claim 1 or 2, wherein The photosensitive layer contains a binder having an acid group, a polymerizable compound, and a photopolymerization initiator. The photosensitive transfer material according to claim 1 or 2, wherein The binder contained in the intermediate layer contains a modified cellulose resin. The photosensitive transfer material according to claim 1 or 2, wherein The intermediate layer has two or more layers. The photosensitive transfer material according to claim 9 of the patent application, wherein Among the two or more layers in the intermediate layer, only the layer closest to the photosensitive layer contains particles having an arithmetic mean particle diameter of 400 nm or less. A resin pattern manufacturing method comprising: The step of attaching the outermost layer on the side of the photosensitive layer in the photosensitive transfer material according to any one of claims 1 to 10 to the support; a step of patterning the photosensitive layer; and a step of developing the photosensitive layer exposed by the pattern, The step of peeling the temporary support is performed after the step of bonding to the support and before the step of developing the photosensitive layer. A wiring manufacturing method comprising: The step of bonding the outermost layer on the side of the photosensitive layer in the photosensitive transfer material according to any one of claims 1 to 10 to a support having a conductive layer on the surface; a step of patterning the photosensitive layer; a step of developing the patterned photosensitive layer to form a resin pattern; a step of etching the conductive layer using the resin pattern as a mask; and The step of peeling off the resin pattern, The step of peeling the temporary support is performed after the step of bonding to the support and before the step of developing the photosensitive layer.