JP7011046B2 - Photosensitive transfer material, resist pattern manufacturing method, circuit wiring manufacturing method, touch panel, and touch panel display device - Google Patents

Description

The present disclosure relates to a photosensitive transfer material, a method for manufacturing a resist pattern, a method for manufacturing a circuit wiring, a touch panel, and a touch panel display device.

For example, in a display device equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), an electrode pattern corresponding to a sensor of a visual recognition unit, a peripheral wiring portion, and a take-out wiring portion are used. A conductive layer pattern such as wiring 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. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

For example, in Japanese Patent No. 2832409, at least (1) a support, (2) an intermediate layer having a thickness of 0.1 to 5 μm provided on the support, and (3) an intermediate layer provided on the intermediate layer. A photopolymerizable resin material containing a photopolymerizable resin layer containing a carboxyl group-containing binder has been disclosed, wherein the intermediate layer contains hydroxypropylmethyl cellulose.
Japanese Unexamined Patent Publication No. 2016-57632 describes (A) a novolak-type phenol resin obtained from metacresol and paracresol, (B) a novolak-type phenol resin obtained from orthocresol, and (C) light to generate acid. A positive photosensitive resin composition containing a compound is disclosed.

When forming a positive photosensitive resin layer on a substrate using a photosensitive transfer material, the substrate, the positive photosensitive resin layer, and the temporary support are attached by attaching the photosensitive transfer material to the substrate. A laminate having at least at least in this order is formed. After exposing such a laminate, a resist pattern is formed by developing the positive photosensitive resin layer.
Here, for the purpose of improving the resolution of the obtained resist pattern or the like, in the above exposure, after the temporary support is peeled off, a photomask having a pattern on the surface of the laminated body on the side where the temporary support is peeled off ( It is being considered to perform exposure (also referred to as "contact exposure") by simply contacting the mask (also referred to as "mask").
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 may be contaminated by the components contained in the laminated body.

An object to be solved by the embodiment according to the present disclosure is to provide a photosensitive transfer material in which contamination of a photomask during contact exposure is suppressed.
Further, the problem to be solved by another embodiment according to the present disclosure is to provide a method for manufacturing a resist pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a circuit wiring, a touch panel, and a touch panel display device. be.

The means for solving the above problems include the following aspects.
<1> Temporary support and
With the middle class,
The positive photosensitive resin layer and the positive photosensitive resin layer are provided in this order.
The temporary support and the intermediate layer are in contact with each other.
The indentation hardness on the surface of the intermediate layer on the side in contact with the temporary support is 5.0 mN or more.
Photosensitive transfer material.
<2> The photosensitive transfer material according to <1>, wherein the intermediate layer contains a cellulose ether compound.
<3> The above <1> or <2>, wherein the intermediate layer includes two or more layers, and the layer in contact with the positive photosensitive resin layer among the layers contained in the intermediate layer contains a cellulose ether compound. > The photosensitive transfer material.
<4> The layer in contact with the temporary support in the intermediate layer contains hydroxypropylmethyl cellulose, and the layer in contact with the positive photosensitive resin layer in the intermediate layer contains hydroxypropyl cellulose. <3> The photosensitive transfer material according to.
<5> Any of the above <1> to <4>, wherein the positive photosensitive resin layer contains a polymer having a structural unit having an acid group protected by an acid decomposable group and a photoacid generator. The photosensitive transfer material according to one.
<6> The photosensitive transfer material according to <5>, wherein the structural unit having an acid group protected by the acid-degradable group includes a structural unit represented by any of the following formulas A1 to A3.

In formula A1, R ¹¹ and R ¹² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or an aryl group. Representing an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ is a single-bonded or divalent linking group. , R ¹⁵ represents a substituent, and n represents an integer from 0 to 4.
In formula A2, R ²¹ and R ²² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is an alkyl group or an aryl group. Representing an aryl group, R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, and R ²⁴ may independently form a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, or an alkenyl group. It represents an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In formula A3, 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. Y represents —S— or —O—.
<7> The photosensitive transfer material according to <5> or <6>, wherein the structural unit having an acid group protected by the acid-degradable group includes a structural unit represented by the following formula A3-2.

In formula A3-2, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group. A group or aryl group may be represented, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. show.
<8> With respect to the substrate, the temporary support of the photosensitive transfer material according to any one of <1> to <7> is brought into contact with the outermost layer on the positive photosensitive resin layer side. And the process of pasting together
The step of peeling off the temporary support of the photosensitive transfer material and
A step of contacting a photomask with a photosensitive transfer material from which the temporary support has been peeled off to perform pattern exposure on the positive photosensitive resin layer.
A method for producing a resist pattern, comprising the step of developing the positive photosensitive resin layer after the exposure step to form a resist pattern, and the step of forming a resist pattern in this order.
<9> A step of contacting and bonding the outermost layer of the photosensitive transfer material according to any one of <1> to <7> on the positive photosensitive resin layer side to the substrate. ,
The step of peeling off the temporary support of the photosensitive transfer material and
A step of contacting a photomask with a photosensitive transfer material from which the temporary support has been peeled off to perform pattern exposure on the positive photosensitive resin layer.
The process of developing the positive photosensitive resin layer to form a resist pattern,
A method for manufacturing a circuit wiring including a step of etching a substrate in a region where a resist pattern is not arranged, and a step of etching the substrate in this order.
<10> A touch panel including circuit wiring manufactured by using the photosensitive transfer material according to any one of <1> to <7>.
<11> A touch panel display device including the touch panel according to <10> above.

According to the embodiment according to the present disclosure, it is possible to provide a photosensitive transfer material in which contamination of a photomask during contact exposure is suppressed.
Further, according to another embodiment according to the present disclosure, it is possible to provide a method for manufacturing a resist pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a circuit wiring, a touch panel, and a touch panel display device.

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.
Regarding 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).
In the present disclosure, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, "(meth) acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth) acrylate" is a concept that includes both acrylate and methacrylate, and "(meth) acrylate" is a concept that includes both acrylate and methacrylate. ) Acryloyl group ”is a concept that includes both an acryloyl group and a methacryloyl group.
In the present disclosure, the amount of each component in a layer such as a positive photosensitive resin layer is the above-mentioned plurality of substances existing in the layer when a plurality of substances corresponding to each component are present in the layer, unless otherwise specified. Means the total amount of.
In addition, the term "process" in the present disclosure is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in the case where it cannot be clearly distinguished from other processes. Is done.
Further, 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. For the measurement of weight average molecular weight by GPC, HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) is used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4.6 mm ID x 15 cm, Tosoh) is used as a column. (Manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Co., Ltd.), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Co., Ltd.), Super HZ2000 (4.6 mm ID x 15 cm, manufactured by Tosoh Co., Ltd.) ) Is connected in series one by one, and THF (tetrahydrogen) can be used as the eluent. 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".
In the present disclosure, the total solid content means the total mass of the components excluding volatile components such as solvents in the composition.
In the present disclosure, the ratio of the constituent units in the resin represents the quality weight ratio unless otherwise specified.
In the present disclosure, the molecular weight when there is a molecular weight distribution represents a weight average molecular weight (Mw) unless otherwise specified.
In the drawings of the present disclosure, the same components are designated by the same reference numerals and detailed description thereof will be omitted.
In the present disclosure, "light" is a concept including active energy rays such as γ-rays, β-rays, electron rays, ultraviolet rays, visible rays, and infrared rays.
Unless otherwise specified, "exposure" in the present disclosure includes not only exposure with emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and exposure with EUV (Extreme ultraviolet) light, but also electron beams. , And exposure to particle beams such as ion beams.

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has a temporary support, an intermediate layer, and a positive photosensitive resin layer in this order, and the temporary support and the intermediate layer are in contact with each other, and the intermediate layer is in contact with the temporary support. The indentation hardness on the surface of the layer on the side in contact with the temporary support is 5.0 mN or more.

The present inventors have found that when contact exposure is performed using the photosensitive transfer material described in Japanese Patent No. 2832409 or Japanese Patent Application Laid-Open No. 2016-57632, the mask may be contaminated.
The photosensitive transfer material described in Japanese Patent No. 2832409 is a photosensitive transfer material having a negative type photosensitive resin layer, and is softer than a photosensitive transfer material having a positive type photosensitive resin layer, so that it has an indentation hardness. Tends to be low. Further, since the photomask and the intermediate layer are adhered to each other during contact exposure, the photosensitive resin layer is peeled off from the substrate when the photomask is peeled off, and Japanese Patent Application Laid-Open No. 2016-57632 contains the components of the intermediate layer and the photosensitive resin layer. The photosensitive transfer material described in 1 contains a positive photosensitive resin layer, but since it does not have a high hardness intermediate layer, it is difficult to suppress plastic deformation of the photosensitive transfer material, and the photosensitive transfer material is included in the positive photosensitive resin layer. In some cases, the components may contaminate the mask.
Therefore, as a result of diligent studies, the present inventors have made contact exposure by having an intermediate layer having an indentation hardness of 5.0 mN or more on the surface on the side in contact with the temporary support in the photosensitive transfer material according to the present disclosure. It was found that the contamination of the mask at the time was suppressed.
It is considered that this is because the indentation hardness of the intermediate layer is the above value, so that the plastic deformation of the photosensitive transfer material at the time of contact exposure is suppressed.

Thus, according to the present disclosure, contamination of the mask during contact exposure is suppressed.
Here, as an advantage of performing contact exposure, there is a point that the shape of the resist pattern obtained after development is good.
The present inventors, as in the conventional case, when a mask is placed on a temporary support for exposure, the exposed light is reflected at the interface of the substrate or the positive photosensitive resin layer to generate a reflected wave. It was found that the photosensitive resin layer was exposed by the standing wave generated by the interference between the light and the incident wave, and a stepped notch was generated in the side surface portion of the resist pattern obtained after development.
Further, the present inventors consider that it is effective to make the distance between the mask and the base material as small as possible in order to suppress the occurrence of the stepped notch, and the temporary support is peeled off to perform contact exposure. I thought it was preferable to do it.
That is, the photosensitive transfer material according to the present disclosure is, for example, fine in that contamination of the mask during contact exposure is suppressed, and the occurrence of the stepped notch is suppressed by performing contact exposure. It is also considered to be useful when forming a resist pattern.
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 intermediate layer 12, a positive photosensitive resin layer 14, and a cover film 16 are laminated in this order.
The intermediate layer 12 is in contact with the temporary support 10, and the indentation hardness on the surface on the side in contact with the temporary support is 5.0 mN or more.

<Middle layer>
In the photosensitive transfer material according to the present disclosure, an intermediate layer that is in contact with a temporary support and has an indentation hardness of 5.0 mN or more on the surface on the side in contact with the temporary support is formed by using the temporary support and a positive photosensitive resin layer. Have in between.
The intermediate layer is a layer that becomes the outermost layer in the photosensitive transfer material after the temporary support is peeled off.

[Indentation hardness]
The indentation hardness on the surface of the intermediate layer on the side in contact with the temporary support is 5.0 mN or more, preferably 5.2 mN or more, and more preferably 5.4 mN or more.
The upper limit of the indentation hardness of the intermediate layer is not particularly limited, but is preferably 50 mN or less. Within this range, problems such as cracks and delamination are unlikely to occur during laminating.

The indentation hardness is measured by the following measuring method.
The cover film is peeled off from the photosensitive transfer material as needed, the photosensitive transfer material is laminated on an alkali-cleaned glass plate (EagleXG manufactured by Corning Inc.), and then the temporary support is peeled off from the interface with the intermediate layer to be intermediate. Expose the layer.
In an environment of 25 ° C and 60% RH (relative humidity), a dynamic ultrafine hardness tester (DUH-W201 manufactured by Shimadzu Corporation) and a round indenter (Tokyo Diamond Tool Co., Ltd.) were applied to the exposed surface of the intermediate layer. A model number 8188) manufactured by Mfg. Co., Ltd. is attached, and a indentation test is performed at a test MODE1 and a load speed of 1.4 mN / s. The load is gradually increased to obtain a load (mN) having a pushing depth of 1.00 ± 0.05 μm, which is used as the pushing hardness.

[Physical characteristics of the middle layer]
The intermediate layer may be made of any material as long as the above-mentioned indentation hardness is within the above-mentioned range, but it is preferably a layer that is removed by development.
The intermediate layer is preferably a water-soluble or water-dispersible layer from the viewpoint that it is easily removed by development.
In the present disclosure, water solubility means that the amount of the target substance dissolved in 100 parts by mass of water at 25 ° C. is 0.1 part by mass or more.
In the present disclosure, water dispersibility means that the amount of precipitate after 24 hours is less than 0.01 part by mass when 100 parts by mass of water at 25 ° C. and 0.1 part by mass of the target substance are mixed. say.

[Cellulose ether compound]
The intermediate layer preferably contains a cellulose ether compound from the viewpoint of adhesion to the positive photosensitive resin layer, peelability from the temporary support, and the like.
The cellulose ether compound is a compound having an etherified structure of cellulose.
The cellulose ether compound is not particularly limited as long as the indentation hardness is 5.0 mN or more, and examples thereof include hydroxypropylmethyl cellulose and hydroxypropyl cellulose, and hydroxypropylmethyl cellulose is preferable from the viewpoint of suppressing mask contamination.

The glass transition temperature (Tg) of the cellulose ether compound is preferably 100 ° C to 200 ° C, more preferably 120 ° C to 180 ° C.
In the present disclosure, the glass transition temperature can be measured using differential scanning calorimetry (DSC).
The specific measurement method is 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 specification, 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 it at a temperature about 50 ° C lower than the expected Tg until the device stabilizes, and then heat it at a heating rate of 20 ° C / min, which is about 30 ° C higher than the temperature at which the glass transition ends. Heat up to 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 Tg to the above-mentioned preferable range, for example, the FOX equation 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, and the purpose is It is possible to control the Tg of the specific polymer.
About the FOX formula The Tg of the homopolymer of the first constituent unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constituent unit is W1, and the Tg of the homopolymer of the second constituent unit is Tg1. Is Tg2, and 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. It is possible to estimate according to the equation.
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.

The weight average molecular weight of the cellulose ether compound is preferably 5,000 to 200,000, more preferably 10,000 to 100,000 from the viewpoint of developability and the like.

As the cellulose ether compound, a commercially available product may be used, and preferred commercially available products are Metrose 60SH-03, Metrose 60SH-06, Metrose 60SH-15 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and NISSO HPC-SSL. , HPC-SL, HPC-L (manufactured by Nippon Soda Co., Ltd.), CMC Daicel (manufactured by Daicel FineChem Co., Ltd.), HEC AL-15 (manufactured by Sumitomo Seika Co., Ltd.) and the like.

The intermediate layer in the present disclosure may contain one type of cellulose ether compound alone, or two or more types may be used in combination.
The content of the cellulose ether compound is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and 25% by mass with respect to the total mass of the intermediate layer. % Or more is particularly preferable.
The upper limit of the content is not particularly limited, and may be 100% by mass or less.

〔particle〕
The intermediate layer in the present disclosure may further contain particles from the viewpoint of improving the adhesion to the positive photosensitive resin layer or the second resin layer described later.
Examples of the particles include inorganic particles and resin particles, and from the viewpoint of suppressing mask contamination, silica particles, alumina particles or resin particles are preferable, silica particles or alumina particles are more preferable, and silica particles are used. It is more preferable to have.

Examples of the inorganic particles include inorganic oxide particles such as silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Particles can be mentioned.

Examples of the resin 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. Polypolymers of vinyl polymers and vinyl compounds such as polyethylene, polypropylene, polystyrene, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, polyvinylpyrrolidone, polyvinylbutyral, polyvinyl alcohol, polyesters, polyurethanes, polyamides Such condensation-based polymers, 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 be mentioned. ..

The surface of the particles can also be treated with an organic or inorganic material to impart dispersion stability. The particles preferably have a hydrophilic surface. For example, the surface of particles having a hydrophobic surface may be hydrophilized.

The volume average particle size of the particles is preferably 10 nm to 200 nm. The volume average particle size is measured using a particle size distribution measuring device using light scattering (for example, Microtrac UPA (registered trademark) EX150 manufactured by Nikkiso Co., Ltd.).

The intermediate layer in the present disclosure may contain one kind of particles alone, or two or more kinds may be used in combination.
The body integration rate of the particles in the intermediate layer (volume ratio occupied by the particles in the intermediate layer) is 5% by volume to 90% by volume with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% by volume to 80% by volume, further preferably 15% by volume to 70% by volume, and particularly preferably 20% by volume to 60% by volume.

[Other additives]
The intermediate layer in the present disclosure may contain a known additive, if necessary, in addition to the cellulose ether compound.
As other additives, other additives used for the positive photosensitive resin layer described later are preferably mentioned.

[Intermediate layer including two or more layers]
The intermediate layer may include two or more layers.
From the viewpoint of manufacturing aptitude, when the intermediate layer contains two or more layers, it is preferable that the intermediate layer contains two layers.
Hereinafter, when the intermediate layer includes two or more layers, details of the layer in contact with the positive photosensitive resin layer contained in the intermediate layer, the layer in contact with the temporary support included in the intermediate layer, and other layers. Will be explained.

-A layer in contact with the positive photosensitive resin layer-
Among the layers contained in the intermediate layer, the layer in contact with the positive photosensitive resin layer (hereinafter, also referred to as “lower layer”) preferably contains a cellulose ether compound.
Since the lower layer contains the cellulose ether compound, the shape of the resist pattern obtained after development is less likely to change even when time has passed after exposure.
In the present disclosure, the property that the shape of the resist pattern does not easily change even if the resist pattern is developed after a lapse of time after exposure is also referred to as "excellent in leaving stability (PED (post exposure delay))".
Further, in the present disclosure, allowing the photosensitive transfer material to stand for a certain period of time after exposure and before development is referred to as "placing after exposure", for example, after exposure and before development. Leaving the photosensitive transfer material for 3 hours is called leaving it for 3 hours.
The reason why the effect of excellent retention stability can be obtained by containing the cellulose ether compound in the lower layer is not clear, but for example, some suppression is given to the increase in developability due to the exposure reaction of the positive photosensitive resin composition. It is presumed that it has an effect.

The cellulose ether compound contained in the lower layer is not particularly limited, but hydroxypropyl cellulose or hydroxypropyl methyl cellulose is preferable, and hydroxypropyl cellulose is more preferable.

The weight average molecular weight of the cellulose ether compound is preferably 5,000 to 200,000, more preferably 10,000 to 100,000 from the viewpoint of developability and the like.

As the cellulose ether compound, a commercially available product may be used, and preferred commercially available products are HPC-SSL (manufactured by Nippon Soda Co., Ltd.), Metrose 60SH-03, Metrose 60SH-06, and Metrose 60SH-15 (all). Shin-Etsu Chemical Co., Ltd.) and the like.

The lower layer may contain one type of cellulose ether compound alone, or two or more types may be used in combination.
The content of the cellulose ether compound is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and 25% by mass, based on the total mass of the lower layer. The above is particularly preferable.
The upper limit of the content is not particularly limited, and may be 100% by mass or less.

-Layer in contact with the temporary support-
When the intermediate layer includes two or more layers, the indentation hardness of the layer in contact with the temporary support in the intermediate layer on the surface on the side in contact with the temporary support is 5.0 mN or more.
When the intermediate layer includes two or more layers, the layer in the intermediate layer in contact with the temporary support is also referred to as an "upper layer".
When the intermediate layer includes two or more layers, the preferred embodiment of the layer in contact with the temporary support in the intermediate layer is the same as the preferred embodiment of the intermediate layer described above.

Further, in the intermediate layer in the present disclosure, the layer in contact with the temporary support in the intermediate layer contains hydroxypropylmethyl cellulose, and the layer in contact with the positive photosensitive resin layer in the intermediate layer contains hydroxypropyl cellulose. Is preferable.

-Other layers-
When the intermediate layer includes three or more layers, another layer is included between the upper layer and the lower layer.
The other layer is not particularly limited, and examples thereof include a layer containing a cellulose ether compound.
Examples of the cellulose ether compound include the cellulose ether compounds contained in the above-mentioned upper layer or lower layer.

[Thickness of intermediate layer]
The thickness of the intermediate layer (when the intermediate layer includes two or more layers, the total thickness of all the layers contained in the intermediate layer) is 0.1 μm to 10 μm from the viewpoint of further improving the effect of contact exposure. Preferably, 0.2 μm to 8 μm is more preferable, and 0.5 μm to 5 μm is particularly preferable.
Further, the thickness of the intermediate layer is preferably thinner than the thickness of the positive photosensitive resin layer described later.

When the intermediate layer contains two or more layers, the thickness of the upper layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 8 μm, and more preferably 0.5 μm to 5 μm from the viewpoint of further improving the effect of contact exposure. Is particularly preferable.
When the intermediate layer contains two or more layers, the thickness of the lower layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 8 μm from the viewpoint of further improving the retention stability and the effect of contact exposure. 0.5 μm to 5 μm is particularly preferable.

[Method of forming the intermediate layer]
The method for forming the intermediate layer is not particularly limited, but the intermediate layer can be formed, for example, by using a composition for forming an intermediate layer.
Specifically, each component contained in the intermediate layer and a solvent are mixed at a predetermined ratio and by an arbitrary method, and the mixture is stirred and dissolved to prepare an intermediate layer forming composition for forming the intermediate layer. Can be done. 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.

By applying the composition for forming an intermediate layer to the temporary support and drying it, the intermediate layer can be easily formed on the temporary support.
Further, the photosensitive resin composition described later may be applied to the cover film described later, and then the composition for forming an intermediate layer may be applied onto the photosensitive resin composition.
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.
When the intermediate layer contains two or more layers, it can be formed by sequentially applying a plurality of intermediate layer forming compositions.

<Temporary support>
The temporary support is a support that supports the intermediate layer and the positive photosensitive resin layer and can be peeled off from the intermediate layer.
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, a biaxially stretched polyethylene terephthalate film is particularly preferable.
In the present disclosure, the temporary support may have a layer that is peeled off together with the temporary support when the temporary support is peeled off.

The thickness of the temporary support is not particularly limited, and is preferably in the range of 1 μm to 200 μm, and more preferably in the range of 5 μm to 100 μm in terms of ease of handling and versatility.
The thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, and light transmission required in the first exposure process. do it.

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.

<Positive photosensitive resin layer>
The photosensitive transfer material according to the present disclosure has a positive photosensitive resin layer.
The positive photosensitive resin layer preferably contains a polymer having a structural unit having an acid group protected by an acid-degradable group and a photoacid generator.
Further, the positive photosensitive resin layer in the present disclosure is preferably a chemically amplified positive photosensitive resin layer.
In the photoacid generators such as onium salts and oxime sulfonate compounds described later, the acid generated in response to active energy rays (active rays) is resistant to the deprotection of the protected acid group in the specific polymer. Since it acts as a catalyst, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, which is a large value such as the power of 10, so-called chemistry. High sensitivity is obtained as a result of amplification.
On the other hand, when a quinonediazide compound is used as a photoacid generator that is sensitive to active energy rays, a carboxy group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less, and it does not correspond to the chemically amplified type. ..

[Polymer component containing a polymer having a structural unit having an acid-degradable and protected acid group]
The positive photosensitive resin layer contains a polymer (also referred to as "specific polymer") having a structural unit (also referred to as "constituent unit A") having an acid group protected by an acid-degradable group. Is preferable.
Further, the positive photosensitive resin 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".
In the specific polymer, the structural unit A having an acid-decomposable and protected acid group in the specific polymer undergoes a deprotection reaction to become an acid group due to the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables a curing reaction.

The positive photosensitive resin layer may further contain a polymer other than the polymer having a structural unit having an acid group protected by acid decomposition.
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 chemically amplified positive photosensitive resin composition 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 compounds corresponding to the surfactants, cross-linking agents and dispersants described later are not included in the polymer components even if they are polymer compounds.

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, or the like.

The positive photosensitive resin layer contains a structural unit represented by any of the above formulas A1 to A3 as the above structural unit A as a specific polymer from the viewpoint of solubility in a developing solution, transferability and the like. It is preferable to contain a polymer (hereinafter, also referred to as “polymer A-1”), and as the specific polymer, the structural unit represented by any of the above formulas A1 to A3 as the above-mentioned structural unit A, and It is more preferable to contain a polymer having an acid group.
The specific polymer contained in the positive photosensitive resin layer may be only one kind or two or more kinds.

-Constituent unit A-
The polymer component preferably contains a polymer A-1 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 type positive photosensitive resin 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-decomposable and protected acid group, a group relatively easily decomposed by an acid (for example, an ester group protected by a group represented by the formula A3, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). (Acetal-based functional groups such as) and groups that are relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used. can.
Among these, the acid-degradable group is preferably a group having a protected structure in the form of acetal.
Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in line width in the obtained circuit wiring.

From the viewpoint of sensitivity and resolution, the structural unit A having an acid group protected by the acid-degradable group preferably contains a structural unit represented by any of the following formulas A1 to A3, and is preferably represented by the formula A3 described later. It is more preferable to include the structural unit represented by -2.

In formula A1, R ¹¹ and R ¹² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or an aryl group. Representing an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ is a single-bonded or divalent linking group. , R ¹⁵ represents a substituent, and n represents an integer from 0 to 4.
In formula A2, R ²¹ and R ²² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is an alkyl group or an aryl group. Representing an aryl group, R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, and R ²⁴ may independently form a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, or an alkenyl group. It represents an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In formula A3, 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. Y represents —S— or —O—.

<< Preferred embodiment of the structural unit represented by the formula A1 >>
In the formula A1, when R ¹¹ or R ¹² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹¹ or R ¹² is an aryl group, a phenyl group is preferable. R ¹¹ and R ¹² are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
In the formula A1, R ¹³ 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 ¹¹ to R ¹³ may have a substituent.
In the formula A1, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, and it is preferable that R ¹¹ or R ¹² and R ¹³ 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 A1, X ¹ 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 ¹ contains -C (= O) NR ^N- , it is preferable that the carbon atom contained in -C (= O) NR ^N- and the carbon atom to which R ¹⁴ 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 A1, the group containing R ¹¹ to R ¹³ and X ¹ are preferably bonded to each other at the para position.
In the formula A1, R ¹⁵ 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 A1, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula A1, R ¹⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer A-1 can be lowered.
More specifically, the structural unit in which R ¹⁴ is a hydrogen atom in the formula A1 is preferably 20% by mass or more with respect to the total content of the structural unit A contained in the polymer A-1.
The content (content ratio: mass ratio) of the structural unit in which R ¹⁴ in the formula A1 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 A1, the structural unit represented by the following formula A1-2 is more preferable from the viewpoint of suppressing deformation of the pattern shape.

In formula A1-2, ^{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, and RB12 represents a substituent} , n. Represents an integer from 0 to 4.
In formula ^A1-2 , hydrogen atom is preferable for RB4.
In the formula A1-2, hydrogen atoms are preferable for ^RB5 to ^RB11 .
Formulas A1-2 and ^RB12 represent substituents, preferably alkyl groups or halogen atoms. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In the formula A1-2, 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 A1 represented by the formula A1, the following structural unit can be exemplified. In addition, ^RB4 represents a hydrogen atom or a methyl group.

<< Preferred embodiment of the structural unit represented by the formula A2 >>
In the formula A2, when R ²¹ and R ²² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ²¹ and R ²² are aryl groups, a phenyl group is preferable. R ¹¹ and R ¹² are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively, and more preferably at least one of them is a hydrogen atom.
In the above general formula A2, R ²³ 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.
R ¹¹ or R ¹² and R ¹³ may be connected to form a cyclic ether.
In the formula A2, it is preferable that R ²⁴ is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R ²⁴ may be further substituted with the same groups as R ²⁴ .
In the formula A2, m is preferably 1 or 2, and more preferably 1.

As a preferable specific example of the structural unit A2 represented by the formula A2, the following structural unit can be exemplified.

<< Preferred embodiment of the structural unit represented by the formula A3 >>
In the formula A3, 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 A3, 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 A3, 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 formula A3, X ⁰ represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
In the formula A3, Y represents —S— or —O—, and —O— is preferable from the viewpoint of exposure sensitivity.

The structural unit represented by the above formula A3 is a structural unit having a carboxy group protected by an acid-degradable group. Since the polymer A-1 contains the structural unit represented by the formula A3, the sensitivity at the time of pattern formation is excellent, and the resolution is more excellent.
In the formula A3, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer A-1 can be lowered.
More specifically, the structural unit in which R ³⁴ is a hydrogen atom in the formula A3 is preferably 20% by mass or more with respect to the total amount of the structural units represented by the formula A3 contained in the polymer A-1.
The content (content ratio: mass ratio) of the structural unit in which R ³⁴ is a hydrogen atom in the structural unit represented by the formula A3 is always determined from the ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity calculated by the method.

Among the structural units represented by the formula A3, the structural unit represented by the following formula A3-2 is more preferable from the viewpoint of further increasing the exposure sensitivity at the time of pattern formation.

In formula A3-2, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group. A group or aryl group may be represented, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. show.

In formula A3-2, R ³¹ , R ³² , R ³³ , R ³⁴ and X ⁰ are synonymous with R ³¹ , R ³² , R ³³ , R ³⁴ and X ⁰ in formula A3, respectively, and the preferred embodiments are also the same. Is.

Among the structural units represented by the formula A3, the structural unit represented by the following formula A3-3 is more preferable from the viewpoint of further increasing the sensitivity at the time of pattern formation.

In formula A3-3, 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 formula A3-3, R ³⁴ is preferably a hydrogen atom.
In formula A3-3, 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 having a carboxy group protected by an acid-degradable group represented by the formula A3. In addition, R ³⁴ represents a hydrogen atom or a methyl group.

The structural unit A contained in the polymer A-1 may be one kind or two or more kinds.
The content of the structural unit A in the polymer A-1 is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, based on the total mass of the polymer A-1. It is more preferably 30% by mass to 70% by mass.
The content (content ratio: mass ratio) of the structural unit A in the polymer A-1 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.

-Constituent unit B-
The polymer A-1 preferably contains a structural unit B having an acid group.
The structural unit B is a structural unit having an acid group that is not protected by a protecting group, for example, an acid-degradable group, that is, an acid group that does not have a protecting group. When the polymer A-1 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 having an acid group (constituent unit B) 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.

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 polymer A-1 is carried out by copolymerizing a monomer having an acid group or by copolymerizing a monomer having an acid anhydride structure and hydrolyzing the acid anhydride. Can be done.
The structural unit having an acid group, which is the structural unit B, is derived from a structural unit derived from a styrene compound, a structural unit derived from a vinyl compound in which an acid group is substituted, or a (meth) acrylic acid. It is more preferable that it is a structural unit. Specifically, examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like, and examples of the monomer having a phenolic hydroxyl group include p-. Examples thereof include hydroxystyrene and 4-hydroxyphenylmethacrylate, and examples of the monomer having an acid anhydride include maleic anhydride and the like.

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 polymer A-1 may be only one kind or two or more kinds.
The polymer A-1 preferably contains 0.1% by mass to 20% by mass of a structural unit having an acid group (constituent unit B) with respect to the total mass of the polymer A-1. It is more preferably contained in an amount of 15% by mass, and further preferably contained in an amount of 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 polymer A-1 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 polymer A-1, other structural units (hereinafter, may be referred to as structural unit C) other than the above-mentioned structural unit A and structural unit B can be used as the effect of the photosensitive transfer material according to the present disclosure. It may be included as long as it does not impair.
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. , Bicyclounsaturated 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.
Various properties of the polymer A-1 can be adjusted by adjusting at least one of the type and the content using the structural unit C. In particular, the Tg of the polymer A-1 can be easily adjusted by appropriately using the structural unit C.
By setting the glass transition temperature to 120 ° C. or lower, the positive photosensitive resin layer containing the polymer A-1 maintains good transferability and peelability from the temporary support at the time of pattern formation. The resolution and sensitivity of the are better.
The polymer A-1 may contain only one type of structural unit C, or may contain two or more types of the constituent unit C.

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 monoacetoacetate 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 polymer A-1. The lower limit value 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.

The fact that the polymer A-1 contains the structural unit having the ester of the acid group in the structural unit B as the structural unit C also optimizes the solubility in a developing solution and the physical properties of the positive photosensitive resin layer. It is preferable from the viewpoint of conversion.
Among them, the polymer A-1 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). A polymer containing a structural unit B derived from acrylic acid and a structural unit (c) derived from cyclohexyl (meth) acrylic acid, 2-ethylhexyl (meth) acrylic acid or n-butyl (meth) acrylic acid is more preferable.
Hereinafter, preferred examples of the polymer A-1 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.

-Glass transition temperature of polymer A-1: Tg-
The glass transition temperature (Tg) of the polymer A-1 in the present disclosure is preferably 90 ° C. or lower, preferably 20 ° C. or higher, from the viewpoint of transferability and the viewpoint of adjusting the heating temperature in the above-mentioned heating step. It is more preferably 30 ° C. or higher and 50 ° C. or lower.

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 target polymer A-1.
Regarding the FOX formula, the Tg of the homopolymer of the first constituent unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constituent unit is W1, and the Tg of the homopolymer of the second constituent unit is Tg1. Is Tg2, and 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. It is possible to estimate according to the equation.
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.

-Acid value of polymer A-1-
From the viewpoint of developability and transferability, the acid value of the polymer A-1 is preferably 0 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 5 mgKOH / g or more and 100 mgKOH / g or less.

The acid value of the polymer in the present disclosure represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer. Specifically, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9/1, and the obtained solution was prepared using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). At ° C, neutralize titration with 0.1 M aqueous sodium hydroxide solution. The acid value is calculated by the following equation with the inflection point of the titration pH curve as the titration end point.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / l sodium hydroxide aqueous solution required for titration (mL)
f: Potency of 0.1 mol / l sodium hydroxide aqueous solution w: Mass (g) of measurement sample (in terms of solid content)

-Molecular weight of polymer A-1: Mw-
The molecular weight of the polymer A-1 is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. Since the weight average molecular weight of the polymer A-1 is 60,000 or less, the melt viscosity of the positive photosensitive resin layer is kept low, and the polymer A-1 is bonded at a low temperature (for example, 130 ° C. or less) when bonded to the substrate. Can be realized.
The weight average molecular weight of the polymer A-1 is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The ratio (dispersity) of the number average molecular weight and the weight average molecular weight of the polymer A-1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

-Method for producing polymer A-1-
The method for producing the polymer A-1 (synthesis method) is not particularly limited, but to give an example, a polymerizable monomer for forming the structural unit A represented by the formula A, a structural unit B having an acid group. Is synthesized by polymerizing with a polymerization initiator in an organic solvent containing a polymerizable monomer for forming the above, and if necessary, another polymerizable monomer for forming the structural unit C. be able to. It can also be synthesized by a so-called polymer reaction.

The positive photosensitive resin layer in the present disclosure contains 50% by mass to 99% by mass of the polymer component with respect to the total solid content of the positive photosensitive resin layer from the viewpoint of exhibiting good adhesion to the substrate. It is preferably contained in a proportion of 9.9% by mass, more preferably in a proportion of 70% by mass to 98% by mass.
Further, the positive photosensitive resin layer contains 50% by mass or more of the polymer A-1 with respect to the total solid content of the positive photosensitive resin layer from the viewpoint of exhibiting good adhesion to the substrate. It is preferably contained in a proportion of 99.9% by mass, and more preferably in a proportion of 70% by mass to 98% by mass.

[Other polymers]
The positive photosensitive resin layer contains the polymer A-1 as a polymer component and the structural unit (a) represented by the formula A as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired. It may further contain a non-polymer (sometimes referred to as "another polymer"). When the positive photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total polymer components. It is preferably 20% by mass or less, and more preferably 20% by mass or less.

The positive photosensitive resin layer may contain only one type of other polymer in addition to the polymer A-1, 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 Co., Ltd.), and Joncryl 690, Jonc. , Polymer 67, and Polymer 586 (above, manufactured by BASF) and the like can also be used.

[Photoacid generator]
The positive photosensitive resin layer preferably contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiating with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
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 positive photosensitive resin layer is 0.1% by mass to 10% by mass with respect to the total mass of the positive photosensitive resin layer from the viewpoint of sensitivity and resolution. Is preferable, and 0.5% by mass to 5% by mass is more preferable.

〔solvent〕
The positive photosensitive resin layer may contain a solvent.
Further, in the photosensitive resin composition forming the positive photosensitive resin layer, in order to easily form the positive photosensitive resin layer, a solvent is once contained to adjust the viscosity of the photosensitive resin composition. The positive photosensitive resin layer can be suitably formed by applying and drying the photosensitive resin composition containing a solvent.
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.
Examples of the solvent having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), and dipropylene glycol methyl ether acetate. (Boiling point 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 (Boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.) can be exemplified.

The content of the solvent when the photosensitive resin composition is applied is preferably 50 parts by mass to 1,900 parts by mass, preferably 100 parts by mass to 100 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is 900 parts by mass.
The content of the solvent in the positive photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, based on the total mass of the positive photosensitive resin layer. It is more preferably 0.5% by mass or less.

[Other additives]
The positive photosensitive resin layer in the present disclosure may contain a known additive, if necessary, in addition to the polymer A-1 and the photoacid generator.

-Plasticizer-
The positive photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a smaller weight average molecular weight than the polymer A-1.
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 polymer A-1 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 alkyl 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 type obtained by mixing Compound X, polymer A-1, and a photoacid generator. If the photosensitive resin composition does not have improved plasticity as compared with the chemically amplified positive photosensitive resin composition formed without containing compound X, it does not fall under the plastic agent in the present disclosure. For example, the arbitrarily added surfactant is not generally used in an amount that causes plasticity in the photosensitive resin composition, and therefore does not fall under the plasticizer in the present specification.

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, and 2% by mass to 20% by mass, based on the total mass of the positive photosensitive resin layer. Is more preferable.
The positive photosensitive resin layer may contain only one type of plasticizer, or may contain two or more types of plasticizer.

-Sensitizer-
The positive photosensitive resin 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 anthracene derivative, aclidene 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 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 positive photosensitive resin layer. ..

-Basic compound-
The positive photosensitive resin layer preferably 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, N-methyl-4-phenylpyridine, and the like. 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-Undesen and the like.
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, and preferably 0.005% by mass to 3% by mass, based on the total mass of the positive photosensitive resin layer. More preferred.

-Heterocyclic compound-
The positive photosensitive resin 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 oxazolines. Further, a heterocyclic monomer having silicon, sulfur, phosphorus and the like can be added.

When the heterocyclic compound is added, the amount of the heterocyclic compound added to the positive photosensitive resin layer is 0.01% by mass to 50% by mass with respect to the total mass of the positive photosensitive resin layer. It is preferably 0.1% by mass to 10% by mass, 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 positive photosensitive resin 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 positive photosensitive resin 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-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are 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.

-Surfactant-
The positive photosensitive resin layer 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 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (registered trademark) (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (manufactured by Toray Dow Corning Co., Ltd.), etc. Each series can be mentioned.
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula I-1 are contained, and the 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. It is more preferably 01% by mass to 3% by mass.

-Other ingredients-
The positive photosensitive resin 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, and the like. Further known additives such as UV absorbers, thickeners, cross-linking agents, and organic or inorganic antiprecipitants 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.

[Method for forming a positive photosensitive resin layer]
A photosensitive resin composition for forming a positive photosensitive resin 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.

A positive photosensitive resin layer can be formed by applying the photosensitive resin composition on the above-mentioned composition for forming an intermediate layer and drying it if necessary.
Further, the photosensitive resin composition may be applied onto a cover film described later to form a positive photosensitive resin layer.
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.
It is also possible to apply a positive photosensitive resin layer on the intermediate layer on which another layer described later is formed.

<Other layers>
The photosensitive transfer material according to the present disclosure may have a layer other than the positive photosensitive resin layer (hereinafter, may be referred to as “other layer”). Examples of other layers include a contrast enhancement layer, a cover film, a layer containing a known ultraviolet absorber, a thermoplastic resin layer, an adhesion layer and the like.

-Cover film-
The photosensitive transfer material according to the present disclosure may have 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, a cover film having a thickness of 1 μm to 2 mm is preferable.

-Thermoplastic resin layer-
From the viewpoint of transferability, the photosensitive transfer material according to the present disclosure preferably further has a thermoplastic resin layer between the temporary support and the intermediate layer.
It is preferable that the thermoplastic resin layer is peeled off between the intermediate layer and the thermoplastic resin layer when the temporary support is peeled off. That is, it is preferable that the thermoplastic resin layer is peeled off together with the temporary support.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-85643, and preferred embodiments of other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of this publication are incorporated herein.
Above all, from the viewpoint of transferability, it is preferable that the thermoplastic resin layer contains at least one thermoplastic resin selected from the group consisting of an acrylic resin and a styrene / acrylic copolymer.

When the photosensitive transfer material according to the present disclosure has another layer such as a thermoplastic resin layer, it is produced according to the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
For example, in the case of producing the photosensitive transfer material according to the present disclosure having a thermoplastic resin layer, a solution (for a thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support is used. (Coating liquid) is applied and dried to provide a thermoplastic resin layer, and then a preparation liquid (intermediate) prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer. The layer composition) is applied and dried to laminate the intermediate layer. A photosensitive resin composition prepared by using a solvent that does not dissolve the intermediate layer is further applied onto the formed intermediate layer, dried, and laminated with a positive photosensitive resin layer to obtain the photosensitive property according to the present disclosure. The transfer material can be suitably produced.

-Contrast enhancement layer-
The photosensitive transfer material according to the present disclosure may have a contrast enhancement layer in addition to the positive photosensitive resin layer.
The contrast enhancement layer is preferably provided between the intermediate layer and the positive photosensitive resin 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). As the photochromic dye component, a diazonium salt, a stillvazolium salt, an arylnitroso salt and the like are known. As the film-forming component, a phenol-based 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 edition, Industrial Research Council ( 1989), Photopolymer Technology, Yamaoka, Nagamatsu ed., Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

-Layer containing UV absorber-
The photosensitive transfer material according to the present disclosure may have a layer containing an ultraviolet absorber (ultraviolet absorbing layer).
The ultraviolet absorbing layer is preferably contained on the side of the positive photosensitive resin layer opposite to the intermediate layer. For example, an embodiment having an ultraviolet absorbing layer between the cover film and the positive photosensitive resin layer can be mentioned.
When a photosensitive transfer material having such an ultraviolet absorbing layer is transferred to a substrate, an ultraviolet absorbing layer is present between the substrate and the positive photosensitive resin layer.
According to such an aspect, it is considered that the reflection of the exposure light by the base material is reduced, and the influence of the exposure by the standing wave generated by the interference between the reflected wave and the incident wave is reduced.
As the ultraviolet absorber, known ultraviolet absorbers can be used without particular limitation, and compounds such as salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, and hindered amine-based compounds, and polymers containing these structures. , Or an inorganic ultraviolet absorber such as a metal oxide.

-Adhesion layer-
The photosensitive transfer material according to the present disclosure may further have an adhesive layer between the cover film and the positive photosensitive resin layer as another layer.
By having the adhesion layer, the adhesion when transferred to a substrate or the like is improved.

(Manufacturing method of resist pattern and manufacturing method of circuit wiring)
The method for manufacturing the resist pattern according to the present disclosure is not particularly limited, but
A step of bringing the temporary support of the photosensitive transfer material according to the present disclosure into contact with the substrate and attaching the outermost layer on the positive photosensitive resin layer side to the substrate.
The step of peeling off the temporary support of the photosensitive transfer material and
A step of contacting a photomask with a photosensitive transfer material from which the temporary support has been peeled off to perform pattern exposure on the positive photosensitive resin layer.
It is preferable to include the steps of developing the positive photosensitive resin layer after the exposure step to form a resist pattern in this order, and the method for manufacturing the circuit wiring according to the present disclosure is the photosensitive according to the present disclosure. There are no particular restrictions as long as it is a method for manufacturing circuit wiring using a sex transfer material.
A step of bringing the temporary support of the photosensitive transfer material according to the present disclosure into contact with the substrate and attaching the outermost layer on the positive photosensitive resin layer side to the substrate.
The step of peeling off the temporary support of the photosensitive transfer material and
A step of contacting a photomask with a photosensitive transfer material from which the temporary support has been peeled off to perform pattern exposure on the positive photosensitive resin layer.
The process of developing the positive photosensitive resin layer to form a resist pattern,
It is preferable to include the step of etching the substrate in the region where the resist pattern is not arranged in this order.
The "outermost layer on the positive photosensitive resin layer side" in the photosensitive transfer material in the present disclosure is the present disclosure having a temporary support, an intermediate layer, and a positive photosensitive resin layer in this order. It means the outermost layer on the positive photosensitive resin layer side, not the outermost layer on the temporary support side in the photosensitive transfer material according to the above. Further, the "outermost layer on the positive photosensitive resin layer side" is the outermost layer on the positive photosensitive resin layer side after the cover film is peeled off when the photosensitive transfer material has a cover film.
Further, the support is also referred to as a "base material", and the support having a conductive layer on the surface is also referred to as a "substrate".

Conventionally, the photosensitive resin 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, for example, a photosensitive agent that generates acid by being irradiated with active light is used to improve the solubility of the exposed part. Therefore, at the time of pattern exposure, both the exposed part and the unexposed part are exposed. 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, it is preferable to use a positive photosensitive resin layer. Further, since the technique of re-exposing the remaining positive photosensitive resin layer to produce a different pattern can be realized only by the positive positive photosensitive resin layer, the present disclosure using the positive photosensitive resin layer is used. In the method for manufacturing a resist pattern according to the present invention or the method for manufacturing a circuit wiring according to the present disclosure, an embodiment in which exposure is performed twice or more is also preferably mentioned.

<Lasting process>
In the method for manufacturing a resist pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, the temporary support of the photosensitive transfer material according to the present disclosure is attached to the substrate on the positive photosensitive resin layer side. It is preferable to include a step (bonding step) in which the outermost layer is brought into contact with the substrate and bonded.
When the photosensitive transfer material according to the present disclosure has the cover film, the bonding is performed after the cover film is peeled off in the bonding step.
The peeling method is not particularly limited and may be peeled by a known method. For example, a method of grasping and peeling off a part of the temporary support using a finger or an instrument such as tweezers can be mentioned.
In the bonding step, the substrate and the photosensitive transfer material from which the cover film has been peeled off, if necessary, are pressure-bonded so that the substrate and the outermost layer on the positive photosensitive resin layer side are in contact with each other. It is preferable to do so. According to the above aspect, the positive photosensitive resin layer having a pattern formed 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 with each other so that the outermost layer on the positive photosensitive resin layer side of the photosensitive transfer material is in contact with the conductive layer, and the substrate and the photosensitive transfer material are pressed and pressed by a roll or the like. And the method of heating is preferred. For bonding, 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 the material of the surface of the support to be bonded, for example, the material of the conductive layer and the positive photosensitive resin layer, the transport speed, the crimping machine to be used, and the like. It can be set as appropriate according to the above. When the cover film is provided on the positive photosensitive resin layer of the photosensitive transfer material, the cover film may be removed from the positive photosensitive resin layer and then pressure-bonded.
When the base material is a resin film, crimping may be performed by roll-to-roll.

[Support (base material)]
In the substrate in which the conductive layer is laminated on the support, 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 formed on the support include any conductive layer used for general wiring or touch panel wiring.
It is also preferable that a plurality of conductive layers are formed on the support.
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.

In the method for manufacturing a resist pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.
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 resist 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 off a temporary support of the photosensitive transfer material (temporary support peeling step).
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>
In the method for manufacturing a resist pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, a photomask is brought into contact with a photosensitive transfer material from which a temporary support has been peeled off to obtain the positive photosensitive resin layer. It is preferable to include a step of pattern exposure (exposure step).
In the exposure process, the exposure mask comes into contact with the intermediate layer.
By exposing the exposure mask in contact with the intermediate layer, the distance between the positive photosensitive resin layer and the mask is reduced, so that there is an advantage that the resolution of the pattern is improved.
In the above exposure step, it is preferable to irradiate the substrate on which at least the intermediate layer and the positive photosensitive resin layer are formed with active light rays through a mask having a pattern.
For example, in this step, the photoacid generator contained in the positive photosensitive resin layer is decomposed to generate an acid, and the catalytic action of the generated acid hydrolyzes the acid-degradable group contained in the coating film component. Then, an acid group, for example, a carboxy group or a phenolic hydroxyl group is generated.
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 line (405 nm) and other active light sources 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 apparatus, 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 positive photosensitive resin layer to be used, but is preferably 5 mJ / cm ² to 200 mJ / cm ² , and preferably 10 mJ / cm ² to 100 mJ / cm ² . More preferred.
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 positive photosensitive resin layer during exposure.

<Development process>
It is preferable that the method for manufacturing a resist pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure includes a step (development step) of developing the positive photosensitive resin layer to form a resist pattern.
The developing step removes the exposed portion of the positive photosensitive resin layer.
The development of the exposed positive photosensitive resin layer in the development step can be performed using a developing solution.
The developing solution is not particularly limited as long as the positive photosensitive resin 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 where the positive photosensitive resin 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 the developer on the positive photosensitive resin layer after exposure with 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 resist pattern according to the present disclosure, or the method for manufacturing a circuit wiring according to the present disclosure, includes a step of washing with water or the like after development, a step of drying a support having the obtained resist pattern, and the like. It may include a known step.

Further, it may have a post-baking step of heat-treating the resist 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 postbake 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 at each step in the method for manufacturing the resist 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 substrate in a region where the resist pattern is not arranged.
In the etching step, the pattern formed from the positive photosensitive resin 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 (preferably 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 resist pattern using a stripping solution (etching resist stripping step) after the etching step.
After the completion of the etching step, the patterned positive photosensitive resin layer remains. If the positive photosensitive resin layer is unnecessary, all the remaining positive photosensitive resin layers may be removed.
As a method of peeling using a stripping liquid, for example, the positive photosensitive resin layer (resist pattern) or the like is added to the stripping liquid being stirred at preferably at 30 ° C to 80 ° C, more preferably 50 ° C to 80 ° C. Examples thereof include a method of immersing the substrate having the substrate for 5 to 30 minutes.
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 resist 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 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 (the 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)
The input device according to the present disclosure preferably includes circuit wiring manufactured by using the photosensitive transfer material according to the present disclosure. Examples of the method for manufacturing the circuit wiring using the photosensitive transfer material according to the present disclosure include the above-mentioned method for manufacturing the circuit wiring according to the present disclosure.
Further, the input device according to the present disclosure is preferably a capacitance type input device.
The input device according to the present disclosure is preferably an input device including circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure.
The method for manufacturing the input device according to the present disclosure preferably includes the method for manufacturing the circuit wiring according to the present disclosure.
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 preferably includes circuit wiring manufactured by using the photosensitive transfer material according to the present disclosure. Examples of the method for manufacturing the circuit wiring using the photosensitive transfer material according to the present disclosure include the above-mentioned method for manufacturing the circuit wiring according to the present disclosure.
Further, the touch panel according to the present disclosure is preferably a touch panel having at least the wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure.
The method for manufacturing the touch panel according to the present disclosure preferably includes 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 including the touch panel according to the present disclosure.
The method for manufacturing the touch panel display device according to the present disclosure preferably includes the method for manufacturing the circuit wiring according to the present disclosure, and more preferably includes the method for manufacturing 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 Japanese Patent Application Laid-Open No. 2012-89102), OGS (One Glass Solution) type, TOR (Touch-on-Lens) type (for example, Japanese Patent Laid-Open No. (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 invention 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 embodiment of the present invention. Therefore, the scope of the embodiment of the present invention 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>
Each component was mixed with the following composition to prepare a photosensitive resin composition 1.

[Composition of Photosensitive Resin Composition 1]
-Specific polymer 1 (the following compound, weight average molecular weight 15,000): 9.66 parts by mass (Tg of the specific polymer 1 was measured by the method described above and found to be 40 ° C.).
-Photoacid generator (compound B below): 0.25 parts by mass-Surfactant (compound C below): 0.01 parts by mass-Additive (compound D below): 0.08 parts by mass-propylene glycol monomethyl ether Acetate [solvent]: 90.00 parts by mass

In the above structure, the numerical value of each structural unit represents the content (mass%) of each structural unit.
Further, the specific polymer 1 was synthesized with reference to the description in paragraphs 0155 to 0156 of JP-A-2018-031847.

<Preparation of Composition 1 for Forming Intermediate Layer>
Each component was mixed with the following composition to prepare a composition 1 for forming an intermediate layer.

[Composition of Composition 1 for Forming Intermediate Layer]
-Pure water: 33.7 parts by mass-Methanol: 62.7 parts by mass-Hypromellose methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH-03): 3.5 parts by mass-Surfactant (DIC Corporation) Made by Megafuck (registered trademark) F444): 0.1 parts by mass

<Preparation of photosensitive transfer material>
On a polyethylene terephthalate film having a thickness of 50 μm (hereinafter referred to as “PET (A)”) which is a temporary support, the composition 1 for forming an intermediate layer is prepared by using a slit-shaped nozzle, and the dry film thickness is 3.0 μm. It was applied in a certain amount. After the intermediate layer forming composition 1 was dried, the photosensitive resin composition 1 was applied in an amount having a dry film thickness of 5.0 μm using a slit-shaped nozzle. The film was dried with warm air at 100 ° C., and finally a polyethylene film (OSM-N, manufactured by Tredegar) was pressure-bonded as a cover film to prepare a photosensitive transfer material.

<Measurement of indentation hardness>
A glass plate (manufactured by Corning Co., Ltd.) in which the cover film was peeled off from the produced photosensitive transfer material and alkaline-cleaned under laminating conditions of a laminating roll temperature of 90 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating rate) of 3.6 m / min. A photosensitive transfer material was laminated on EagleXG), and then the temporary support was peeled off from the interface with the intermediate layer to expose the intermediate layer.
In an environment of 25 ° C and 60% RH, a round indenter (model number 8188 manufactured by Tokyo Diamond Tool Mfg. Co., Ltd.) was attached to a dynamic ultrafine hardness tester (DUH-W201 manufactured by Shimadzu Corporation) for the intermediate layer. A indentation test was performed at test MODE1 and a load speed of 1.4 mN / s. The load was gradually increased to obtain a load (mN) such that the pushing depth was 1.00 ± 0.05 μm, which was used as an index of film hardness.
The measurement results are shown in Table 1.

<Manufacturing of substrate>
A roll-shaped substrate (copper substrate) in which a copper layer was formed by a sputtering method at a thickness of 250 nm on a polyethylene terephthalate (PET) film having a thickness of 200 μm was used.

<Evaluation of photosensitive transfer material: Evaluation of mask contamination>
The cover film was peeled off from the produced photosensitive transfer material, and laminated on the copper substrate under laminating conditions of a laminating roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating rate) of 1.0 m / min. The sample was cut into 10 cm squares to make sample pieces. The temporary support is peeled off from the sample piece from the boundary surface with the intermediate layer, an alkali-cleaned glass plate (EagleXG manufactured by Corning Inc.) is placed on the sample piece, lightly pressed by hand, and then exposed through the glass at an exposure amount of 100 mJ / cm ² . Exposure was performed with a high-pressure mercury lamp. After exposure, place a 3 kg weight on the glass plate, slowly peel off the glass after 10 minutes, check for the presence or absence of components contained in the photosensitive transfer material on the glass, and use it as an index of mask contamination during contact exposure. did.
If there was adhesion to the glass, it was described as "Yes" in the "Mask Contamination" column in Table 1, and if it was not, it was described as "No".

<Evaluation of photosensitive transfer material: Evaluation of retention stability>
The cover film was peeled off from the produced photosensitive transfer material, and laminated on the copper substrate under laminating conditions of a laminating roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating rate) of 1.0 m / min. The sample was cut into 10 cm squares to make sample pieces. The temporary support is peeled off from the sample piece from the boundary surface with the intermediate layer, a photomask having a line / space = 10 μm / 10 μm pattern is brought into contact with the intermediate layer, and exposure with a high-pressure mercury lamp is performed with an exposure amount of 100 mJ / cm ² . went. After the exposure, the sample was left for 3 hours and subjected to dip development for 40 seconds using a 1.0% aqueous sodium carbonate solution.
Separately, a sample prepared in the same manner except that it was left to stand for 24 hours after exposure was prepared. The line widths of the obtained samples having different placement times were measured at 5 points in the substrate surface, and the average value was used as the line width data. Using this, (line width of the sample left for 3 hours / line width of the sample left for 24 hours) was used as an index value of the retention stability. It can be said that the closer the index value is to 1, the smaller the variation in line width is even when the leaving time after exposure changes, and the higher the process suitability. The index value is preferably 0.80 to 1.20, and more preferably 0.90 to 1.10.
Generally, when the photosensitive resin layer is of the positive type, the line becomes thinner because the solubility is improved by leaving it, and the index value becomes larger than 1. Further, when the photosensitive resin layer is a negative type, the solubility of the photosensitive resin layer is lowered by leaving the photosensitive resin layer, so that the index value is smaller than 1.

(Example 2)
In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner as in Example 1 except that the following composition 2 for forming an intermediate layer was used instead of the composition 1 for forming an intermediate layer. The evaluation results are shown in Table 1.

<Preparation of composition 2 for forming an intermediate layer>
The intermediate layer forming composition 2 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was as follows.

[Composition of Composition 2 for Forming Intermediate Layer]
-Pure water: 33.7 parts by mass-Methanol: 62.7 parts by mass-Hydroxypropylmethyl cellulose (Metros 60SH-06 manufactured by Shin-Etsu Chemical Co., Ltd.): 3.5 parts by mass-Surfactant (manufactured by DIC Corporation) Megafuck (registered trademark) F444): 0.1 part by mass

(Example 3)
<Preparation of composition 3 for forming an intermediate layer>
The intermediate layer forming composition 3 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was as follows.

[Composition of Composition 3 for Forming Intermediate Layer]
-Pure water: 33.7 parts by mass-Methanol: 61.2 parts by mass-Hydroxypropyl cellulose (HPC-SSL manufactured by Nippon Soda Co., Ltd.): 5.0 parts by mass-Surfactant (Megafuck manufactured by DIC Corporation) (Registered trademark) F444): 0.1 part by mass

<Preparation of photosensitive transfer material>
The composition 1 for forming an intermediate layer was applied onto PET (A) using a slit-shaped nozzle in an amount having a dry film thickness of 2.0 μm. After the intermediate layer forming composition 1 is dried, the intermediate layer forming composition 3 is placed on top of the intermediate layer forming composition 1 and the total dry film thickness with the intermediate layer forming composition 1 is 4.0 μm using a slit-shaped nozzle. It was applied in a certain amount.
After the intermediate layer forming composition 3 was dried, the photosensitive resin composition 1 was applied onto the photosensitive resin composition 1 in an amount such that the dry film thickness was 5.0 μm.
Then, it was dried with warm air at 100 ° C., and finally a polyethylene film (OSM-N manufactured by Tredegar) was pressure-bonded as a cover film to prepare a photosensitive transfer material. The obtained photosensitive transfer material was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 4)
A polymer novolak-EVE (1-ethoxyethyl protected product) having the following structure was synthesized by the same method as in Example 1 of JP-A-2003-98671. Using the synthesized novolak resin, a positive photosensitive resin composition 2 was prepared by the following formulation.

<Composition of Positive Photosensitive Resin Composition 2>
Polymer Novolac-EVE (1-ethoxyethyl protected body, structure below): 95.8 parts-Photoacid generator (PAG-1, JP-A-2002-528451) Synthesized according to the method described in paragraph 0108 of the following publication. Compound of structure. Ts moiety represents p-toluenesulfonyl group.): 2 parts ・ Sensitizer: (Sensing agent 1, manufacturer: manufactured by Kawasaki Kasei Co., Ltd., 9,10-dibutoxyanthracene, structure below): 2 Parts ・ Additive (Compound D above): 0.1 parts ・ Surface active agent (Compound C above): 0.1 parts ・ Propropylene glycol monomethyl ether acetate: 900 parts

Using the obtained positive photosensitive resin composition 2, a photosensitive transfer material was prepared in the same manner as in Example 1 and evaluated. However, the roll temperature at the time of laminating was 150 ° C., and the laminating speed was 1 m / min. Further, in the evaluation of the retention stability, it was impossible to form a pattern using a photomask having a pattern of line / space = 10 μm / 10 μm, so a photo having a pattern of line / space = 40 μm / 40 μm. I used a mask.

(Example 5)
In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner except that the intermediate layer was coated so that the dry film thickness was 4.5 μm.

(Example 6)
In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner except that the intermediate layer was coated so that the dry film thickness was 1.0 μm.

(Comparative Example 1)
In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the intermediate layer forming composition 3 was used instead of the intermediate layer forming composition 1. The evaluation results are shown in Table 1.

(Comparative Example 2)
In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the following composition 4 for forming an intermediate layer was used instead of the composition 1 for forming an intermediate layer. The evaluation results are shown in Table 1.

<Preparation of composition 4 for forming an intermediate layer>
The intermediate layer forming composition 4 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was as follows.

[Composition of Composition 4 for Forming Intermediate Layer]
-Pure water: 33.7 parts by mass-Methanol: 62.7 parts by mass-Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval PVA-205): 3.5 parts by mass-Surfactant (manufactured by DIC Co., Ltd., Mega Fuck (registered trademark) F444): 0.1 parts by mass

(Comparative Example 3)
In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the following composition 5 for forming an intermediate layer was used instead of the composition 1 for forming an intermediate layer. The evaluation results are shown in Table 1.

<Preparation of composition 5 for forming an intermediate layer>
The intermediate layer forming composition 5 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was as follows.

[Composition of Composition 5 for Forming Intermediate Layer]
-Pure water: 33.7 parts by mass-Methanol: 62.7 parts by mass-Hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., HEC AL-15): 3.5 parts by mass-Surfactant (manufactured by DIC Corporation) , Megafuck® F444): 0.1 parts by mass

(Comparative Example 4)
In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the following composition 6 for forming an intermediate layer was used instead of the composition 1 for forming an intermediate layer. The evaluation results are shown in Table 1.

<Preparation of composition 6 for forming an intermediate layer>
The intermediate layer forming composition 6 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was as follows.

[Composition of Composition 6 for Forming Intermediate Layer]
-Pure water: 33.7 parts by mass-Methanol: 62.7 parts by mass-Carboxymethyl cellulose (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., cellogen 5A): 3.5 parts by mass-surfactant (manufactured by DIC Corporation, Megafuck (registered trademark) F444): 0.1 parts by mass

(Comparative Example 5)
<Preparation of Photosensitive Resin Composition 3>
Each component was mixed with the following composition to prepare a photosensitive resin composition 3.

[Composition of Photosensitive Resin Composition 3]
-Methyl methacrylate / methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate copolymer (molar ratio = 55/28/12/5, weight average molecular weight = 80,000, 35% by mass solution, solvent is methyl ethyl ketone / 1 -Methoxy-2-propanol = 2/1): 100.0 parts by mass, dodecapropylene glycol diacrylate: 15.0 parts by mass, tetraethylene glycol dimethacrylate: 3.5 parts by mass, p-toluenesulfonamide: 1. 2 parts by mass, 4,4'-bis (diethylamino) benzophenone: 0.12 parts by mass, benzophenone: 2.3 parts by mass, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer (25 parts by mass) % Dichloromethane solution): 4.5 parts by mass ・ Tribromomethylphenyl sulfone: 0.25 parts by mass ・ Leuco crystal violet: 0.25 parts by mass ・ Malakite green: 0.02 parts by mass

<Preparation of photosensitive transfer material>
The composition 1 for forming an intermediate layer was applied onto PET (A) using a slit-shaped nozzle in an amount having a dry film thickness of 1.0 μm. After the intermediate layer forming composition 1 was dried, the photosensitive resin composition 2 was applied in an amount having a dry film thickness of 5.0 μm. The film was dried with warm air at 100 ° C., and finally a polyethylene film (OSM-N, manufactured by Tredegar) was pressure-bonded as a cover film to prepare a photosensitive transfer material.
The photosensitive resin layer formed in Comparative Example 2 is a negative photosensitive resin layer.
The obtained photosensitive transfer material was evaluated in the same manner as in Example 1. However, in the evaluation of the retention stability, the resolution of the negative photosensitive resin layer is insufficient, and it is impossible to form a pattern using a photomask having a line / space = 10 μm / 10 μm pattern. Therefore, a photomask having a pattern of line / space = 40 μm / 40 μm was used. The evaluation results are shown in Table 1.

From the results shown in Table 1, it can be seen that the photosensitive transfer material according to the present disclosure suppresses contamination of the mask during contact exposure.
Further, it can be seen that the photosensitive transfer material in the above-mentioned examples is also excellent in retention stability.
In Comparative Examples 1 to 5, since the indentation hardness value in the intermediate layer was low, the components contained in the intermediate layer adhered to the glass.

(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 obtained in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.). An intermediate photomask is used using a photomask provided with a pattern (hereinafter, also referred to as "pattern A") shown in FIG. 2, which has a structure in which a conductive layer pad is connected in one direction after the temporary support is peeled off. Contact exposure was performed in contact with the layer.
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 a aligned state, and the pattern was developed and washed with water.
In the pattern B shown in FIG. 3, the gray portion G is a 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 positive photosensitive resin layer was peeled off with a stripping solution (10 mass% sodium hydroxide aqueous solution) to obtain a circuit wiring substrate.
As a result, a circuit wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and the pattern was beautiful.

(Examples 102 to 106)
When the photosensitive transfer materials obtained in Examples 2 to 6 were used and the same evaluation as in Example 101 was performed, the pattern was clean with no peeling or chipping.

10: Temporary support, 12: Intermediate layer, 14: Positive photosensitive resin layer, 16: Cover film, 100: Photosensitive transfer material, SL: Solid line part, G: Gray part, DL: Dotted line part

The disclosure of Japanese patent application 2018-65544 filed on March 29, 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 (12)

Temporary support and
With the middle class,
The positive photosensitive resin layer and the positive photosensitive resin layer are provided in this order.
The temporary support and the intermediate layer are in contact with each other.
The indentation hardness on the surface of the intermediate layer on the side in contact with the temporary support is 5.0 mN or more.
Photosensitive transfer material. The photosensitive transfer material according to claim 1, wherein the intermediate layer contains a cellulose ether compound. The first or second aspect of the present invention, wherein the intermediate layer includes two or more layers, and the layer in contact with the positive photosensitive resin layer among the layers contained in the intermediate layer contains a cellulose ether compound. Photosensitive transfer material. The photosensitive layer according to claim 3, wherein the layer in the intermediate layer in contact with the temporary support contains hydroxypropylmethyl cellulose, and the layer in the intermediate layer in contact with the positive photosensitive resin layer contains hydroxypropyl cellulose. Sex transfer material. The photosensitive transfer material according to claim 2 or 3, wherein the cellulose ether compound contains hydroxypropylmethyl cellulose. The one according to any one of claims 1 to 5 , wherein the positive photosensitive resin layer contains a polymer having a structural unit having an acid group protected by an acid-degradable group and a photoacid generator. The photosensitive transfer material described. The photosensitive transfer material according to claim 6 , wherein the structural unit having an acid group protected by the acid-degradable group includes a structural unit represented by any of the following formulas A1 to A3.

In formula A1, R ¹¹ and R ¹² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or an aryl group. Representing an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ is a single-bonded or divalent linking group. , R ¹⁵ represents a substituent, and n represents an integer from 0 to 4.
In formula A2, R ²¹ and R ²² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is an alkyl group or an aryl group. Representing an aryl group, R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, and R ²⁴ may independently form a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, or an alkenyl group. It represents an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In formula A3, 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. Y represents —S— or —O—. The photosensitive transfer material according to claim 6 or 7 , wherein the structural unit having an acid group protected by the acid-degradable group includes a structural unit represented by the following formula A3-2.

In formula A3-2, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group. A group or aryl group may be represented, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. show. A step of bringing the temporary support of the photosensitive transfer material according to any one of claims 1 to 8 into contact with the substrate and attaching the outermost layer on the positive photosensitive resin layer side to the substrate. When,
The step of peeling off the temporary support of the photosensitive transfer material and
A step of contacting a photomask with a photosensitive transfer material from which the temporary support has been peeled off to perform pattern exposure of the positive photosensitive resin layer.
A method for producing a resist pattern, comprising the step of developing the positive photosensitive resin layer after the exposure step to form a resist pattern, and the step of forming a resist pattern in this order. A step of bringing the outermost layer of the photosensitive transfer material according to any one of claims 1 to 8 on the positive photosensitive resin layer side into contact with the substrate and bonding the substrate.
The step of peeling off the temporary support of the photosensitive transfer material and
A step of contacting a photomask with a photosensitive transfer material from which the temporary support has been peeled off to perform pattern exposure of the positive photosensitive resin layer.
The step of developing the positive photosensitive resin layer to form a resist pattern, and
A method for manufacturing a circuit wiring including a step of etching a substrate in a region where a resist pattern is not arranged, and a step of etching the substrate in this order. A touch panel including circuit wiring manufactured by using the photosensitive transfer material according to any one of claims 1 to 8 . A touch panel display device including the touch panel according to claim 11 .

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