JP7074776B2 - Photosensitive transfer material and its manufacturing method, resin pattern manufacturing method, and circuit wiring manufacturing method. - Google Patents

Description

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

In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. The conductive layer pattern such as is provided inside the touch panel.
Generally, in forming a patterned layer, the number of steps for obtaining the required pattern shape is small, so a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is used. (Also referred to as a "photosensitive layer"), a method of developing after exposure through a mask having a desired pattern is widely used.

As a method for producing such a photosensitive transfer material, for example, Japanese Patent Application Laid-Open No. 2008-076952 describes the production of a photosensitive resin transfer material having a photosensitive resin layer, an intermediate layer, and a cover film on a support in this order. The method is an intermediate between a photosensitive resin layer coating step of applying a coating liquid for forming a photosensitive resin layer containing a colorant, a binder and a photosensitive resin on a support, and a thermoplastic resin containing a thermoplastic resin on a cover film. The intermediate layer coating step of applying the layer-forming coating liquid, the surface on which the photosensitive resin layer-forming coating liquid of the support is applied, and the surface of the cover film on which the intermediate layer-forming coating liquid is applied. A heating step of heating the cover film coated with the coating liquid for forming the intermediate layer is performed between the intermediate layer coating step and the bonding step, which includes a bonding step of bonding to obtain a photosensitive resin transfer material. Further, a method for producing a photosensitive resin transfer material, including the above, is described.
Japanese Patent Application Laid-Open No. 2004-086089 has at least one photosensitive adhesive layer and a photosensitive phosphor layer between a support and a cover film, and the above-mentioned photosensitive phosphor layer and the above-mentioned support. A cushion layer made of a thermoplastic resin is provided between the layers, and the water-soluble photosensitive resin contained in the photosensitive phosphor layer contains 0.5 to 0.5 to an azide compound made of a loadanine skeleton as a photosensitive component addition group. It is a modified polyvinyl alcohol containing 3.0 mol% and having a degree of polymerization of 300 to 1100, and the water-soluble photosensitive resin contained in the photosensitive adhesive layer contains 1.5 azido compounds composed of a loadanine skeleton as a photosensitive component addition group. Described is a phosphor transfer film characterized by being a modified polyvinyl alcohol having a degree of polymerization of 1100 to 3000 and containing ~ 5.0 mol%.

When forming a photosensitive layer on a substrate using a photosensitive transfer material, by attaching the photosensitive transfer material to the substrate, a laminate having at least a substrate, a photosensitive layer, and a temporary support is formed in this order. Will be done. After exposing such a laminate, a resin pattern is formed by developing the photosensitive layer.
Here, for the purpose of improving the resolution of the obtained resin pattern, eliminating the influence of foreign matter in the temporary support, and the like, in the above exposure, after the temporary support was peeled off, the temporary support of the laminated body was peeled off. It has been studied to bring a mask having a pattern into contact with a side surface for exposure (also referred to as "contact exposure").
When the mask is brought into contact with the laminated body after the temporary support is peeled off and exposed as described above, the mask sticks to the surface of the laminated body, and the mask once contacted becomes difficult to move. It may be difficult to align the mask.
In the present disclosure, the above-mentioned state in which the once-contacted mask becomes difficult to move is also referred to as "low (inferior) slipperiness to the mask", and it is easy to move the once-contacted mask again. It is also called "high (excellent) slipperiness against mask".

An object to be solved by one embodiment of the present disclosure is to provide a photosensitive transfer material having excellent slipperiness against a mask during contact exposure and a method for producing the same.
Further, an object to be solved by another embodiment of the present disclosure is to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material and a method for manufacturing a circuit wiring.

The means for solving the above problems include the following aspects.
<1> The cover film has a photosensitive layer, an intermediate layer, an adhesive layer, and a temporary support in this order, the intermediate layer contains particles, and the intermediate layer and the adhesive layer are formed. The intermediate layer and the adhesive layer are in contact with each other and can be peeled off, and the surface of the intermediate layer after the intermediate layer and the adhesive layer are peeled off has irregularities formed by the particles. Sex transfer material.
<2> The photosensitive transfer material according to <1>, wherein the particles include at least one particle selected from the group consisting of silica particles, alumina particles, and organic polymer particles.
<3> The photosensitive transfer material according to <1> or <2>, wherein the average particle size of the particles is 10 nm to 200 nm.
<4> The photosensitive transfer material according to any one of <1> to <3>, wherein the content of the particles with respect to the total mass of the intermediate layer is 1% by mass to 80% by mass.
<5> The photosensitive layer according to any one of <1> to <4>, wherein the photosensitive layer contains a binder polymer having an acid group protected by an acid-degradable group and a photoacid generator. Sex transfer material.
<6> The photosensitive transfer material according to any one of <1> to <4>, wherein the photosensitive layer contains a binder polymer having an acid group, a polymerizable compound, and a photopolymerization initiator.
<7> Any of the above <1> to <6>, wherein the intermediate layer contains at least one selected from the group consisting of a modified cellulose resin, polyvinyl alcohol, and polyvinylpyrrolidone as a binder polymer for the intermediate layer. The photosensitive transfer material according to one.
<8> A step of applying a photosensitive layer forming composition on a cover film to form a photosensitive layer, and a step of applying an intermediate layer forming composition containing at least particles on the photosensitive layer to form an intermediate layer. A method for producing a photosensitive transfer material, which comprises a step of bonding a temporary support having an adhesive layer so that the adhesive layer is in contact with the intermediate layer.
<9> The step of peeling the cover film of the photosensitive transfer material according to any one of <1> to <7> and the photosensitive layer of the photosensitive transfer material from which the cover film has been peeled off. A step of bringing the outermost layer on the side into contact with a support having a conductive layer and sticking them together, a step of peeling off the temporary support, the adhesive layer, and the intermediate layer, and an exposure mask on the intermediate layer. A method for producing a resin pattern, which comprises a step of pattern-exposing the photosensitive layer through the exposure mask and a step of developing the photosensitive layer to form a resin pattern in this order.
<10> The step of peeling the cover film of the photosensitive transfer material according to any one of <1> to <7> and the photosensitive layer of the photosensitive transfer material from which the cover film has been peeled off. A step of bringing the outermost layer on the side into contact with a support having a conductive layer and sticking them together, a step of peeling off the temporary support, the adhesive layer, and the intermediate layer, and an exposure mask on the intermediate layer. The step of pattern-exposing the photosensitive layer through the exposure mask, the step of developing the photosensitive layer to form a resin pattern, and the step of etching the conductive layer using the formed resin pattern as a mask. A process of manufacturing a circuit wiring including the process of processing and this order.

According to one embodiment of the present disclosure, it is possible to provide a photosensitive transfer material having excellent slipperiness against a mask during contact exposure and a method for producing the same.
Further, according to another embodiment of the present disclosure, it is possible to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material and a method for manufacturing a circuit wiring.

FIG. 1 is a schematic view showing an example of the layer structure of the photosensitive transfer material according to the present disclosure. FIG. 2 is a schematic view showing the pattern A. FIG. 3 is a schematic view showing the pattern B.

Hereinafter, the contents of the present disclosure will be described. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
Further, the numerical range represented by using "-" in the present disclosure means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present disclosure, "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either.
Further, in the present disclosure, the amount of each component in the composition is the total amount of the plurality of applicable substances present in the composition when a plurality of the substances corresponding to each component are present in the composition, unless otherwise specified. Means.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the notation of a group (atomic group) in the present disclosure, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, the chemical structural formula in the present disclosure may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, for the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) are used. The molecular weight is detected by the solvent THF (tetrahydrofuran) and the differential refractometer by the gel permeation chromatography (GPC) analyzer and converted using polystyrene as a standard substance.

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has a photosensitive layer, an intermediate layer, an adhesive layer, and a temporary support in this order on a cover film, the intermediate layer containing particles, and the intermediate layer. And the adhesive layer are in contact with each other, the intermediate layer and the adhesive layer can be peeled off, and the surface of the intermediate layer after the intermediate layer and the adhesive layer are peeled off is formed by the particles. It has the formed unevenness.

The present inventors have low slipperiness against a mask when contact exposure is performed using the transfer film described in JP-A-2008-076952 or JP-A-2004-086089, and after the mask is once brought into contact with the mask, the present inventors have low slipperiness against the mask. We have found that it can be difficult to change the mask position due to alignment.

Therefore, as a result of diligent studies, the present inventors have found that when the above-mentioned photosensitive transfer material according to the present disclosure is used, it is excellent in slipperiness against a mask during contact exposure.
The detailed mechanism by which the above effects are obtained is unknown, but it is speculated as follows.
The photosensitive transfer material according to the present disclosure is peeled off at the interface between the adhesive layer and the intermediate layer when the temporary support is peeled off. Therefore, the mask and the intermediate layer come into contact with each other during contact exposure.
Here, since the surface of the intermediate layer according to the present disclosure has irregularities formed by particles contained in the intermediate layer, it is considered that the mask becomes slippery even after being in contact with the intermediate layer once, and the mask slipperiness is excellent. Be done.
By using such a photosensitive transfer material having excellent slipperiness against the mask during contact exposure, it is considered that the alignment of the mask during contact exposure becomes easy and the pattern by the photosensitive layer is easily formed at the target position. Be done.

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

FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, an adhesive layer 18, an intermediate layer 12, a photosensitive layer 14, and a cover film 16 are laminated in this order.
The intermediate layer 12 contains particles, and irregularities due to the particles are formed on the surface of the intermediate layer 12 at the interface between the intermediate layer 12 and the adhesive layer 18 (not shown).
Hereinafter, the constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described.

<Temporary support>
The temporary support is a support that supports the adhesive layer, the intermediate layer, and the photosensitive layer, and is peeled off together with the adhesive layer after transfer of the photosensitive layer and the like and before exposure.
The temporary support used in the present disclosure may or may not have light transmission.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like. Of these, polyethylene terephthalate film is preferable, and biaxially stretched polyethylene terephthalate film is particularly preferable.

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

Preferred embodiments of the provisional support are described in, for example, paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of this publication are incorporated in the present specification.

<Adhesive layer>
The adhesive layer is peeled off together with the temporary support when the temporary support is peeled off.
The peeling force between the temporary support and the adhesive layer is preferably 0.001 N / 25 mm or more in order to make it difficult to peel off at the interface between the temporary support and the adhesive layer.
Further, the peeling force between the adhesive layer and the photosensitive layer is preferably 0.5 N / 25 mm or less so that the adhesive layer and the photosensitive layer can be peeled off at the interface.
The peeling force is measured by performing a 180 ° peeling test at a tensile speed of 300 mm / min in a room temperature environment (23 ° C.).

The material of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known adhesive or a layer containing an adhesive can be mentioned.

[Adhesive]
Examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. As an example of the adhesive, "Characteristic evaluation of release paper / release film and adhesive tape and its control technology", Information Mechanism, 2004, Acrylic adhesive described in Chapter 2, UV (UV) curable adhesive. Agents, silicone adhesives and the like can be mentioned. The acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of a (meth) acrylic monomer (that is, a (meth) acrylic polymer).
When a pressure-sensitive adhesive is contained, a pressure-sensitive adhesive may be further contained.

〔glue〕
Examples of the adhesive include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, silicone adhesives and the like. A urethane resin adhesive or an acrylic resin adhesive is preferable from the viewpoint that the adhesive strength is relatively high and the adhesive strength can be easily controlled by introducing a heat-crosslinked or photocrosslinked structure.

[Method of forming an adhesive layer]
The method for forming the adhesive layer is not particularly limited, and a method of laminating a temporary support on which the adhesive layer is formed so as to be in contact with the adhesive layer and an intermediate layer, and a method of forming the adhesive layer alone into an intermediate layer. Examples thereof include a method of laminating in contact with each other, a method of applying the above-mentioned adhesive or a composition containing an adhesive on an intermediate layer, and the like.
As the temporary support on which the adhesive layer is formed, a commercially available one may be used, for example, E-MASK AW303D, E-MASK RP207 (both manufactured by Nitto Denko Corporation), PanaProtect HP25, Panaprotect. MK38S (both manufactured by Panac Co., Ltd.), etc. can be mentioned.

[Characteristics of adhesive layer]
The thickness of the adhesive layer in the photosensitive transfer material according to the present disclosure is preferably 5 μm to 100 μm in terms of both adhesive strength and handleability.
The thickness of the adhesive layer is preferably 0.01 μm or more and 50 μm or less, more preferably 0.1 μm or more and 20 μm or less, and most preferably 0.2 μm or more and 10 μm or less.
When the thickness of the adhesive layer is 0.01 μm or more, the particles are suppressed from being buried in the photosensitive layer at the time of laminating, and good slipperiness at the time of mask contact may be easily exhibited. Further, when it is 50 μm or less, the peelability between the adhesive layer and the photosensitive layer may be good.

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

[Unevenness]
The fact that the surface of the intermediate layer after peeling the intermediate layer and the adhesive layer has irregularities formed by particles means that the surface of the intermediate layer after peeling has irregularities derived from the shape of the particles. Means that.
When the intermediate layer contains the binder polymer for the intermediate layer described later, the unevenness may be formed by exposing the particles from the layer of the binder polymer for the intermediate layer, or one of the particles by the binder polymer for the intermediate layer. It may be formed by covering a part or the whole.
Further, in the present disclosure, it is confirmed by observing the surface of the intermediate layer after peeling using a scanning electron microscope (SEM) that the surface of the intermediate layer after peeling has irregularities formed by particles. It is possible.

〔particle〕
The particles contained in the intermediate layer are preferably metal oxide particles or organic polymer particles from the viewpoint of slipperiness against mask, and at least selected from the group consisting of silica particles, alumina particles and organic polymer particles. It is more preferable to contain one kind of particles.
Silica particles (refractive index: 1.4 to 1.5), alumina particles (refractive index: 1.6 to 1.65) and organic polymer particles (refractive index: 1.4 to 1.7) have their refractive indexes. However, since it is close to the refractive index of an organic substance (refractive index: 1.4 to 1.6) such as a resin contained in the photosensitive layer, scattering of light is suppressed and the linearity of the resist pattern is improved, which is preferable.

-Metal oxide particles-
The metal of the metal oxide particles in the present disclosure shall also include metalloids such as B, Si, Ge, As, Sb and Te.
Examples of 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, and B. , Al, Si, Ge, Sn, Pb, Sb, Bi, Te and the like, oxide particles containing atoms are preferable, and silica, alumina, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide. , Or antimony / tin oxide is more preferred, silica, alumina, titanium oxide, titanium composite oxide or zirconium oxide is even more preferred, and silica or alumina is particularly preferred.

-Organic polymer particles-
Examples of the organic polymer particles include homopolymers and copolymers of acrylic acid-based monomers such as acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester, and cellulose-based polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate. , Polyethylene, Polypropylene, Polystyrene, Vinyl Chloride Copolymer, Vinyl Chloride-Vinyl Acetate Copolymer, Polyvinylpyrrolidone, Polyvinylbutyral, Polypolymers of Vinyl Polymers and Vinyl Compounds, Polyester, Polyurethane, Polypolymer Condensation polymers such as, rubber-based thermoplastic polymers such as butadiene-styrene copolymers, polymers obtained by polymerizing and cross-linking photopolymerizable or thermopolymerizable compounds such as epoxy compounds, melamine compounds and the like. can.
Among these, acrylic resin particles are preferably mentioned as the organic polymer particles, and polymethylmethacrylate particles are more preferable.

-surface treatment-
The surface of the particles used in the present disclosure can also be treated with an organic material or an inorganic material in order to impart dispersion stability. The particles preferably have a hydrophilic surface. For example, particles obtained by hydrophilizing the surface of particles having a hydrophobic surface may be used.

-Particle size-
The average particle size of the particles is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm, further preferably 30 nm to 100 nm, and even more preferably 50 nm to 80 nm, from the viewpoint of improving the slipperiness against the mask. Is particularly preferable.
The average particle diameter of the particles can be obtained as an arithmetic mean value by measuring 20 particle diameters of the intermediate layer section observed using a transmission electron microscope.

The intermediate layer may contain one kind of particles alone, or two or more kinds may be used in combination.
The content of the particles with respect to the total mass of the intermediate layer is preferably 1% by mass to 80% by mass, more preferably 2% by mass to 30% by mass, from the viewpoint of slipperiness against the mask. It is more preferably from% to 10% by mass.

[Binder polymer for intermediate layer]
The intermediate layer used in the present disclosure preferably further contains a binder polymer for the intermediate layer.
The binder polymer for the intermediate layer is preferably a water-soluble or alkali-soluble polymer.
In the present disclosure, "water-soluble" means that the solubility of pH 7.0 in water at 25 ° C is 0.1% by mass or more, and "alkali-soluble" means pH 8. at 25 ° C. It means that the solubility in water of an alkaline aqueous solution of 5 or more is 0.1% by mass or more.
Further, the above-mentioned "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or may be water-soluble and alkali-soluble.

Examples of the binder polymer for the intermediate layer include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, and phenol / cresol (m-, p-, or m- /. Novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having hydroxy group (for example, homopolymer or co-polymer of hydroxyalkyl (meth) acrylate) Polymers), starches, glycogens, chitins, agaroses, carrageenans, purulans, arabic gum, soya gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, polyurethane resin, polyvinyl alcohol, polyvinyl formal , Polyvinylpyrrolidone, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol and the like.

Among these, the binder polymer is preferably at least one resin selected from the group consisting of modified cellulose resin and polyvinyl alcohol from the viewpoint of particle dispersibility and pattern forming property, and the photosensitive layer is positive. In the case of the type photosensitive layer, a modified cellulose resin is more preferable. The modified cellulose resin is more preferable because it can prevent deformation and deterioration of the pattern.
Further, as the modified cellulose resin, hydroxyalkylated cellulose or carboxyalkyl cellulose is preferable from the viewpoint of particle dispersibility and pattern forming property.
Preferred examples of the hydroxyalkylated cellulose include hydroxymethyl cellulose, hydroxyethyl cellulose, polyhydroxyethylated cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, glioxalized hydroxypropylmethyl cellulose, hydroxypropylmethylcellulose phthalate and the like.
Preferred examples of the carboxyalkyl cellulose include carboxymethyl cellulose and carboxyethyl cellulose.
Above all, from the viewpoint of particle dispersibility and pattern formation, at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is preferable, and hydroxypropylmethyl cellulose is more preferable.
When the photosensitive layer is a negative photosensitive layer, the binder polymer for the intermediate layer preferably contains polyvinyl alcohol from the viewpoint of particle dispersibility and pattern formation. The inclusion of polyvinyl alcohol is more preferable because it improves the sensitivity and the quality of the pattern.
Further, when the photosensitive layer is a negative photosensitive layer, it is preferable to contain polyvinylpyrrolidone as the binder polymer for the intermediate layer from the viewpoint of the adhesion between the photosensitive layer and the intermediate layer.

The weight average molecular weight of the binder polymer for the intermediate layer is preferably 1,000 or more, preferably 2,000 to more, from the viewpoints of particle dispersibility, pattern forming property, solubility in a developing solution after exposure, and transferability. It is more preferably 100,000, and even more preferably 10,000 to 50,000.

The intermediate layer may contain one kind of binder polymer for the middle layer alone or two or more kinds.
The content of the binder polymer for the intermediate layer in the intermediate layer is the total mass of the intermediate layer from the viewpoints of adhesion between the intermediate layer and the photosensitive layer, pattern forming property, solubility in a developing solution after exposure, and transferability. On the other hand, it is preferably 10% by mass or more and 98% by mass or less, more preferably 20% by mass or more and 95% by mass or less, further preferably 40% by mass or more and 90% by mass or less, and 65% by mass or more. It is particularly preferably 85% by mass or less.

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

[Average film thickness of intermediate layer]
The average film thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and even more preferably 0.3 μm to 2 μm from the viewpoint of pattern formation.
For the film thickness, use a stylus type surface shape measuring instrument (for example, Dektak manufactured by Bruker AXS Co., Ltd.) or a three-dimensional optical profiler (for example, NewView manufactured by Zygo Co., Ltd.) to peel off a part of the film and cover the stepped portion. It can be measured as a thickness.
Further, the average film thickness of the intermediate layer is preferably thinner than the average film thickness of the photosensitive layer described later.

[Method of forming the intermediate layer]
The method for forming the intermediate layer is not particularly limited, but each component and a solvent (preferably an aqueous solvent) are mixed at a predetermined ratio and by any method, and the intermediate layer is formed by stirring and dissolving. The composition for forming an intermediate layer for this purpose can be formed by applying it on a photosensitive layer described later. For example, it is also possible to prepare a composition by preparing a solution in which each component is previously dissolved in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can also be used after being filtered using a filter having a pore size of 5 μm or the like.
Examples of the water-based solvent include water-soluble solvents such as water and alcohols.

The method for applying the composition for forming the intermediate layer is not particularly limited, and the composition can be applied by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
It is also possible to apply an intermediate layer on the photosensitive layer on which other layers described later are formed.

<Photosensitive layer>
The photosensitive transfer material according to the present disclosure has a photosensitive layer.
Further, the photosensitive layer in the present disclosure may be a positive type photosensitive layer or a negative type photosensitive layer.
In the case of a positive photosensitive layer, the photosensitive layer is preferably a chemically amplified positive photosensitive layer.
In the photoacid generators such as onium salts and oxime sulfonate compounds described later, the acid generated in response to active radiation (active light) is protected in the binder polymer having an acid group protected by an acid degradable group. Since it acts as a catalyst for the deprotection of the acid group, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, to the power of 10. As a result of so-called chemical amplification, high sensitivity can be obtained.
On the other hand, when a naphthoquinone diazide compound (also referred to as "NQD") is used as a photoacid generator sensitive to active radiation, a carboxy group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less. , Not applicable to chemical amplification type.

When the photosensitive layer is a positive photosensitive layer, the photosensitive layer preferably contains a binder polymer and a photoacid generator from the viewpoint of pattern formation. Further, from the viewpoint of pattern forming property, the binder polymer preferably contains a binder polymer having an acid group protected by an acid-degradable group, and contains a structural unit having an acid group protected by an acid-degradable group. It is more preferable to contain the polymer having.
When the photosensitive layer is a negative photosensitive layer, the photosensitive layer preferably contains a binder polymer having an acid group, a polymerizable compound, and a photopolymerization initiator from the viewpoint of pattern forming property.
When the photosensitive layer is a negative photosensitive layer, for example, the photosensitive resin composition layer described in JP-A-2016-224162 may be used as the negative photosensitive layer.

[Polymer component containing a polymer having a structural unit having an acid group protected by an acid-degradable group]
When the photosensitive layer in the present disclosure is a positive photosensitive layer, it is preferable that the photosensitive layer contains a binder polymer having an acid group protected by an acid-degradable group.
The binder polymer having an acid group protected by an acid-degradable group is a polymer having a structural unit (also referred to as “constituent unit A”) having an acid group protected by an acid-degradable group (“specific polymer”). It is also preferable that it is.).
Further, the positive photosensitive layer may contain another polymer in addition to the polymer having the structural unit A. In the present disclosure, the polymer having the structural unit A and other polymers are also collectively referred to as "polymer component".
The specific polymer can be developed with a developing solution because the acid group protected by the acid-degradable group in the specific polymer undergoes a deprotection reaction to become an acid group due to the action of the catalytic amount of the acidic substance generated by the exposure. Become.
A preferred embodiment of the structural unit A will be described below.

The photosensitive layer may further contain a polymer other than a polymer having a structural unit having an acid group protected by an acid-degradable group.
Further, it is preferable that all the polymers contained in the polymer components are polymers having at least a structural unit having an acid group described later.
Further, the photosensitive layer may further contain a polymer other than these. Unless otherwise specified, the above-mentioned polymer component in the present disclosure is meant to include other polymers added as needed. The compound corresponding to the cross-linking agent and the dispersant described later is not included in the polymer component even if it is a polymer compound.

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

From the viewpoint of solubility in the developing solution and transferability, the photosensitive layer preferably contains a polymer having the structural unit A1 represented by the following formula A1 as the structural unit A, and the structural unit A is the following formula. It is preferable to contain a specific polymer having a structural unit A1 represented by A1 and having a glass transition temperature of 90 ° C. or lower, and the structural unit A is represented by the following formula A1 and described later. It is more preferable to contain a specific polymer having a structural unit B having an acid group and having a glass transition temperature of 90 ° C. or lower.
The specific polymer contained in the photosensitive layer may be only one kind or two or more kinds.

-Constituent unit A-
The polymer component preferably contains a polymer having at least a structural unit A having an acid group protected by an acid-degradable group. By including the polymer having the constituent unit A in the polymer component, an extremely sensitive chemically amplified positive photosensitive layer can be obtained.
As the "acid group protected by an acid-degradable group" in the present disclosure, known acid groups and acid-degradable groups can be used, and the present invention is not particularly limited. Specific examples of the acid group include a carboxy group and a phenolic hydroxyl group. Further, as the acid group protected by the acid-degradable group, a group relatively easily decomposed by an acid (for example, in the structural unit A1 represented by the formula A1 is protected by a -CR ³¹ R ³² (OR ³³ ) group. An acetal-based functional group such as an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group), a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl ester group such as a tert-butyl ester group, tert-butyl). A tertiary alkyl carbonate group such as a carbonate group) can be used.
Among these, the acid-degradable group is preferably a group having a protected structure in the form of acetal.

<< Structural unit A1 >>
The structural unit A having an acid group protected by the acid-degradable group is preferably the structural unit A1 represented by the following formula A1 from the viewpoint of sensitivity and resolution.

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

In the formula A1, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferable. R ³¹ and R ³² are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
In the formula A1, R ³³ represents an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
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 and R ³³ may be linked to form a cyclic ether, and it is preferable that R ³¹ or R ³² and R ³³ are linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the formula A1, X ⁰ represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
The structural unit A1 represented by the above formula A1 is a structural unit having a carboxy group protected by an acid-degradable 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 superior to the resolution.

In the formula A1, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the specific polymer can be lowered.
More specifically, it is preferable that the structural unit in which R ³⁴ is a hydrogen atom in the formula A is 20% by mass or more with respect to the total amount of the structural unit A1 contained in the specific polymer.
The content (content ratio: mass ratio) of the structural unit in which R ³⁴ is a hydrogen atom in the structural unit A1 is calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.

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

In the formula A2, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ to R ⁴¹ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A2, R ³⁴ is preferably a hydrogen atom.
In the formula A2, hydrogen atoms are preferable for R ³⁵ to R ⁴¹ .

The following structural units can be exemplified as a preferable specific example of the structural unit A1 having a carboxy group protected by an acid-degradable group represented by the formula A1. In addition, R ³⁴ represents a hydrogen atom or a methyl group.

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

In formula A3, ^RB1 and ^RB2 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of ^RB1 and ^RB2 is an alkyl group or an aryl group, and ^RB3 is an alkyl group or an aryl group. Representing an aryl group, ^RB1 or ^RB2 and ^RB3 may be linked to form a cyclic ether, ^RB4 represents a hydrogen atom or a methyl group, and XB is a single ^- bonded or divalent linking group. , R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In the formula A3, when ^RB1 or ^RB2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When ^RB1 or ^RB2 is an aryl group, a phenyl group is preferable. ^RB1 and ^RB2 are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
In the formula A3, ^RB3 represents an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
Further, the alkyl group and the aryl group in ^RB1 to ^RB3 may have a substituent.
In the formula A3, ^RB1 or ^RB2 and ^RB3 may be linked to form a cyclic ether, and it is preferable that ^RB1 or ^RB2 and ^RB3 are linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In formula A3, ^XB represents a single bond or a divalent linking group, a single bond or an alkylene group, -C (= O) O-, -C (= O) NR ^N- , -O- or a combination thereof. Is preferable, and a single bond is more preferable. The alkylene group may be linear, has a branch, may have a cyclic structure, or may have a substituent. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. When X ^B contains -C (= O) O-, it is preferable that the carbon atom contained in -C (= O) O- and the carbon atom to which RB ⁴ is bonded are directly bonded. When X ^B contains -C (= O) NR ^N- , it is preferable that the carbon atom contained in -C (= O) NR ^N- and the carbon atom to which ^RB4 is bonded are directly bonded. ^RN represents an alkyl group or a hydrogen atom, and an alkyl group or a hydrogen atom having 1 to 4 carbon atoms is preferable, and a hydrogen atom is more preferable.
In the formula A3, it is preferable that the group containing ^{RB1 to RB3 (that is, the —O-CR B1 RB2 (OR B3 ) group ) and} X ^B are bonded to each other at the para position.
In the formula A3, ^RB12 represents a substituent, and an alkyl group or a halogen atom is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In the formula A3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula A3, ^RB4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the specific polymer can be lowered.
More specifically, the structural unit in which ^RB4 is a hydrogen atom in the formula A3 is preferably 20% by mass or more with respect to the total content of the structural unit A contained in the specific polymer.
The content (content ratio: mass ratio) of the structural unit in which ^RB4 in the formula A3 is a hydrogen atom in the structural unit A is calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.

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

In formula A4, ^{RB4 represents a hydrogen atom or a methyl group, RB5 to RB11} independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^RB12 represents a substituent, and n is 0. Represents an integer of ~ 4.
In the formula A4, ^RB4 is preferably a hydrogen atom.
In the formula A4, ^RB5 to ^RB11 are preferably hydrogen atoms.
In the formula A4, ^RB12 represents a substituent, and an alkyl group or a halogen atom is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In the formula A4, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

As a preferable specific example of the structural unit A4 represented by the formula A4, the following structural unit can be exemplified. In addition, ^RB4 represents a hydrogen atom or a methyl group.

<< Content of constituent unit A >>
The structural unit A contained in the specific polymer may be one kind or two or more kinds.
The content of the structural unit A in the specific polymer is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and 30% by mass to the total mass of the specific polymer. It is more preferably 70% by mass.
The content (content ratio: mass ratio) of the structural unit A in the specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.
Further, after decomposing all the polymer components into constituent units (monomer units), the ratio of the constituent unit A is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer components. It is more preferably 10% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.

[Structural unit B]
The specific polymer preferably contains a structural unit B having an acid group.
The structural unit B is a structural unit containing a protecting group, for example, an acid group that is not protected by an acid-degradable group, that is, an acid group that does not have a protecting group. When the specific polymer contains the structural unit B, the sensitivity at the time of pattern formation becomes good, it becomes easy to dissolve in an alkaline developer in the developing process after pattern exposure, and the developing 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 as a structural unit (constituent unit B) containing an acid group using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Further, the pKa of the acid group is preferably −5 or more.

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

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

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

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

[Other building blocks]
In the specific polymer, other structural units (hereinafter, may be referred to as structural unit C) other than the above-mentioned structural unit A and structural unit B do not impair the effect of the photosensitive transfer material according to the present disclosure. It may be included in the range.
The monomer forming the structural unit C is not particularly limited, and is, for example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester. , Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups with an aliphatic cyclic skeleton, and other unsaturated compounds. Saturated compounds can be mentioned.
By adjusting at least one of the type and content of the structural unit C, various properties of the specific polymer can be adjusted. In particular, by appropriately using the structural 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 structural unit C, or may contain two or more types.

Specifically, the constituent unit C is styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth). Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Examples thereof include structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetate acetate mono (meth) acrylate. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-246623 can be mentioned.

Further, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical properties of the obtained transfer material. Specific examples of the monomers forming these constituent units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. And benzyl (meth) acrylate and the like. Among them, as the structural unit C, a structural unit derived from cyclohexyl (meth) acrylate is preferably mentioned.

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

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

It is also preferable that the specific polymer contains the structural unit having the ester of the acid group in the structural unit B as the structural unit C from the viewpoint of optimizing the solubility in the developing solution and the physical properties of the photosensitive layer.
Among them, the specific polymer preferably contains a structural unit having a carboxylic acid group as the structural unit B, and further preferably contains a structural unit C containing a carboxylic acid ester group as a copolymerization component, for example, (meth) acrylic acid. A polymer containing the derived structural unit B and 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 disclosure will be given, but the present disclosure is not limited to the following examples. The ratio of the structural units and the weight average molecular weight in the following exemplified compounds are appropriately selected in order to obtain preferable physical properties.

[Polymer glass transition temperature: Tg]
The glass transition temperature (Tg) of the specific polymer in the present disclosure is preferably 90 ° C. or lower. When the Tg is 90 ° C. or lower, the photosensitive layer has high adhesion and is more excellent in transferability.
The Tg is more preferably 60 ° C. or lower, and even more preferably 40 ° C. or lower.
The lower limit of 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 forming property is maintained, and when a cover film is used, for example, a decrease in peelability when the cover film is peeled off is suppressed.
Further, the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or lower, more preferably 60 ° C. or lower, and 40 ° C. or lower from the viewpoint of transferability. Is more preferable.

The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
The specific measuring method was carried out according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011). As the glass transition temperature in the present disclosure, the extrapolated glass transition start temperature (hereinafter, may be referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, hold the device at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus stabilizes, and then heat the device at a heating rate of 20 ° C./min, which is about 30 ° C. than the temperature at which the glass transition is completed. ℃ Heat to a high temperature and draw a DTA curve or DSC curve.
The extra glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification is a straight line extending the baseline on the low temperature side of the DTA curve or the DSC curve to the high temperature side, and the stepwise change portion of the glass transition. It is calculated as the temperature at the intersection with the tangent line drawn at the point where the slope of the curve becomes maximum.

As a method for adjusting the Tg of the polymer to the above-mentioned preferable range, for example, the FOX formula is used as a guideline from the Tg of the homopolymer of each structural unit of the target polymer and the mass ratio of each structural unit. , It is possible to control the Tg of the specific polymer of interest.
The FOX formula will be described below by taking as an example a copolymer containing a first structural unit and a second structural unit.
The Tg of the homopolymer of the first structural unit contained in the copolymer is Tg1, the mass fraction of the copolymer of the first structural unit is W1, and the Tg of the homopolymer of the second structural unit is Tg2. When the mass fraction in the copolymer of the second constituent unit is W2, the Tg0 (K) of the copolymer containing the first constituent unit and the second constituent unit is as follows. Therefore, it is possible to estimate.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
Using the FOX formula described above, the type and mass fraction of each structural unit contained in the copolymer can be adjusted to obtain a copolymer having a desired Tg.
It is also possible to adjust the Tg of the polymer 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 kept low, and bonding at a low temperature (for example, 130 ° C. or less) can be realized when bonding to the substrate.
The weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
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. It is known to those skilled in the art.
For the measurement of weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) was used as a column. .6 mm ID x 15 cm, manufactured by Tosoh Corporation, Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, one each manufactured by Tosoh Corporation, connected in series, and THF (tetratetra) can be used as the eluent.
The measurement conditions are a sample concentration of 0.2% by mass, a flow velocity of 0.35 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and a differential refractive index (RI) detector. be able to.
The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", " It can be prepared using any of 7 samples of "A-2500" and "A-1000".

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

[Method for producing a specific polymer]
The method for producing the specific polymer (synthesis method) is not particularly limited, but to give an example, a polymerizable monomer for forming the structural unit A1 represented by the formula A1 and a structural unit B having an acid group are formed. It can be synthesized by polymerizing with a polymerization initiator in an organic solvent containing a polymerizable monomer for forming a polymerizable monomer and, if necessary, a polymerizable monomer for forming another structural unit C. can. It can also be synthesized by a so-called polymer reaction.

The photosensitive layer in the present disclosure contains the polymer component in a ratio of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive layer from the viewpoint of exhibiting good adhesion to the substrate. Is preferable, and it is more preferable to contain it in a ratio of 70% by mass to 98% by mass.
Further, the photosensitive layer may contain the specific polymer in a proportion of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive layer from the viewpoint of exhibiting good adhesion to the substrate. It is preferably contained in a proportion of 70% by mass to 98% by mass, more preferably.

[Other polymers]
The photosensitive layer is a polymer that does not contain the constituent unit A (when referred to as "another polymer", as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired, in addition to the specific polymer as a polymer component. There is.) May be further included. When the photosensitive layer contains other polymers, the blending amount of the other polymers is preferably 50% by mass or less, more preferably 30% by mass or less, and 20% by mass, based on the total polymer components. It is more preferably% or less.

The photosensitive layer may contain only one type of other polymer in addition to the specific polymer, or may contain two or more types.
As another 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 (all manufactured by Sartmer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all manufactured by Toagosei Inc.), and Joncryl 690, Jonc. , Styrene 67, Joncryl 586 (above, manufactured by BASF) and the like can also be used.

[Photoacid generator]
When the photosensitive layer in the present disclosure is a positive photosensitive layer, it is preferable that the photosensitive layer contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiating with radiation (also referred to as an active ray) such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. be.
As the photoacid generator used in the present disclosure, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm and generates an acid is preferable, but its chemical structure is not limited. In addition, a photoacid generator that is not directly sensitive to active light with a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
As the photoacid generator used in the present disclosure, a photoacid generator that generates an acid having a pKa of 4 or less is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator having a pKa of 2 or less is more preferable. A photoacid generator that generates the acid of the above is particularly preferable. The lower limit of pKa is not particularly determined, but is preferably -10.0 or more, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
Further, the photoacid generator preferably contains at least one compound selected from the group consisting of the onium salt compound described later and the oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and the oxime sulfonate compound. It is more preferable to include.

Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds and the like. Among these, from the viewpoint of sensitivity, resolution, and adhesion, the photoacid generator is preferably an oxime sulfonate compound. These photoacid generators can be used alone or in combination of two or more. Specific examples of the trichloromethyl-s-triazines and the diazomethane derivative include the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149.

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

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

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

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

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

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

The photoacid generator may be used alone 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, preferably 0.5% by mass, based on the total mass of the photosensitive layer from the viewpoint of sensitivity and resolution. It is more preferably to 5% by mass.

[Polymerizable compound]
When the photosensitive layer in the present disclosure is a negative photosensitive layer, it is preferable that the photosensitive layer contains a polymerizable compound.
As the polymerizable compound, an ethylenically unsaturated compound is preferable.
The ethylenically unsaturated compound is a component that 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.

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

The bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
Specific examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, new). Nakamura Chemical Industry Co., Ltd.), 1,9-Nonandiol diacrylate (A-NOD-N, Shin Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, new) Nakamura Chemical Industry Co., Ltd.) and the like.
Further, as the bifunctional ethylenically unsaturated compound, a bifunctional ethylenically unsaturated compound having a bisphenol structure is also preferably used.
Examples of the bifunctional ethylenically unsaturated compound having a bisphenol structure include the compounds described in paragraphs 0072 to 0080 of JP-A-2016-224162.
Specific examples thereof include alkylene oxide-modified bisphenol A di (meth) acrylate, such as 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane and 2,2-bis (4- (methacryloxyethoxy) ethoxy). Propoxy) phenyl) propane and the like are preferable.

The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerintri (meth) acrylate skeleton.

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

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

Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds (preferably trifunctional or higher functional urethane (meth) acrylate compounds).
Examples of the trifunctional or higher functional urethane (meth) acrylate compound include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Co., Ltd.) and the like.

Further, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group, and a carboxy group is preferable.
Examples of the ethylenically unsaturated compound having an acid group include a 3- to 4-functional ethylenically unsaturated compound having an acid group (pentaerythritol tri and tetraacrylate (PETA)) having a carboxy group introduced into the skeleton (acid value =). 80 mgKOH / g to 120 mgKOH / g)), a 5- to 6-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA)) in which a carboxy group is introduced into the skeleton (acid value = 25 mgKOH / g). ~ 70 mgKOH / g))), and the like.
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

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

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

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

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

When the photosensitive layer contains a bifunctional ethylenically unsaturated compound and a trifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional ethylenically unsaturated compound is all contained in the photosensitive layer. 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, based on the ethylenically unsaturated compound.
Further, in this case, the content of the trifunctional or higher functional ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, preferably 15% by mass to 80% by mass, based on all the ethylenically unsaturated compounds contained in the photosensitive layer. The mass% is more preferable, and 20% by mass to 70% by mass is further preferable.
Further, in this case, the content of the bifunctional or higher functional ethylenically unsaturated compound is 40% by mass or more 100 with respect to the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound. It is preferably less than mass%, more preferably 40% by mass to 90% by mass, further preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass. ..

When the photosensitive layer contains a bifunctional or higher functional ethylenically unsaturated compound, the photosensitive layer may further contain a monofunctional ethylenically unsaturated compound.
Further, when the photosensitive layer contains a bifunctional or higher ethylenically unsaturated compound, the ethylenically unsaturated compound contained in the photosensitive layer may contain a bifunctional or higher ethylenically unsaturated compound as a main component. 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 the ethylenically unsaturated compound contained in the photosensitive layer. With respect to the total content of ethylene, 60% by mass to 100% by mass is preferable, 80% by mass to 100% by mass is more preferable, and 90% by mass to 100% by mass is particularly preferable.

When the photosensitive layer contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group or a carboxylic acid anhydride thereof), the photosensitive layer has an acid group. The content of the ethylenically unsaturated compound is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, still more preferably 1% by mass to 10% by mass, based on the photosensitive layer.

[Binder polymer with acid group]
When the photosensitive layer in the present disclosure is a negative photosensitive layer, the photosensitive layer preferably contains a binder polymer having an acid group.
As the binder polymer having an acid group, an alkali-soluble resin is preferable.
Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like.
Among them, the carboxy group is preferably mentioned as the acid group.
The binder polymer having an acid group is not particularly limited, but is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, from the viewpoint of alkali developability. Is particularly preferable.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more (hereinafter, may be referred to as Specified Polymer A) is not particularly limited as long as the above acid value conditions are satisfied, and is appropriately selected from known resins. Can be used.
For example, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716, paragraphs 0033 to paragraph 0052 of JP-A-2010-237589. Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more among the polymers described in the above, and carboxy groups having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP2016-224162A. The contained acrylic resin or the like can be preferably used as the specific polymer A in the present disclosure.
Here, the (meth) acrylic resin refers to a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.
The total ratio of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the (meth) acrylic resin is preferably 30 mol% or more, more preferably 50 mol% or more.

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

The acid value of the binder polymer having an acid group used in the present disclosure is preferably 60 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, from the viewpoint of alkali developability. It is more preferably 60 mgKOH / g to 110 mgKOH / g.
In the present disclosure, acid value means a value measured according to the method described in JIS K0070 (1992).

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

Further, as the binder polymer having an acid group, any film-forming resin other than the specific polymer A can be appropriately selected and used according to the purpose. For example, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin and the like can be preferably mentioned.

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

[Photopolymerization initiator]
When the photosensitive layer in the present disclosure is a negative photosensitive layer, it is preferable that the photosensitive layer contains a photopolymerization initiator. The photopolymerization initiator receives active light such as ultraviolet rays and visible light to start the polymerization of the polymerizable compound (ethylenically unsaturated compound).
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α-”. Aminoalkylphenone-based photopolymerization initiator "), photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as" α-hydroxyalkylphenone-based polymerization initiator "), acylphosphine oxide structure. Photopolymerization initiator (hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”), photopolymerization initiator having an N-phenylglycine structure (hereinafter, “N-phenylglycine-based photopolymerization initiator””. Also known as)) and the like.

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

Further, it is also preferable that the photopolymerization initiator contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivative. The 2,4,5-triarylimidazole dimer and its derivative may be a compound represented by the following formula PI.

In the formula PI, it is preferable that at least one of X ¹ and X ² is a chlorine atom. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each have an independent substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and 1. Is more preferable. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each have an independent substituent, the substitution position is not particularly limited, and it is preferably an ortho-position or a para-position. p and q are independently integers of 1 to 5, more preferably integers of 1 to 3, and even more preferably 1.

Examples of the compound represented by the formula PI include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer. , 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, Examples include 5-diphenylimidazole dimer. In addition, the substituent of the aryl group of the two 2,4,5-triarylimidazoles may be the same and may give a target compound, or may give a different asymmetric compound.

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

Commercially available photopolymerization initiators include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01, BASF). (Manufactured by), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) , 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2- Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2) -Methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Product name: IRGACURE 369, manufactured by BASF), 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name: IRGACURE 1173, manufactured by BASF), 1-hydroxycyclohexylphenylketone (trade name:) IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF), oxime ester-based photopolymerization initiator (trade name: Lunar 6) , DKSH Japan Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole) Dimeric) (trade name: B-CIM, manufactured by Hampford) and the like.

The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1.0, based on the total mass of the photosensitive layer. More preferably, it is by mass or more.
The content of the photopolymerization initiator is preferably 10% by mass or less, 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 disclosure may contain known additives, if necessary.

-Surfactant-
The photosensitive layer in the present disclosure preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic) or amphoteric surfactants can be used, but the preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based and fluorine-based surfactants. .. In addition, under the following product names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop (manufactured by JEMCO), Megafuck (registered trademark, manufactured by DIC Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (registered trademark, Asahi Glass Co., Ltd.), PolyFox (OMNOVA Co., Ltd.), SH-8400 (Toray Dow Corning Co., Ltd.), etc. series Can be mentioned.
Further, the surfactant contains a structural unit A and a structural unit B represented by the following formula I-1, and is a polystyrene-equivalent weight average measured by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent. A copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

In formula (I-1), R ⁴⁰¹ and R ⁴⁰³ 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 carbon. An alkyl group having a number of 1 to 4 is represented, L is an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less. , Q represents a numerical value of 20% 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. show.

L is preferably a branched alkylene group represented by the following formula (I-2). ^R405 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 is preferable in terms of compatibility and wettability to the surface to be coated. 2 or 3 alkyl groups are more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

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

In addition, the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362 can also be used.

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

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

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

-solvent-
The photosensitive layer may contain a solvent.
Further, in the composition for forming a photosensitive layer for forming the photosensitive layer, in order to easily form the photosensitive layer, the viscosity of the composition for forming the photosensitive layer is adjusted by temporarily containing a solvent to form the photosensitive layer containing the solvent. The above-mentioned photosensitive layer can be suitably formed by applying and drying the composition for use.
As the solvent used in the present disclosure, 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, propylene glycol monoalkyl ether acetates, and diethylene glycol dialkyl ethers. , Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like can be exemplified. Further, specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP-A-2011-22149, and the contents thereof are incorporated in the present specification.

Further, in addition to the above-mentioned solvent, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, capric acid, 1-octanol, 1 -Solvents such as nonar, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate can also be added.
Only one type of solvent may be used, or two or more types may be used.
The solvent that can be used in the present disclosure may be used alone or in combination of two. When two or more kinds of solvents are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers are used in combination, diacetates and diethylene glycol dialkyl ethers are used in combination, or esters and butylene glycol alkyl ether acetates are used in combination. It is preferable to use it in combination with the like.

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

The content of the solvent when the composition for forming a photosensitive layer is applied is preferably 50 parts by mass to 1,900 parts by mass, preferably 100 parts by mass, per 100 parts by mass of the total solid content in the composition for forming a photosensitive layer. It is more preferably parts to 900 parts by mass.
The content of the solvent in the photosensitive layer is preferably 2% by mass or less, more preferably 1% by mass or less, and 0.5% by mass or less, based on the total mass of the photosensitive layer. Is even more preferable.

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

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

For example, even a compound having an alkyleneoxy group having the above structure (referred to as “Compound X”) is a chemically amplified positive photosensitive layer obtained by mixing Compound X, a specific polymer, and a photoacid generator. If the forming composition does not improve the plasticity as compared with the chemically amplified positive photosensitive layer forming composition formed without containing the compound X, it does not fall under the plasticizing agent in the present disclosure. For example, the arbitrarily added surfactant is not generally used in an amount that brings plasticity to the composition for forming a photosensitive layer, and therefore does not fall under the plasticizer in the present disclosure.

Examples of the plasticizer include, but are not limited to, compounds having the following structures.

From the viewpoint of adhesion, the content of the plasticizer is preferably 1% by mass to 50% by mass, more preferably 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, or may contain two or more types of plasticizer.

-Sensitizer-
When the photosensitive layer in the present disclosure is a positive photosensitive layer, the photosensitive layer may further contain a sensitizer.
The sensitizer absorbs the active light beam and becomes an electronically excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the photoacid generator undergoes a chemical change and decomposes to produce an acid.
By containing a sensitizer, the exposure sensitivity can be improved.

As the sensitizer, a compound selected from the group consisting of an anthracene derivative, acridone derivative, thioxanthone derivative, coumarin derivative, base styryl derivative, and distyrylbenzene derivative is preferable, and anthracene derivative is more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-Dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.

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

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

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

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

Examples of the sensitizing dye include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone compound, a thioxanthone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, and a triazole compound (for example, 1, 2). , 4-Triazole), stylben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.

Examples of dyes or pigments include fuchsin, phthalocyanine green, auramine base, chalcoxide green S, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, and malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE). GREEN), Basic Blue 20, Diamond Green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH) and the like.

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

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

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

The hydrogen donor is not particularly limited as long as it can give hydrogen to the photopolymerization initiator during the reaction of the exposed portion, and is, for example, bis [4- (dimethylamino) phenyl] methane, bis [4- ( Diethylamino) phenyl] methane, leuco crystal violet and the like. These can be used alone or in combination of two or more.

When the photosensitive layer contains a hydrogen donor, the content thereof is preferably 0.01% by mass to 10% by mass, preferably 0.05% by mass to 5% by mass, based on the total mass of the photosensitive layer. More preferably, it is more preferably 0.1% by mass to 2% by mass.

-Basic compound-
When the photosensitive layer in the present disclosure is a positive photosensitive layer, it is preferable that the photosensitive layer further contains a basic compound.
As the basic compound, it can be arbitrarily selected and used from the basic compounds used in the chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-22149, the contents of which are incorporated in the present specification.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, and tri. Examples thereof include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
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, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinolin, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholin, 4-methylmorpholin, 1,5-diazabicyclo [4.3.0] -5-nonen, and 1,8-diazabicyclo [5.3.0] -7-Undecene, N-cyclohexyl-N'-[2- (4-morpholinyl) ethyl] thiourea and the like can be mentioned.
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, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

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

-Heterocyclic compound-
The photosensitive layer in the present disclosure may contain a heterocyclic compound.
The heterocyclic compound in the present disclosure is not particularly limited. For example, compounds having an epoxy group or oxetanyl group in the molecules described below, heterocyclic compounds containing an alkoxymethyl group, various cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones), and nitrogen-containing monomers such as cyclic amines and oxazoline. Further, a heterocyclic monomer having d-electrons such as silicon, sulfur and phosphorus can be added.

When the heterocyclic compound is added, the amount of the heterocyclic compound added to the photosensitive layer is preferably 0.01% by mass to 50% by mass, preferably 0.1% by mass, based on the total mass of the photosensitive layer. It is more preferably% to 10% by mass, and even more preferably 1% by mass to 5% by mass. The above range is preferable from the viewpoint of adhesion and etching resistance. Only one kind of heterocyclic compound may be used, or two or more kinds may be used in combination.

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

Compounds having an epoxy group in the molecule are available as commercial products. For example, commercial products described in paragraph 0189 of JP-A-2011-22149, such as JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings, Inc.), and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-. 1000, EPPN-501, EPPN-502 (all 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 (above Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Eporide GT400, Serviners B0134, B0177 (manufactured by Daicel Corporation) and the like can be mentioned.
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, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.

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

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 disclosure, it is preferable that the heterocyclic compound is a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

-Alkoxysilane compound-
The photosensitive layer may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound is preferably mentioned.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxypropyl. Trialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Of these, γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane is more preferred, γ-glycidoxypropyltrialkoxysilane is even more preferred, and 3-glycidoxypropyltrimethoxysilane is particularly preferred. preferable. These can be used alone or in combination of two or more.

-Other ingredients-
The photosensitive layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, and the like. Further known additives such as thickeners, cross-linking agents, and organic or inorganic anti-precipitation agents can be added.
Preferred embodiments of other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated in the present specification.

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

-Method of forming the photosensitive layer-
A composition for forming a photosensitive layer for forming a photosensitive layer can be prepared by mixing each component and a solvent in an arbitrary ratio and by an arbitrary method and stirring and dissolving them. For example, it is also possible to prepare a composition by preparing a solution in which each component is previously dissolved in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

By applying the composition for forming a photosensitive layer on a cover film and drying it, the photosensitive transfer material according to the present disclosure having a photosensitive layer on a temporary support can be obtained.
The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
Further, it is also possible to form a photosensitive layer on the cover film on which another layer described later is formed.

<Cover film>
Further, the photosensitive transfer material according to the present disclosure has a cover film.
Examples of the cover film include a resin film and paper, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like. Of these, polyethylene terephthalate film is preferable, and biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the cover film is not particularly limited, and for example, one having a thickness of 1 μm to 2 mm is preferable.

<Other layers>
Even if the photosensitive transfer material according to the present disclosure has a layer other than the temporary support, the adhesive layer, the intermediate layer, the photosensitive layer and the cover film (hereinafter, may be referred to as “other layer”). good. Examples of other layers include a contrast enhancement layer and a peeling layer.

-Contrast enhancement layer-
The photosensitive transfer material according to the present disclosure may have a contrast enhancement layer in addition to the above-mentioned photosensitive layer.
The contrast enhancement layer (CEL) absorbs a large amount of light with respect to the exposure wavelength before exposure, but the absorption gradually decreases with exposure, that is, a material having high light transmittance (light extinction). It is a layer containing) (referred to as a sex pigment component). Diazonium salts, stillvazolium salts, arylnitroso salts and the like are known as photochromic dye components. As the film-forming component, a phenolic resin or the like is used.
In addition, as the contrast enhancement layer, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to paragraph 0055 of JP-A-6-332167, Photopolymer Handbook, Photopolymer Social gathering, Industrial Research Council ( 1989), Photopolymer Technology, Yamaoka, Nagamatsu ed., Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

-Release layer-
In order to improve the peelability between the cover film and the photosensitive layer, a peeling layer may be provided between the cover film and the photosensitive layer.
The release layer is not particularly limited, and a release layer known in the field of transfer film or the like can be used.
Examples of the peeling layer include a layer containing a thermoplastic resin, and the thermoplastic resin layer described in paragraph 0026 of Japanese Patent No. 4502784 is preferably used as the peeling layer.
The method for forming the release layer is not particularly limited, and the release layer may be formed by a method such as applying a composition containing a thermoplastic resin described in paragraphs 0189 to 0193 of JP-A-2014-85643 to a cover film. Further, a cover film on which a release layer is formed in advance may be obtained and used.
When a release layer is provided between the cover film and the photosensitive layer, it is also preferable that the photosensitive layer is formed on the release layer in the step of forming the photosensitive layer.

(Manufacturing method of photosensitive transfer material)
The method for producing a photosensitive transfer material according to the present disclosure is as follows.
A step of applying a photosensitive layer forming composition on a cover film to form a photosensitive layer (photosensitive layer forming step), and a process of forming the photosensitive layer.
A step of applying a composition for forming an intermediate layer containing at least particles on the photosensitive layer to form an intermediate layer (intermediate layer forming step).
It is preferable to include a step of bonding the temporary support having the adhesive layer so that the adhesive layer is in contact with the intermediate layer (temporary support bonding step).
As the composition for forming a photosensitive layer and the composition for forming an intermediate layer in the method for producing a photosensitive transfer material, the above-mentioned ones described in the photosensitive transfer material are preferably used.
According to the method for producing a photosensitive transfer material according to the present disclosure, it is easy to obtain a photosensitive transfer material having irregularities formed by particles on the surface of the intermediate layer after the adhesive layer and the intermediate layer are peeled off.
Further, the method for producing the photosensitive transfer material according to the present disclosure is preferably a method for obtaining the photosensitive transfer material according to the present disclosure.

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

<Intermediate layer forming process>
The method for producing a photosensitive transfer material according to the present disclosure preferably includes a step of applying a composition for forming an intermediate layer containing at least the particles on the photosensitive layer to form the intermediate layer.
The method for applying the composition for forming the intermediate layer is not particularly limited, and a known method may be used, and examples thereof include known methods such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, the method for forming the intermediate layer is as described above.

<Temporary support bonding process>
The method for producing a photosensitive transfer material according to the present disclosure preferably includes a step of adhering a temporary support having an adhesive layer so that the adhesive layer is in contact with the intermediate layer.
The step of laminating the temporary support is not particularly limited, and a known method may be used, and examples thereof include a method of laminating the temporary support so that the adhesive layer and the intermediate layer are in contact with each other.
The term "laminate" as used in the present disclosure refers to laminating a temporary support having an adhesive layer so as to be in contact with the intermediate layer so that air bubbles do not easily enter between the intermediate layer and the adhesive layer. From the viewpoint of suppressing the pressure and improving the adhesion between the intermediate layer and the adhesive layer, it is preferable to use at least one of heating and pressing.

As a device used when laminating a temporary support having an adhesive layer so as to be in contact with an intermediate layer, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity is used. Can be used.
It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.

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

<Other processes>
The method for producing a photosensitive transfer material according to the present disclosure may further include other steps.
Examples of the other step include a step of forming another layer contained in the above-mentioned photosensitive transfer material.
The method for forming the other layer is not particularly limited, and the layer may be formed by a known method.

(Manufacturing method of resin pattern and manufacturing method of circuit wiring)
The method for producing the resin pattern according to the present disclosure is not particularly limited, but the step of peeling the cover film in the photosensitive transfer material according to the present disclosure and the above-mentioned in the photosensitive transfer material from which the cover film has been peeled off. A step of bringing the outermost layer on the photosensitive layer side into contact with a support having a conductive layer and sticking them together, a step of peeling off the temporary support, the adhesive layer, and the intermediate layer, and the intermediate layer. It is preferable to include, in this order, a step of bringing the exposure mask into contact and pattern-exposing the photosensitive layer through the exposure mask, and a step of developing the photosensitive layer to form a resin pattern.
The method for manufacturing the circuit wiring according to the present disclosure is not particularly limited as long as it is a method for manufacturing the circuit wiring using the photosensitive transfer material according to the present disclosure, but the above-mentioned cover in the photosensitive transfer material according to the present disclosure. A step of peeling the film, a step of bringing the outermost layer of the photosensitive transfer material from which the cover film has been peeled off on the photosensitive layer side into contact with a support having a conductive layer, and a step of bonding the temporary support. A step of peeling the adhesive layer and the intermediate layer, a step of bringing an exposure mask into contact with the intermediate layer, and pattern-exposing the photosensitive layer through the exposure mask, and developing the photosensitive layer. It is preferable to include a step of forming the resin pattern and a step of etching the conductive layer using the formed resin pattern as a mask in this order.
The "outermost layer on the photosensitive layer side" in the photosensitive transfer material in the present disclosure refers to the photosensitive layer having a temporary support, an adhesive layer, an intermediate layer, and a photosensitive layer in this order. Needless to say, it is the outermost layer on the photosensitive layer side of the transfer material.
Further, the support is also referred to as a "base material", and the support having the conductive layer is also referred to as a "substrate".

Conventionally, the photosensitive layer is divided into a negative type in which a portion irradiated with active light remains as an image and a positive type in which a portion not irradiated with active light remains as an image, depending on the difference in the photosensitive system. In the positive type, by irradiating with active light rays, for example, in order to improve the solubility of the exposed part by using a photosensitive agent that generates acid by being irradiated with active light rays, both the exposed part and the unexposed part are exposed at the time of pattern exposure. If the pattern is not cured and the obtained pattern shape is defective, the substrate can be reused (reworked) by full exposure or the like. Therefore, from the viewpoint of excellent so-called reworkability, the positive type is preferable. Further, since the technique of re-exposing the remaining photosensitive layer to produce a different pattern can be realized only by the positive photosensitive layer, the method for manufacturing the resin pattern according to the present disclosure or the circuit wiring according to the present disclosure. When a positive photosensitive layer is used in the above manufacturing method, an embodiment in which exposure is performed twice or more is also preferable.

<Cover film peeling process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure preferably includes a step of peeling the cover film in the photosensitive transfer material according to the present disclosure (cover film peeling step). ..
The peeling method is not particularly limited and may be peeled by a known method. For example, a method of grasping and peeling a part of the temporary support using a finger or an instrument such as tweezers can be mentioned.

<Lasting process>
In the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, the outermost layer on the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off is a conductive layer. It is preferable to include a step of bringing the support into contact with the support (bonding step).
In the bonding step, it is preferable to press the photosensitive transfer material from which the substrate and the cover film have been peeled off so that the conductive layer and the outermost layer on the photosensitive layer side come into contact with each other. According to the above aspect, the patterned photosensitive layer after exposure and development can be suitably used as an etching resist when etching the conductive layer.
The method of pressure-bonding the substrate and the photosensitive transfer material from which the cover film has been peeled off is not particularly limited, and a known transfer method or laminating method can be used.
Specifically, the substrate and the photosensitive transfer material are overlapped so that the outermost layer on the photosensitive layer side of the photosensitive transfer material is in contact with the conductive layer, and the substrate and the photosensitive transfer material are pressed by a roll or the like, or pressurized and heated. The method to be carried out is preferably mentioned. For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
The crimping pressure and temperature in the bonding step are not particularly limited, and are appropriately depending on the surface material of the support to be bonded, for example, the material of the conductive layer and the photosensitive layer, the transport speed, the crimping machine to be used, and the like. Can be set. When the cover film is provided on the photosensitive layer of the photosensitive transfer material, the cover film may be removed from the photosensitive layer and then pressure-bonded.
When the base material is a resin film, crimping may be performed by roll-to-roll.

[Support (base material)]
The support is preferably a glass base material or a film base material, and more preferably a film base material. In the circuit wiring manufacturing method according to the present disclosure, in the case of touch panel wiring, it is particularly preferable that the support is a sheet-shaped resin composition.
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 translucent base material such as a glass base material, and tempered glass typified by Corning's gorilla glass can be used. Further, as the above-mentioned transparent base material, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
When a film base material is used as the base material, it is more preferable to use a base material having less optical strain and a base material having high transparency, and specific materials include polyethylene terephthalate (PET). Examples thereof include polyethylene terephthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

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

When the support has a plurality of conductive layers, in the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, at least one of the plurality of conductive layers is metal-oxidized. It is preferable to include an object.
As the conductive layer, it is preferable that the electrode pattern corresponds to the sensor of the visual recognition portion used in the capacitive touch panel or the wiring of the peripheral extraction portion.

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

<Temporary support peeling process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure is a step of peeling the temporary support, the adhesive layer, and the intermediate layer (temporary support peeling step). It is preferable to include.
The method for peeling the temporary support in the temporary support peeling step is not particularly limited, and the temporary support may be peeled by a known method.

<Exposure process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure is a step of bringing an exposure mask into contact with the intermediate layer and pattern-exposing the photosensitive layer through the exposure mask (exposure step). ) Is preferably included.
By bringing the exposure mask into contact with the intermediate layer for exposure, the distance between the photosensitive layer and the mask is reduced, so that the resolution of the pattern is improved, and the influence of foreign matter in the temporary support can be eliminated.
In the above exposure step, it is preferable to irradiate the substrate on which at least the intermediate layer and the photosensitive layer are formed with active light rays through a mask having a pattern.
When the photosensitive layer is of the positive type, the photoacid generator is decomposed and acid is generated in this step. Due to the catalytic action of the generated acid, the acid-degradable group contained in the photosensitive layer is decomposed to generate an acid group, for example, a carboxy group or a phenolic hydroxyl group.
When the photosensitive layer is a negative type, the polymerizable compound is polymerized in this step.
In the present disclosure, the detailed arrangement and specific size of the pattern in the mask are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit board manufactured in the present disclosure and to make the area occupied by the take-out wiring as small as possible, at least a part of the pattern (particularly a touch panel) is desired. The electrode pattern and the portion of the take-out wiring) are preferably thin wires of 100 μm or less, and more preferably 70 μm or less.

Examples of the active light include visible light, ultraviolet light, and electron beam, but visible light or ultraviolet light is preferable, and ultraviolet light is particularly preferable.
As an exposure light source using active light, 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 excima laser generator, or the like can be used, and g-line (436 nm) and i-line (365 nm) can be used. , H-rays (405 nm) and other active rays having a wavelength of 300 nm or more and 450 nm or less can be preferably used. Further, if necessary, the irradiation light can be adjusted through a spectroscopic filter such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter.
As the exposure device, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, 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, but is preferably 5 mJ / cm ² to 200 mJ / cm ² , and more preferably 10 mJ / cm ² to 100 mJ / cm ² .
Further, it is also preferable to perform heat treatment before development for the purpose of improving the rectangularness and linearity of the pattern after exposure. By the so-called PEB (Post Exposure Bake) process, it is possible to reduce the roughness of the pattern edge due to the standing wave generated in the photosensitive layer during exposure.

<Development process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure preferably includes a step (development step) of developing the photosensitive layer to form a resin pattern.
When the photosensitive layer is of the positive type, the exposed portion of the photosensitive layer is removed by development. When the photosensitive layer is a negative type, the unexposed portion of the photosensitive layer is removed by development.
Further, in the developing step, the intermediate layer may be removed together with the portion removed by the development of the photosensitive layer.
The exposed photosensitive layer can be developed by using a developing solution in the developing step.
The developing solution is not particularly limited as long as the photosensitive layer can be developed, and a known developing solution such as the developing solution described in JP-A-5-72724 can be used. The developer is preferably a developer in which the portion of the photosensitive layer from which the photosensitive layer is removed has a dissolution-type development behavior. As the developing solution, an alkaline aqueous solution is preferable, and for example, an alkaline aqueous solution containing a compound having pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is more preferable. The developer may further contain an organic solvent miscible with water, a surfactant and the like. Examples of the developer preferably used in the present disclosure include the developer described in paragraph 0194 of International Publication No. 2015/093271.

The development method is not particularly limited and may be any of paddle development, shower development, shower and spin development, dip development and the like. Here, the shower development will be described. By spraying a developer on the photosensitive layer and the intermediate layer after exposure by a shower, the exposed portion can be removed. Further, after the development, it is preferable to spray a cleaning agent or the like with a shower and rub it with a brush or the like to remove the development residue. The liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.
Further, the development may be performed immediately after the exposure, but the time from the exposure to the development may be about 0.5 hours to several hours after the exposure.
Further, the method for manufacturing a resin pattern according to the present disclosure, or the method for manufacturing a circuit wiring according to the present disclosure, is known such as a step of washing with water or the like after development, a step of drying a support having the obtained pattern, and the like. May include the steps of.

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

The transport speed of the support in each step of the method for manufacturing the resin pattern according to the present disclosure or the method for manufacturing the circuit wiring according to the present disclosure is not particularly limited, but is 0.5 m / m / except for the time of exposure. It is preferably min to 10 m / min, and more preferably 2.0 m / min to 8.0 m / min except during exposure.

<Etching process>
The method for manufacturing a circuit wiring according to the present disclosure preferably includes a step (etching step) of etching the conductive layer using the formed resin pattern as a mask.
In the etching step, the pattern formed from the photosensitive layer by the developing step is used as an etching resist, and the conductive layer is etched.
Etching of the conductive layer can be applied by a known method such as the method described in paragraphs 0048 to 0054 of JP-A-2010-152155, and the method by dry etching such as known plasma etching. ..
For example, as an etching method, a commonly used wet etching method of immersing in an etching solution can be mentioned. As the etching solution used for wet etching, an acidic type or alkaline type etching solution may be appropriately selected according to the etching target.
As the acidic type etching solution, an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or phosphoric acid, an acidic component and ferric chloride, ammonium fluoride, or permanganese Examples thereof include a mixed aqueous solution of a salt such as potassium acid. As the acidic component, a component in which a plurality of acidic components are combined may be used.
The alkaline type etching solution includes an aqueous solution of an alkaline component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or a salt of an organic amine such as tetramethylammonium hydroxide, an alkaline component and potassium permanganate. A mixed aqueous solution of salts such as, etc. is exemplified. As the alkaline component, a component in which a plurality of alkaline components are combined may be used.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. In the present disclosure, it is preferable that the pattern used as an etching mask (etching pattern) exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the pattern is prevented from being peeled off during the etching step, and the portion where the pattern does not exist is selectively etched.

After the etching step, in order to prevent contamination of the process line, if necessary, a step of cleaning the support having the etched conductive layer (cleaning step) and a support having the etched conductive layer. A step of drying the body (drying step) may be performed. Examples of the cleaning step include cleaning the substrate with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.). As for the drying step, for example, an air blow may be used, and the air blow pressure (about 0.1 kg / cm ² to 5 kg / cm ² ) may be appropriately adjusted for drying.

<Etching resist peeling process>
The method for manufacturing a circuit wiring according to the present disclosure preferably includes a step of peeling the photosensitive layer with a stripping liquid (etching resist stripping step) after the etching step.
After the completion of the etching step, the patterned photosensitive layer remains. If the photosensitive layer is unnecessary, all the remaining photosensitive layers may be removed.
As a method of peeling using a stripping solution, for example, a substrate having the photosensitive layer or the like is added to the stripping solution being stirred at preferably at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 5 minutes to 30 minutes. A method of soaking for a minute can be mentioned.
As the stripping solution, for example, an inorganic alkaline component such as sodium hydroxide or potassium hydroxide, or an organic alkaline component such as a tertiary amine or a quaternary ammonium salt may be used as water, dimethylsulfoxide, N-methylpyrrolidone, or. , A stripping solution dissolved in a mixed solution of these. A stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.

Further, in the circuit wiring manufacturing method according to the present disclosure, the exposure step, the developing step and the etching step may be repeated twice or more, if necessary.
As an example of the exposure step, the developing step and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure may include any other step. For example, the following steps can be mentioned, but the steps are not limited to these steps.

<Step to reduce visible light reflectance>
The method for manufacturing a circuit wiring according to the present disclosure includes a step of reducing the visible light reflectance on the surface of the conductive layer, for example, a part or all of the surface of the conductive layer on the support. It is possible.
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, by oxidizing copper to obtain copper oxide, it is possible to reduce the visible light reflectance by blackening the copper.
Preferable embodiments of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Laid-Open No. 2013-206315. There is a description and the contents of this publication are incorporated herein by reference.

<Step of forming an insulating film on the etched support having the conductive layer, and step of forming a new conductive layer on the insulating film>
The method for manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on a support having the conductive layer, for example, a formed wiring (etched conductive layer), and a new method on the insulating film. It is also preferable to include a step of forming a conductive layer.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
The process of forming a new conductive layer on the insulating film is not particularly limited. A photosensitive material having conductivity may be used to form a new conductive layer of a desired pattern by photolithography.

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

Further, in the method for manufacturing a circuit wiring according to the present disclosure, the support has a plurality of conductive layers on both surfaces thereof, and the circuit is sequentially or simultaneously with respect to the conductive layers formed on both surfaces of the support. It is also preferable to form. With such a configuration, 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 for a touch panel. Wiring can be formed.

(Wiring and wiring board)
The wiring according to the present disclosure is a wiring manufactured by the manufacturing method of the circuit wiring according to the present disclosure. Further, as the wiring, circuit wiring is preferably mentioned.
The wiring board according to the present disclosure is a board having wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure.
The use of the wiring board according to the present disclosure is not limited, but for example, a wiring board for a touch panel is preferable.

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

(Touch panel and touch panel display device)
The touch panel according to the present disclosure is a touch panel having at least the wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure. Further, the touch panel according to the present disclosure preferably has at least a transparent substrate, electrodes, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least the wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure, and is preferably a touch panel display device having the touch panel according to the present disclosure.
As the detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Above all, the capacitance method is preferable.

The touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-51751), and a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125). The one described in FIG. 19 of the publication, the one described in FIG. 1 or FIG. 5 of JP2012-89102, OGS (One Glass Solution) type, TOR (Touch-on-Lens) type (for example, JP-A). (The one described in FIG. 2 of Japanese Patent Application Laid-Open No. 2013-5472), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.) can be mentioned.

As the touch panel related to this disclosure and the touch panel display device related to this disclosure, "Latest Touch Panel Technology" (July 6, 2009, published by Techno Times Co., Ltd.), supervised by Yuji Mitani, "Touch Panel Technology and Development" ( (December 2004, CMC Publishing), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiments of the present disclosure. Therefore, the scope of the embodiments of the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

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

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

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

-Synthesis of ATH-
Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to the three-necked flask and cooled to 20 ° C. After dropping camphorsulfonic acid (0.0070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mol equivalent), the temperature is 20 ° C ± 2 ° C for 1.5 hours. After stirring, the temperature was raised to 35 ° C. and the mixture was stirred for 2 hours. After spreading Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalsite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) on Nutche in this order, the reaction solution is filtered. The filtrate was obtained. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C. to make 140.8 parts by mass of tetrahydrofuran-2-yl acrylate (ATHF) colorless oil. Obtained as a product (yield 99.0%).

[Photoacid generator]
Photoacid generator B-1: A compound having the structure shown below (a compound described in paragraph 0227 of JP2013-047765, which was synthesized according to the method described in paragraph 0204).

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

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

<Preparation of composition 1 for forming an intermediate layer>
The following components were mixed and filtered through a filter made of polytetrafluoroethylene having a pore size of 5.0 μm to obtain a composition 1 for forming an intermediate layer.
Water: 930.0 parts by mass Methanol: 930.0 parts by mass Polymer A-11: 95.0 parts by mass Particles G-1: 25.0 parts by mass Surfactant E-11: 0.05 parts by mass

[Polymer (binder polymer for intermediate layer)]
Polymer A-111: Metrose 60SH-03 (hydroxypropylmethylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.)

〔particle〕
Particle G-1: Snowtex (registered trademark) OYL (silica particles, average particle diameter 50 nm to 80 nm, solid content 20% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

[Surfactant]
Surfactant E-11: Megafuck F-444 (manufactured by DIC Corporation)

<Preparation of photosensitive transfer material>
The photosensitive resin composition 1 was applied onto a polyethylene terephthalate film having a thickness of 25 μm as a cover film using a slit-shaped nozzle so that the dry film thickness was 3.0 μm. After the above coating, it was dried in a convection oven at 100 ° C. for 2 minutes to form a photosensitive layer. After forming the photosensitive layer, the intermediate layer forming composition 1 was applied onto the photosensitive layer so that the dry film thickness was 1.0 μm. Then, it was dried in a convection oven at 100 ° C. for 2 minutes to prepare a film A having an intermediate layer on the photosensitive layer.
Further, E-MASK AW303D manufactured by Nitto Denko Corporation was prepared as a film B as a temporary support with an adhesive layer containing a urethane adhesive.
Finally, the film A and the film B were thermally laminated at a speed of 90 ° C. and 5 m / min so that the intermediate layer of the film A and the adhesive layer of the film B were in contact with each other to prepare a photosensitive transfer material.

<Making a resin pattern>
After peeling off the cover film, the prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (lamination rate) of 3.6 m / min.
Then, the temporary support with the adhesive layer is peeled off, and the photosensitive layer of the photosensitive transfer material and the mask having a line-and-space pattern (Duty ratio 1: 1) with a line width of 3 to 20 μm made of glass are exposed. The contacts were made while adjusting the position (alignment), exposed to an ultra-high pressure mercury lamp via the above mask, allowed to stand for 30 minutes, and then developed to form a resin pattern. Development was carried out by shower development for 40 seconds using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C.

<Creation of circuit wiring pattern>
A circuit wiring pattern is created by etching the patterned sample with a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.) at 23 ° C for 30 seconds and removing the resist using a 4 mass% sodium hydroxide solution. did.

(Example 2)
The amount of the particles G-1 added to the intermediate layer forming composition 1 is 50.0 parts by mass (since the solid content of the particles G-1 is 20% by mass, the particles in the total solid content of the intermediate layer forming composition 1). The photosensitive transfer material was prepared in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass), and a resin pattern and a circuit wiring pattern were formed. ..

(Example 3)
The amount of the particles G-1 added to the intermediate layer forming composition 1 is 100.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 is 20% by mass), and the polymer A-11 is used. A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the particles was 80 parts by mass, and a resin pattern and a circuit wiring pattern were formed.

(Example 4)
The amount of the particles G-1 added to the intermediate layer forming composition 1 is 200.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 is 40% by mass), and the polymer A-11 A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the particles was 60 parts by mass, and a resin pattern and a circuit wiring pattern were formed.

(Example 5)
The amount of the particles G-1 added to the intermediate layer forming composition 1 is 300.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 is 60% by mass), and the polymer A-11 A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the particles was 40 parts by mass, and a resin pattern and a circuit wiring pattern were formed.

(Example 6)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-2, and the addition amount was 50.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-2: Snowtex OL (silica particles, average particle diameter: 40 nm to 50 nm, solid content 20% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 7)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-3, and the addition amount was 25.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-3: Snowtex O-40 (silica particles, average particle diameter: 20 nm to 25 nm, solid content 40% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 8)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-4, and the addition amount was 200.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 40% by mass). ), A photosensitive transfer material was prepared in the same manner as in Example 1 except that the content of the polymer A-11 was 60 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-4: Snowtex O (silica particles, average particle diameter: 10 nm to 15 nm, solid content 20% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 9)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-5, and the addition amount was 200.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was prepared in the same manner as in Example 1 except that the content of the polymer A-11 was 60 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-5: Snowtex ZL (silica particles, average particle diameter: 70 nm to 100 nm, solid content 40% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 10)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-6, and the addition amount was 25.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-6: Snowtex MP-2040 (silica particles, average particle diameter: 170 nm to 230 nm, solid content 40% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 11)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-7, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-7: Seahoster KE-W10 (amorphous silica particles, average particle diameter: 100 nm, solid content 15% by mass, manufactured by Nippon Shokubai Co., Ltd.)

(Example 12)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-8, and the addition amount was 200.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-8: Soliostar SP01-150 (organic-inorganic composite compound particles, average particle diameter: 150 nm, solid content 5% by mass, manufactured by Nippon Shokubai Co., Ltd.)

(Example 13)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-9, and the addition amount was 117.6 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-9: Epostal MX030W (acrylic crosslinked particles, average particle diameter: 40 nm, solid content 10% by mass, manufactured by Nippon Shokubai Co., Ltd.)

(Example 14)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-10, and the addition amount was 117.6 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-10: Epostal MX050W (Acrylic crosslinked particles, average particle diameter: 70 nm, solid content 10% by mass, manufactured by Nippon Shokubai Co., Ltd.)

(Example 15)
The particles G-1 in the intermediate layer forming composition 1 were changed to particles G-11, and the addition amount was 117.6 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-11: Epostal MX100W (Acrylic crosslinked particles, average particle diameter: 150 nm, solid content 10% by mass, manufactured by Nippon Shokubai Co., Ltd.)

(Example 16)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-12, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-12: SokenMP-451 (non-crosslinked acrylic particles, average particle diameter: 150 nm, manufactured by Soken Chemical Co., Ltd.) was mixed with water so that the solid content was 15% by mass, and dispersed using a paint shaker. ..

(Example 17)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-13, and the addition amount was 37.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-13: Tuftic F-167 (crosslinked polymethyl methacrylate particles, average particle diameter: 300 nm, solid content 27% by mass, manufactured by Toyobo Co., Ltd.)

(Example 18)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-14, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-14: Tospearl 120 (siloxane particles, average particle diameter: 2000 nm, manufactured by Momentive Performance Materials) was mixed with water so that the solid content was 15% by mass, and dispersed using a paint shaker. ..

(Example 19)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-15, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-15: Trepearl EP (epoxy resin particles, average particle diameter: 200 nm to 300 nm, manufactured by Toray Industries, Inc.) was mixed with water so that the solid content was 15% by mass, and dispersed using a paint shaker.

(Example 20)
Particle G-1 in the intermediate layer forming composition 1 was changed to particle G-16, and the addition amount was 50.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 was 10% by mass). ), A photosensitive transfer material was produced in the same manner as in Example 1 except that the content of the polymer A-11 was 90 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Particle G-16: Alumina sol AS-200 (alumina particles, average particle diameter: 7 nm to 15 nm, solid content 10% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 21)
The polymer A-11 was changed to the polymer A-12, and the amount of the particles G-1 added was 50.0 parts by mass (the content of the particles in the total solid content of the composition 1 for forming the intermediate layer was 10% by mass). Further, the particles G-4 were added to make the addition amount 150.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 1 is 30% by mass), and the polymer A-12 was contained. A photosensitive transfer material was produced in the same manner as in Example 1 except that the amount was 60 parts by mass, and a resin pattern and a circuit wiring pattern were formed.
Polymer A-12: Nisso HPC-SSL (hydroxypropyl cellulose, manufactured by Nippon Soda Corporation)

(Example 22)
Photosensitive transfer in the same manner as in Example 21 except that the temporary support E-MASK AW303D was changed to E-MASK RP207 (a temporary support with an adhesive layer containing an acrylic adhesive, manufactured by Nitto Denko KK). Materials were made to form resin patterns and circuit wiring patterns.

(Example 23)
A photosensitive transfer material was produced in the same manner as in Example 21 except that the temporary support E-MASK AW303D was changed to PanaProtect HP25 (a temporary support with an adhesive layer containing an acrylic adhesive, manufactured by Panac Co., Ltd.). Then, a resin pattern and a circuit wiring pattern were formed.

(Example 24)
A photosensitive transfer material was prepared in the same manner as in Example 21 except that the temporary support E-MASK AW303D was changed to PanaProtect MK38S (a temporary support with an adhesive layer containing an acrylic adhesive, manufactured by Panac Co., Ltd.). Then, a resin pattern and a circuit wiring pattern were formed.

(Example 25)
The photosensitive transfer material was prepared by the same method as in Example 1 except that the photosensitive resin composition 1 was changed to the photosensitive resin composition 2 and the intermediate layer forming composition 1 was changed to the intermediate layer forming composition 2. After that, a resin pattern and a wiring pattern were made.

<Preparation of Photosensitive Resin Composition 2>
The following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 5.0 μm to obtain a photosensitive resin composition.
PGMEA: 453.6 parts by mass Polymer A-2: 125.0 parts by mass Polymerizable compound C-1: 30.0 parts by mass Polymerizable compound C-2: 20.0 parts by mass Photopolymerization initiator B-CIM: 4.0 parts by mass Sensitizing dye PYR-1: 0.1 parts by mass Hydrogen donor LCV: 0.65 parts by mass Dye MKG: 0.03 parts by mass

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

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

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

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

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

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

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

<Preparation of composition 2 for forming an intermediate layer>
The following components were mixed and filtered through a filter made of polytetrafluoroethylene having a pore size of 5.0 μm to obtain a composition 2 for forming an intermediate layer.
Water: 915.0 parts by mass Methanol: 915.0 parts by mass Polymer A-13: 63.3 parts by mass Polymer A-14: 31.65 parts by mass Particles G-17: 12.5 parts by mass Surfactant E -11: 0.05 parts by mass

[Polymer (binder polymer for intermediate layer)]
Polymer A-13: Kuraray Poval PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.)
Polymer A-14: Polyvinylpyrrolidone (PVP-) K-30 (Polyvinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd.)

〔particle〕
Particle G-17: Snowtex YL (silica particles, average particle diameter 50 nm to 80 nm, solid content 40% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 26)
The amount of the particles G-17 added was 25.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass), and the content of the polymer A-13 was 60 parts by mass. A photosensitive transfer material was produced in the same manner as in Example 25 except that the content of the polymer A-14 was 30 parts by mass, and a resin pattern and a circuit wiring pattern were formed.

(Example 27)
The amount of the particles G-17 added is 50.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 is 20% by mass), and the total of the polymer A-13 and the polymer A-14 is set. It was carried out except that the content was 80 parts by mass and the content ratio of the polymer A-13 to the polymer A-14 was polymer A-13: polymer A-14 = 2: 1 (mass ratio). A photosensitive transfer material was prepared in the same manner as in Example 25, and a resin pattern and a circuit wiring pattern were formed.

(Example 28)
The amount of the particles G-17 added is 100.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 is 40% by mass), and the total of the polymer A-13 and the polymer A-14 is set. It was carried out except that the content was 60 parts by mass and the content ratio of the polymer A-13 to the polymer A-14 was polymer A-13: polymer A-14 = 2: 1 (mass ratio). A photosensitive transfer material was prepared in the same manner as in Example 25, and a resin pattern and a circuit wiring pattern were formed.

(Example 29)
The addition amount of the particles G-17 is 150.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 is 60% by mass), and the total of the polymer A-13 and the polymer A-14. It was carried out except that the content was 40 parts by mass and the content ratio of the polymer A-13 to the polymer A-14 was polymer A-13: polymer A-14 = 2: 1 (mass ratio). A photosensitive transfer material was prepared in the same manner as in Example 25, and a resin pattern and a circuit wiring pattern were formed.

(Example 30)
The particles G-17 in the intermediate layer forming composition 2 were changed to the particles G-18, and the addition amount was 33.3 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90 parts by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: the polymer A-14. A photosensitive transfer material was produced in the same manner as in Example 25 except that the ratio was 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.
Particle G-18: Snowtex 30L (silica particles, average particle diameter: 10 nm to 15 nm, solid content 30% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 31)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-19, and the addition amount was 20.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.
Particle G-19: Snowtex 50 (silica particles, average particle diameter: 20 nm to 25 nm, solid content 48% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 32)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-20, and the addition amount was 133.3 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 40% by mass). ), The total content of the polymer A-13 and the polymer A-14 is set to 60% by mass, and the content ratio of the polymer A-13 to the polymer A-14 is set to the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.
Particle G-20: Snowtex 30 (silica particles, average particle diameter: 10 nm to 15 nm, solid content 30% by mass, manufactured by Nissan Chemical Industry Co., Ltd.)

(Example 33)
The particles G-17 in the intermediate layer forming composition 2 were changed to the particles G-5, and the addition amount was 25.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 34)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-6, and the addition amount was 25.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 35)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-7, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 36)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-8, and the addition amount was 200.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 37)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-9, and the addition amount was 117.6 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 38)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-10, and the addition amount was 117.6 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 39)
The particles G-17 in the intermediate layer forming composition 2 were changed to particles G-11, and the addition amount was 117.6 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 40)
The particles G-17 in the intermediate layer forming composition 2 were changed to the particles G-12, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 41)
The particles G-17 in the intermediate layer forming composition 2 were changed to the particles G-13, and the addition amount was 37.0 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 42)
The particles G-17 in the intermediate layer forming composition 2 were changed to the particles G-14, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 43)
The particles G-17 in the intermediate layer forming composition 2 were changed to the particles G-15, and the addition amount was 66.7 parts by mass (the content of the particles in the total solid content of the intermediate layer forming composition 2 was 10% by mass). ), The total content of the polymer A-13 and the polymer A-14 is 90% by mass, and the content ratio of the polymer A-13 and the polymer A-14 is the polymer A-13: polymer. A photosensitive transfer material was produced in the same manner as in Example 25 except that A-14 = 2: 1 (mass ratio), and a resin pattern and a circuit wiring pattern were formed.

(Example 44)
A photosensitive transfer material was prepared in the same manner as in Example 26, except that the temporary support E-MASK AW303D was changed to E-MASK RP207 (a temporary support having an adhesive layer, manufactured by Nitto Denko KK). A resin pattern and a circuit wiring pattern were formed.

(Example 45)
A photosensitive transfer material was prepared in the same manner as in Example 26 except that the temporary support E-MASK AW303D was changed to PanaProtect HP25 (a temporary support with an adhesive layer containing an acrylic adhesive, manufactured by Panac Co., Ltd.). Then, a resin pattern and a circuit wiring pattern were formed.

(Example 46)
A photosensitive transfer material was prepared in the same manner as in Example 26 except that the temporary support E-MASK AW303D was changed to PanaProtect MK38S (a temporary support with an adhesive layer containing an acrylic adhesive, manufactured by Panac Co., Ltd.). Then, a resin pattern and a circuit wiring pattern were formed.

(Comparative Example 1)
A photosensitive transfer material was prepared in the same manner as in Example 1 except that the particles G-1 were not added in the preparation of the intermediate layer forming composition 1, and a resin pattern and a circuit wiring pattern were formed.

(Comparative Example 2)
A photosensitive transfer material was prepared in the same manner as in Example 25 except that particles G-17 were not added in the preparation of the intermediate layer forming composition 2, and a resin pattern and a circuit wiring pattern were formed.

(Comparative Example 3)
A photosensitive transfer material was prepared in the same manner as in Example 1 except that a 25 μm-thick polyethylene terephthalate film having no adhesive layer was used instead of the E-MASK AW303D manufactured by Nitto Denko Corporation as a temporary support. , Resin pattern and circuit wiring pattern were formed.

(Comparative Example 4)
A photosensitive transfer material was prepared in the same manner as in Example 25 except that a 25 μm-thick polyethylene terephthalate film having no adhesive layer was used instead of the E-MASK AW303D manufactured by Nitto Denko Corporation as a temporary support. , Resin pattern and circuit wiring pattern were formed.

(evaluation)
<Evaluation of unevenness formation>
After peeling off the cover film, the photosensitive transfer material produced in each Example or Comparative Example is laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating rate) of 3.6 m / min. did. Then, the temporary support and the adhesive layer were peeled off, and the formation of irregularities on the surface of the photosensitive layer was confirmed by SEM. Those with irregularities were evaluated as "yes", and those without irregularities or those with irregularities crushed and pushed into the film were evaluated as "none".
The evaluation results are shown in Table 1 or Table 2.

<Evaluation of slipperiness against mask>
After peeling off the cover film, the photosensitive transfer material produced in each Example or Comparative Example is laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating speed) of 3.6 m / min. did.
After that, the temporary support and the adhesive layer are peeled off, and the intermediate layer of the photosensitive transfer material is brought into contact with a glass mask having a line-and-space pattern (duty ratio 1: 1) having a line width of 3 μm to 20 μm. (Contact) was performed, and the static friction coefficient was calculated using a static friction meter Heidon 10 manufactured by Shinto Kagaku Co., Ltd. The evaluation results are shown in Table 1 or Table 2. The evaluation result is preferably 3 to 5, more preferably 4 or 5, and even more preferably 5.
It is considered that the smaller the coefficient of static friction, the better the slipperiness against the mask during contact exposure, and the easier the alignment after the mask is brought into contact with the medium interference.

〔Evaluation criteria〕
5: Static friction coefficient is less than 0.3 4: Static friction coefficient is 0.3 or more and less than 0.5 3: Static friction coefficient is 0.5 or more and less than 1.0 2: Static friction coefficient is 1.0 or more and less than 1.6 1: Static friction coefficient is 1.6 or more

<Evaluation of linearity>
The prepared photosensitive transfer material was peeled off from the cover film and then laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (lamination rate) of 3.6 m / min.
After that, the temporary support and the adhesive layer are peeled off, and the intermediate layer of the photosensitive transfer material is brought into contact with a mask having a line-and-space pattern (Duty ratio 1: 1) having a line width of 10 μm made of glass, and the above mask is applied. The line-and-space pattern with a line width of 10 μm was exposed to a ghi line (435 nm, 405 nm, 365 nm) with an ultra-high pressure mercury lamp at an exposure amount of 10 μm after development, and then allowed to stand for 30 minutes before development. .. Development was carried out using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C. and shower development was carried out for 40 seconds to prepare a resin pattern.
The sample on which the above resin pattern is formed is etched with a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.) at 23 ° C. for 30 seconds, and the resist is peeled off using a 4 mass% sodium hydroxide solution to perform a wiring pattern. Was produced. The line width of the wiring pattern was measured at 100 points, the LWR (standard deviation of the line width) was calculated, and the linearity of the wiring was evaluated. The evaluation results are shown in Table 1 or Table 2. Among 1 to 5, the larger the value, the better the linearity of the wiring pattern is evaluated, which is preferable.

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

<Evaluation of wiring>
After peeling off the cover film, the photosensitive transfer material produced in each Example or Comparative Example is laminated on a PET substrate with a copper layer under laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating rate) of 3.6 m / min. did.
After that, the temporary support and the adhesive layer are peeled off, and a mask having an intermediate layer of the photosensitive transfer material, a line-and-space pattern (Duty ratio 1: 1) made of glass with a line width of 3 μm to 20 μm, and an alignment mark. Was contacted while adjusting the exposure position (alignment), exposed to an ultra-high pressure mercury lamp via the above mask, allowed to stand for 30 minutes, and then developed. Development was carried out using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C. and shower development was carried out for 40 seconds to prepare a resin pattern.
Furthermore, the patterned sample is etched with a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.) at 23 ° C. for 30 seconds, and the resist is peeled off using a 4 mass% sodium hydroxide solution to make an alignment mark. The wiring pattern to have was produced.
The position of the alignment mark of the metal wiring pattern was confirmed, and the one that was manufactured according to the target position was regarded as "good", and the one that was deviated from the target position was regarded as "bad". The evaluation results are shown in Table 1 or Table 2.
"According to the target position" means that the error from the target is within 50 μm.

In Table 1 or Table 2, the description of the particle content indicates the particle content with respect to the total mass of the intermediate layer.
From the results shown in Table 1, the photosensitive transfer material according to the embodiment of the present application has excellent slipperiness against mask during contact exposure, and the obtained wiring is formed at a desired position. Therefore, during contact exposure. It can be seen that the alignment of is easy.
Further, in Comparative Example 1 or Comparative Example 2, since the intermediate layer does not contain particles, the slipperiness against the mask at the time of contact exposure is inferior, and as a result, the metal wiring is the target position in the evaluation of the obtained wiring. It can be seen that it was not made according to the street.
In Comparative Example 3 or Comparative Example 4, a temporary support having no adhesive layer is used, and when such a temporary support is used, the temporary support and the intermediate layer do not adhere to each other and are photosensitive. Since the transfer material could not be manufactured, it was impossible to evaluate the slipperiness against the mask, the linearity of the wiring, and the wiring.

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

Next, the pattern was exposed using a photomask provided with an opening of the pattern shown in FIG. 3 (hereinafter, also referred to as “pattern B”) in an aligned state, and the pattern was developed and washed with water.
In the pattern B shown in FIG. 3, the gray portion G is the light-shielding portion, and the dotted line portion DL is a virtual representation of the alignment alignment frame.
Then, the copper layer was etched with Cu-02, and the remaining photosensitive layer was peeled off with a stripping solution (10 mass% sodium hydroxide aqueous solution) to obtain a wiring board.
As a result, a wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and the pattern was beautiful.

The disclosure of Japanese Patent Application No. 2018-909701 filed on January 24, 2018 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated by reference herein.

Claims (9)

The cover film has a photosensitive layer, an intermediate layer, an adhesive layer, and a temporary support in this order.
The intermediate layer contains particles
The average particle size of the particles is 10 nm to 200 nm, and the particles have an average particle diameter of 10 nm to 200 nm.
The intermediate layer and the adhesive layer are in contact with each other,
The intermediate layer and the adhesive layer can be peeled off,
A photosensitive transfer material having irregularities on the surface of the intermediate layer after the intermediate layer and the adhesive layer are peeled off. The photosensitive transfer material according to claim 1, wherein the particles include at least one particle selected from the group consisting of silica particles, alumina particles, and organic polymer particles. The photosensitive transfer material according to claim 1 or 2 , wherein the content of the particles with respect to the total mass of the intermediate layer is 1% by mass to 80% by mass. The photosensitive transfer material according to any one of claims 1 to 3 , wherein the photosensitive layer contains a binder polymer having an acid group protected by an acid-degradable group and a photoacid generator. The photosensitive transfer material according to any one of claims 1 to 3 , wherein the photosensitive layer contains a binder polymer having an acid group, a polymerizable compound, and a photopolymerization initiator. The invention according to any one of claims 1 to 5 , wherein the intermediate layer contains at least one selected from the group consisting of a modified cellulose resin, polyvinyl alcohol, and polyvinylpyrrolidone as a binder polymer for the intermediate layer. Photosensitive transfer material. A step of applying a composition for forming a photosensitive layer on a cover film to form a photosensitive layer,
A step of applying a composition for forming an intermediate layer containing at least particles onto the photosensitive layer to form an intermediate layer.
A step of adhering a temporary support having an adhesive layer so that the adhesive layer is in contact with the intermediate layer is included.
The average particle size of the particles is 10 nm to 200 nm.
A method for manufacturing a photosensitive transfer material. The step of peeling off the cover film in the photosensitive transfer material according to any one of claims 1 to 6 .
A step of bringing the outermost layer of the photosensitive transfer material from which the cover film has been peeled off on the photosensitive layer side into contact with a support having a conductive layer and bonding them together.
A step of peeling the temporary support, the adhesive layer, and the intermediate layer,
A step of bringing an exposure mask into contact with the intermediate layer and pattern-exposing the photosensitive layer through the exposure mask.
A method for producing a resin pattern, which comprises a step of developing the photosensitive layer to form a resin pattern and the process of forming the resin pattern in this order. The step of peeling off the cover film in the photosensitive transfer material according to any one of claims 1 to 6 .
A step of bringing the outermost layer of the photosensitive transfer material from which the cover film has been peeled off on the photosensitive layer side into contact with a support having a conductive layer and bonding them together.
A step of peeling the temporary support, the adhesive layer, and the intermediate layer,
A step of bringing an exposure mask into contact with the intermediate layer and pattern-exposing the photosensitive layer through the exposure mask.
The process of developing the photosensitive layer to form a resin pattern and
A method for manufacturing a circuit wiring, comprising a step of etching the conductive layer using the formed resin pattern as a mask in this order.

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