JPWO2020116068A1 - Transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method - Google Patents

Abstract

It has a temporary support having a thickness of 7 μm to 18 μm and a chemically amplified positive photosensitive resin layer, and the temporary support is at least on the side where the chemically amplified positive photosensitive resin layer is provided. Provided are a transfer material having irregularities on the opposite surface, and an application thereof.

Description

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

In photolithography used for forming circuit wiring in a touch panel or the like, the use of a photosensitive transfer material has been studied for the reasons of reducing the number of steps and making the thickness of the photosensitive layer uniform. As the photosensitive transfer material, a transfer material having a temporary support and a photosensitive layer is usually used. The photosensitive layer is roughly classified into a negative type in which an exposed portion remains after development and a positive type in which an unexposed portion remains after development. In photolithography using a transfer material, the photosensitive layer of the transfer material provided on the substrate is exposed in a pattern through, for example, a mask (also referred to as “photomask”; the same applies hereinafter) (hereinafter, referred to as “pattern exposure”). A desired pattern can be formed by then developing.

As a transfer material that can be used for photolithography, for example, Japanese Patent Application Laid-Open No. 2010-72589 states that the melt viscosity at 110 ° C. is 10,000 Pa on a temporary support having a thickness of 12 μm or more and 40 μm or less, either directly or through an intermediate layer only. A photosensitive transfer material having a photosensitive resin layer of s or more and 30,000 Pa · s or less is disclosed.

Further, Japanese Patent Application Laid-Open No. 2017-78852 discloses a positive type dry film resist having a resist layer on a temporary support, and the total light haze of the temporary support is 0.3% or less. Has been done.

In photolithography using a transfer material, in order to prevent contamination of the mask used during exposure, it is possible to expose the photosensitive layer through the temporary support without peeling the temporary support from the transfer material before exposure. be. On the other hand, when the photosensitive layer is exposed through the temporary support, there may be a problem that the linearity of the obtained pattern is lowered due to the diffusion of light caused by the temporary support. Therefore, for example, in Japanese Patent Application Laid-Open No. 2017-78852, light diffusion in the temporary support is reduced by using a temporary support having a low haze.

However, as the circuit wiring becomes finer and higher in definition, when the photosensitive layer is exposed via the temporary support, the pattern obtained is obtained as the standing time elapses from the exposure to the next step (for example, development). The problem that the line width of is narrower than the design value (referred to as "Post Exposure Delay", hereinafter referred to as "PED") may occur. Among various photosensitive layers, PED tends to be remarkable when a chemically amplified positive photosensitive layer is exposed via a temporary support. In the exposed chemically amplified positive photosensitive layer, it is considered that the acid generated by the exposure causes the polarity change of the photosensitive layer in a chain reaction. Therefore, it is considered that the chemically amplified positive photosensitive layer is particularly susceptible to the influence of the standing time from the exposure to the next step. As a result, the circuit wiring size changes greatly depending on the PED, and there is a possibility that dimensional variation may occur. With the increase in definition of circuit wiring, more effective technology is required as a countermeasure technology for PED.

This disclosure has been made in view of the above circumstances.
One aspect of the present disclosure is to provide a transfer material capable of reducing the amount of change in the line width of a pattern with the lapse of standing time after exposure.
Another aspect of the present disclosure is to provide a method for producing a resin pattern in which the amount of change in the line width of the pattern with the passage of the standing time after exposure is reduced.
Another aspect of the present disclosure is an object of the present invention to provide a method for manufacturing a circuit wiring in which the amount of change in the line width of a pattern with the passage of a standing time after exposure is reduced.
Another aspect of the present disclosure is to provide a method for manufacturing a touch panel in which the amount of change in the line width of a pattern with the passage of a standing time after exposure is reduced.

Means for solving the above problems include the following aspects.
<1> A temporary support having a thickness of 7 μm to 18 μm and a chemically amplified positive photosensitive resin layer are provided, and the temporary support is provided with at least the chemically amplified positive photosensitive resin layer. A transfer material with irregularities on the surface opposite to the side.
<2> The transfer material according to <1>, wherein the temporary support contains particles and the haze value of the temporary support is 0.50% or less.
<3> The transfer material according to <1> or <2>, wherein the temporary support has irregularities only on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided.
<4> An intermediate layer containing a water-soluble resin provided in contact with the chemically amplified positive photosensitive resin layer is provided between the temporary support and the chemically amplified positive photosensitive resin layer <1. > The transfer material according to any one of <3>.
<5> The transfer material according to <4>, wherein the thickness of the intermediate layer is 0.1 μm to 3.0 μm.
<6> The chemically amplified positive photosensitive resin layer contains a polymer containing a structural unit having a group in which an acid group is protected by an acid-degradable group, and an acid generator, <1> to <5. > The transfer material according to any one of.
<7> The polymer containing a structural unit having a group in which the acid group is protected by an acid-degradable group is represented by a structural unit represented by the formula A1, a structural unit represented by the formula A2, and a structural unit represented by the formula A3. The transfer material according to any one of <1> to <6>, which is a polymer containing at least one structural unit selected from the group consisting of structural units.

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 Representing an alkyl or aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, where R ¹⁴ represents a hydrogen atom or methyl group and X ¹ is a single bond or It represents a 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 Representing an alkyl group or 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, or an alkoxy. It represents a group, an alkenyl group, 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, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is Representing an alkyl or aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, where R ³⁴ represents a hydrogen atom or methyl group and X ⁰ is a single bond or Represents a divalent linking group.
<8> A step of bringing the substrate and the transfer material according to any one of <1> to <7> into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the substrate and the transfer material. The step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support and the step of pattern exposing the chemically amplified positive photosensitive resin layer after the pattern exposure step are performed. A method for manufacturing a resin pattern, including a step of developing and forming a resin pattern.
<9> A substrate having a conductive layer and the transfer material according to any one of <1> to <7> are attached by contacting the substrate and the chemically amplified positive photosensitive resin layer in the transfer material. The step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the step of bonding and the step of bonding via the temporary support, and the step of pattern-exposing the chemical-amplified positive photosensitive resin layer after the step of pattern exposure. A step of developing the sex resin layer to form a resin pattern, a step of etching the conductive layer exposed in a region where the resin pattern is not formed, and a step of removing the resin pattern after the etching step. A method of manufacturing circuit wiring, including.
<10> A substrate having a conductive layer and the transfer material according to any one of <1> to <7> are attached by contacting the substrate and the chemically amplified positive photosensitive resin layer in the transfer material. The step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the step of bonding and the step of bonding via the temporary support, and the step of pattern-exposing the chemical-amplified positive photosensitive resin layer after the step of pattern exposure. A step of developing the sex resin layer to form a resin pattern, a step of etching the conductive layer exposed in a region where the resin pattern is not formed, and a step of removing the resin pattern after the etching step. A method for manufacturing a touch panel including ,.

According to one aspect of the present disclosure, it is possible to provide a transfer material capable of reducing the amount of change in the line width of the pattern with the lapse of the standing time after exposure.
According to another aspect of the present disclosure, it is possible to provide a method for producing a resin pattern in which the amount of change in the line width of the pattern with the lapse of the standing time after exposure is reduced.
According to another aspect of the present disclosure, it is possible to provide a method for manufacturing a circuit wiring in which the amount of change in the line width of the pattern with the lapse of the standing time after exposure is reduced.
According to another aspect of the present disclosure, it is possible to provide a method for manufacturing a touch panel in which the amount of change in the line width of the pattern with the lapse of the standing time after exposure is reduced.

FIG. 1 is a schematic view showing an example of the layer structure of the transfer material according to the present disclosure. FIG. 2 is a schematic view showing an example of a method for manufacturing a resin pattern and a method for manufacturing a circuit wiring according to the present disclosure. FIG. 3 is a schematic view showing the pattern A.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the purpose of the present disclosure.

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 a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present disclosure, "(meth) acrylic" means both acrylic and methacrylic, or either one, and "(meth) acrylate" means both acrylate and methacrylate, or either one. do.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. ..
In the present disclosure, the term "process" is included in the term "process" as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes. ..
In the notation of a group (atomic group) in the present disclosure, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, the chemical structural formula may be described by a simplified structural formula in which a hydrogen atom is omitted.

<Transfer material>
The transfer material according to the present disclosure has a temporary support having a thickness of 7 μm to 18 μm and a chemically amplified positive photosensitive resin layer (hereinafter, may be referred to as “photosensitive resin layer”). The temporary support has at least irregularities on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided.

The transfer material according to the present disclosure can reduce the amount of change in the line width of the pattern with the lapse of the standing time after exposure. Although the reason why the transfer material according to the present disclosure exerts the above effect is not clear, it is presumed as follows.
The PED is used for the standing time after exposure in the exposed portion of the chemically amplified positive photosensitive resin layer (hereinafter referred to as “unavoidable exposed portion”) that is inevitably formed in a region wider than the design dimension of the pattern. It is considered that this is caused by the diffusion of acid and the progress of acid-catalyzed reaction with the lapse of time. When the photosensitive resin layer is pattern-exposed via the temporary support, the light emitted from the light source passes through the temporary support and reaches the photosensitive resin layer. Further, for example, when the photosensitive resin layer is pattern-exposed using a mask, there is an interval corresponding to the thickness of the temporary support between the mask and the photosensitive resin layer. Therefore, when the photosensitive resin layer is exposed through the temporary support, an unavoidable exposed portion is likely to be formed due to the diffusion and diffraction of light caused by the temporary support. Since the acid diffusion and the acid catalytic reaction proceed in the unavoidable exposed portion, the polarity of the photosensitive resin layer may change exponentially with the lapse of the standing time after the exposure. Therefore, when a chemically amplified positive photosensitive resin layer is used as the photosensitive layer, it is considered that PED is likely to be caused by the formation of the unavoidable exposed portion.
In the conventional techniques described in JP-A-2010-72589 and JP-A-2017-78852, the relationship between the thickness of the temporary support and PED has not been investigated, so the formation of an unavoidable exposed portion is fundamental. It is considered difficult to avoid it.
On the other hand, since the transfer material according to the present disclosure has a temporary support having a thickness of 7 μm to 18 μm and a chemically amplified positive photosensitive resin layer, the distance between the mask and the photosensitive resin layer becomes small, and the temporary support is temporarily provided. Even when the photosensitive resin layer is exposed via the support, the formation of an unavoidable exposed portion can be suppressed. Therefore, it is considered that the transfer material according to the present disclosure can reduce the amount of change in the line width of the pattern with the lapse of the standing time after exposure. Further, the transfer material according to the present disclosure has at least a temporary support having irregularities on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided, so that the surface of the temporary support slides. Improves sex. Therefore, it is possible to perform mask alignment by sliding each other in a state where the mask and the surface of the temporary support are in contact with each other, and it is suitable for so-called contact exposure in which the surface of the mask and the temporary support are brought into contact with each other for exposure. .. In contact exposure, the distance between the mask and the photosensitive resin layer can be made smaller, so that the amount of change in the line width of the pattern with the lapse of the standing time after exposure can be reduced.

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

An example of the transfer material according to the present disclosure will be described with reference to the drawings. FIG. 1 schematically shows an example of the layer structure of the transfer material according to the present disclosure. For example, the transfer material 100 shown in FIG. 1 has a temporary support 12, a chemically amplified positive photosensitive resin layer 14, and a protective film 16. The chemically amplified positive photosensitive resin layer 14 preferably contains a polymer having a structural unit having a group in which an acid group is protected by an acid-degradable group, and a photoacid generator.

[Temporary support]
The transfer material according to the present disclosure has a temporary support having a thickness of 7 μm to 18 μm. Further, the temporary support in the present disclosure has at least irregularities on the surface on the side opposite to the side on which the chemically amplified positive photosensitive resin layer is provided. The transfer material according to the present disclosure has a thickness of 7 μm to 18 μm, and has at least a temporary support having irregularities on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided. Since the formation of an unavoidable exposed portion when the chemically amplified positive photosensitive resin layer is exposed via the temporary support can be suppressed, the amount of change in the line width of the pattern with the lapse of the standing time after the exposure ( Hereinafter, it may be simply referred to as “line width change amount”).

The thickness of the temporary support is 18 μm or less, preferably 16 μm or less, more preferably 14 μm or less, and further preferably 12 μm or less. By adjusting the upper limit of the thickness of the temporary support within the above numerical range, the amount of change in line width can be reduced.

The thickness of the temporary support is 7 μm or more, preferably 8 μm or more. By adjusting the lower limit of the thickness of the temporary support within the above numerical range, the handleability of the temporary support can be improved.

The thickness of the temporary support can be measured by the following method.
In the cross-sectional observation image in the thickness direction of the temporary support, the arithmetic mean value of the thickness of the temporary support measured at 10 randomly selected points is obtained, and the obtained value is defined as the thickness of the temporary support. A cross-sectional observation image of the temporary support in the thickness direction can be obtained by using a scanning electron microscope (SEM) or a laser microscope.

The temporary support has at least irregularities on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided. From the viewpoint of reducing the amount of change in line width, the temporary support preferably has irregularities only on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided. In the present disclosure, "having irregularities on the surface" specifically means that the surface roughness Ra is 0.002 μm or more.

The surface roughness Ra of the temporary support on the uneven side is preferably 0.005 μm to 1 μm, more preferably 0.01 μm to 1 μm, from the viewpoint of reducing the amount of change in line width. It is more preferably 04 μm to 0.5 μm. The surface roughness Ra of the temporary support on the side having irregularities is preferably 0.5 μm or less from the viewpoint of suppressing light scattering during exposure.

The surface roughness Ra of the temporary support can be measured by the following method.
For the measurement surface of the temporary support, a three-dimensional optical profiler (New View7300, manufactured by Zygo) is used to obtain a surface profile of the temporary support under the following conditions. As the measurement and analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed with the above analysis software (MeroPro ver8.3-2-Microscope Application), and histogram data is obtained in the Surface Map screen. Arithmetic mean roughness is calculated from the obtained histogram data, and the obtained value is defined as surface roughness Ra.

(Measurement condition)
Objective lens: 50x Zoom: 0.5x Measurement area: 1.00mm x 1.00mm
(Analysis conditions)
Removed: plane
Filter: off
FilterType: average
Remove spikes: on
Spike Height (xRMS): 7.5

Examples of the temporary support include a glass base material, a resin film, and the like. Among the above, as the temporary support, a resin film is preferable from the viewpoint of strength, flexibility and the like. When the temporary support has a multi-layer structure, the above-mentioned glass base material, resin film, or the like may be used as the base material.

Examples of the resin contained in the resin film include cycloolefin polymer, polyethylene terephthalate, cellulose triacetate, polystyrene, polycarbonate and the like. Among the above, polyethylene terephthalate is preferable as the resin contained in the resin film from the viewpoint of optical properties, solvent resistance, and heat resistance.

Examples of the resin film include a cycloolefin polymer film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among the above, the resin film is preferably a polyethylene terephthalate film from the viewpoint of optical properties, solvent resistance, and heat resistance.

Examples of commercially available resin films include Lumirror (registered trademark; the same applies hereinafter) 12QS62 and Lumirror 16QS62 (both manufactured by Toray Industries, Inc.).

The temporary support preferably contains particles. Since the temporary support contains particles, irregularities can be formed on the surface of the temporary support, and therefore, the transfer material according to the present disclosure is suitable for contact exposure capable of high resolution. Examples of the particles contained in the temporary support include organic particles and inorganic particles.
The term "containing particles" as used herein means, for example, that the particles may be dispersed in the temporary support, or a layer containing the particles is separately formed on the temporary support and integrated with the temporary support. It may be in a state where it can be treated as a modified film, or it may be a combination thereof. These embodiments can be selected according to other required characteristics such as the material and thickness of the temporary support.

Examples of the organic particles include organic resin particles such as acrylic resin particles, polyester particles, polyurethane particles, polycarbonate particles, polyolefin particles, and polystyrene particles.

Examples of the inorganic particles include silicon oxide (silica) particles, titanium oxide (titania) particles, zirconium oxide (zirconia) particles, magnesium oxide (magnesia) particles, aluminum oxide (alumina) particles and the like.

Among the above, the particles contained in the temporary support are preferably inorganic particles, more preferably silicon oxide (silica) particles, from the viewpoint of optical properties.

The haze value of the temporary support is preferably 0.50% or less, more preferably 0.45% or less, and more preferably 0.35% or less, from the viewpoint of reducing the amount of change in line width. Especially preferable. The lower limit of the haze value of the temporary support is not limited. The haze value of the temporary support may be appropriately determined in the range of 0% or more, for example. The haze value of the temporary support can be measured by a method according to JIS K7136: 2000 using a haze meter.

Among the above, as the temporary support, a temporary support containing particles and having a haze value of 0.50% or less is preferable. By using a temporary support containing particles and having a haze value of 0.50% or less, irregularities can be formed on the surface of the temporary support, and light diffusion in the temporary support containing particles can be reduced. Therefore, the amount of change in line width can be reduced.

The temporary support may have a single-layer structure consisting of only one layer, or may have a multi-layer structure including two or more layers. Further, the temporary support may include a base material and a layer containing the particles on at least one surface of the base material. As the base material, for example, the above-mentioned glass base material, resin film, or the like can be applied.

The method for producing the temporary support is not limited, and a known production method can be appropriately applied. When the temporary support is a resin film, the resin film can be produced by a known production method such as extrusion molding. Further, if necessary, the thickness of the temporary support may be adjusted by stretching (for example, biaxial stretching) or the like.

[Chemically amplified positive photosensitive resin layer]
The transfer material according to the present disclosure has a chemically amplified positive photosensitive resin layer. The transfer material according to the present disclosure can improve the sensitivity in exposure by having a chemically amplified positive photosensitive resin layer.

The chemically amplified positive photosensitive resin layer is not limited, and a known chemically amplified positive photosensitive resin layer can be applied. The chemically amplified positive photosensitive resin layer preferably contains an acid-degradable resin from the viewpoint of sensitivity, resolution and removability, and contains a heavy component having a group in which the acid group is protected by the acid-degradable group. It is more preferable to contain a coalescence and a photoacid generator. The acid-decomposable resin is not limited as long as it is a resin capable of partially decomposing a part of its molecular structure by action with an acid. Examples include polymers containing.

When a photoacid generator such as an onium salt or an oxime sulfonate compound, which will be described later, is used, the acid group generated in response to active radiation (also referred to as active light) is an acid-degradable group in the polymer. It acts as a catalyst in the deprotection reaction at the protected group. Since the acid produced by the action of one photon contributes to many deprotection reactions, the quantum yield exceeds 1, which is a large value such as the power of 10, which is high as a result of so-called chemical amplification. Sensitivity is obtained. On the other hand, when a quinonediazide compound is used as a photoacid generator that is sensitive to active radiation, 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.

The chemically amplified positive photosensitive resin layer may contain other polymers described later in addition to the polymer containing a structural unit having a group in which the acid group is protected by an acid-degradable group. In the present disclosure, a polymer containing a structural unit having a group in which an acid group is protected by an acid-degradable group and other polymers are collectively referred to as a "polymer component".

[Polymer having a structural unit in which the acid group has a group protected by an acid-degradable group: Polymer A]
The chemically amplified positive photosensitive resin layer contains a polymer (hereinafter, "polymer") containing a structural unit having a group in which an acid group is protected by an acid-degradable group (hereinafter, may be referred to as "constituent unit A"). It may be referred to as "A"). A group in which the acid group in the structural unit A is protected by an acid-degradable group is converted into an acid group by the action of an acid generated by exposure. Therefore, the solubility of the exposed chemically amplified positive photosensitive resin layer in the developing solution is increased.

The polymer A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof. The polymer A may contain 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, etc.).

(Constituent unit having an acid group protected by an acid-degradable group: Constituent unit A)
Polymer A contains a structural unit in which the acid group has a group protected by an acid-degradable group.

In the present disclosure, the "group in which an acid group is protected by an acid-degradable group" means a group having a structure in which an acid group is protected by an acid-degradable group. A group whose acid group is protected by an acid-degradable group can be converted into an acid group by the action of an acid.

In the present disclosure, the "acid group" refers to a proton dissociative group having a pKa of 12 or less. As the acid group, a known acid group such as a carboxy group or a phenolic hydroxy group can be applied. The acid group is preferably a carboxy group or a phenolic hydroxy group.

The acid-degradable group is not limited, and a known acid-degradable group can be applied. Examples of the acid-degradable group include an acid-degradable group capable of protecting an acid group in the form of an acetal (for example, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group), and an acid decomposition capable of protecting an acid group in the form of an ester. Examples include a sex group (for example, a tert-butyl group).

Examples of the group in which the acid group is protected by an acid-degradable group include a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, and a tetrahydrofuranyl ester contained in a structural unit represented by the formula A3 described later). Acetal-based functional groups such as groups), groups that are relatively difficult to decompose with an acid (for example, tertiary alkyl ester groups such as tert-butyl ester groups, tertiary alkyl carbonate groups such as tert-butyl carbonate groups), etc. Can be used.

Among the above, the group in which the acid group is protected by an acid-degradable group is preferably a group having a structure in which a carboxy group or a phenolic hydroxy group is protected in the form of acetal.

The structural unit A is at least one type of configuration selected from the group consisting of the structural unit represented by the formula A1, the structural unit represented by the formula A2, and the structural unit represented by the formula A3 from the viewpoint of sensitivity and resolution. It is preferably a unit, and more preferably at least one structural unit selected from the group consisting of the structural unit represented by the formula A1 and the structural unit represented by the formula A3. It is particularly preferable that the structural unit is at least one selected from the group consisting of the structural unit represented by 2 and the structural unit represented by the formula A3-3 described later. The structural unit represented by the formula A1 and the structural unit represented by the formula A2 are structural units having a group in which a phenolic hydroxy group is protected by an acid-degradable group. The structural unit represented by the formula A3 is a structural unit having a group in which the carboxy group is protected by an acid-degradable group.

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 Representing an alkyl or aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, where R ¹⁴ represents a hydrogen atom or methyl group and X ¹ is a single bond or It represents a 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 Representing an alkyl group or 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, or an alkoxy. It represents a group, an alkenyl group, 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, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is Representing an alkyl or aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, where R ³⁴ represents a hydrogen atom or methyl group and X ⁰ is a single bond or Represents a divalent linking group.

-Preferable embodiment of the structural unit represented by the formula A1-
In formula A1, R ¹¹ and R ¹² independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. The aryl group is preferably a phenyl group. Among the above, ^{it is preferable that R 11} and R ¹² are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.

In the formula A1, R ¹³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

In formula A1, the alkyl and aryl groups in ^{R 11} , R ¹² and R ^{13 may have substituents.}

In formula A1, ^{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 preferably 5 or 6, and more preferably 5.

In the formula A1, X ¹ is preferably a single bond, an alkylene group, -C (= O) O-, -C (= O) NR ^N- , -O- or a combination thereof, and is a single bond. Is more preferable. The alkylene group may have a linear structure, a branched structure, a cyclic structure, or a substituent. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. When X ¹ contains -C (= O) O-, it is preferable that the carbon atom contained in -C (= O) O- and the carbon atom to which R ¹⁴ is bonded are directly bonded. When ^{containing, -C (= O) NR N} - - X 1 is -C (= O) NR ^N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R 14} is bonded is directly bonded is preferable. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

In the formula A1, the group containing ^{R 11} , R ¹² and R ^{13 and X 1} are preferably bonded to each other at the para position from the viewpoint of steric hindrance of the acid protecting group. That is, the structural unit represented by the formula A1 is preferably the structural unit represented by the following formula A1-1. ^R 11 in the formula ^{A1-1, R 12, R 13,} R 14, R 15, X 1, and n, respectively, ^R 11 in the formula ^{A1, R 12, R 13,} R 14, R 15, X 1, And n are synonymous.

In the formula ^{A1, R 15} is preferably an alkyl group or a halogen atom. 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 is preferably 0 or 1, more preferably 0.

In the formula A1, R ¹⁴ is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer A can be lowered.
^{More specifically, the content of 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.
^{The content of the structural unit in which R 14} in the formula A1 is a hydrogen atom in the structural unit A is confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-nuclear magnetic resonance spectrum (NMR) measurement.} can do.

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 the formula ^{A1-2, R B4} represents a hydrogen atom or a methyl ^group, R ^{B5 to R B11} each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon ^{atoms, R B12} is a substituted group Represents, and n represents an integer of 0 to 4.

In formula A1-2, R ^B4 is preferably a hydrogen atom.
In the formula ^A1-2, R ^{B5 to R B11} is preferably a hydrogen atom.
Wherein ^{A1-2, R B12} is an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In formula A1-2, n is preferably 0 or 1, more preferably 0.

In the formula ^A1-2, a group containing R ^{B5 to R B11,} and the carbon atom ^{to which R B4} is bonded, in view of the steric hindrance of the acid protecting group, it is preferably bonded at para positions.

The following structural units can be exemplified as preferable specific examples of the structural units represented by the formula A1. Incidentally, R ^B4 in the structural unit of the following represents a hydrogen atom or a methyl group.

-Preferable embodiment of the structural unit represented by the formula A2-
In formula A2, R ²¹ and R ²² independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ²¹ and R ²² is an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. The aryl group is preferably a phenyl group. Among the above, R ²¹ and R ²² are preferably independent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and more preferably at least one of them is a hydrogen atom.

In the formula A2, R ²³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

In the formula A2, the alkyl group and the aryl group in ^{R 21} , R ²² and R ^{23 may have a substituent.}

In the formula A2, R ²⁴ is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms, respectively. .. R ²⁴ may be further substituted with a group similar to R ^24.

In the formula A2, m is preferably 1 or 2, and more preferably 1.

The following structural units can be exemplified as preferable specific examples of the structural units represented by the formula A2.

-Preferable embodiment of the structural unit represented by the formula A3-
In formula A3, 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. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. The aryl group is preferably a phenyl group. Among the above, 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 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

The alkyl group and aryl group in R ^{31 to} R ^{33 may have a substituent.}

In formula A3, ^{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 preferably 5 or 6, and more preferably 5.

In formula A3, X ⁰ is preferably a single bond or an arylene group, and more preferably a single bond. The arylene group may have a substituent.

In the formula A3, R ^34, from the viewpoint of capable of a glass transition temperature of the polymer A (Tg) lower, is preferably a hydrogen atom.
^{More specifically, the content of the structural unit in which R 34} is a hydrogen atom in the formula A3 is 20% by mass or more with respect to the total content of the structural unit represented by the formula A3 contained in the polymer A. Is preferable.
^{The content of the structural unit in which R 34} is a hydrogen atom in the structural unit represented by the formula A3 is the peak intensity calculated by a conventional method from the ^{13 C-nuclear magnetic resonance spectrum (NMR) measurement.} It can be confirmed by the strength ratio of.

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 the formula ^{A3-3, R 34} is preferably a hydrogen atom.
In formula A3-3, R ^{35 to} R ⁴¹ are preferably hydrogen atoms.

The following structural units can be exemplified as preferable specific examples of the structural units represented by the formula A3. ^{In addition, R 34} in the following constitutional unit represents a hydrogen atom or a methyl group.

The structural unit A contained in the polymer A may be used alone or in combination of two or more.

The content of the structural unit A in the polymer A is preferably 15% by mass or more, more preferably 15% by mass to 90% by mass, and 15% by mass with respect to the total mass of the polymer A. It is particularly preferably ~ 70% by mass.
The content of the structural unit A in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-NMR measurement.}

(Constituent unit having an acid group: Constituent unit B)
The polymer A preferably contains a structural unit having an acid group (hereinafter, may be referred to as “constituent unit B”). When the polymer A contains the structural unit B, the sensitivity at the time of pattern formation is improved, the polymer A is easily dissolved in an alkaline developer in the developing process after pattern exposure, and the developing time can be shortened.

The acid group in the structural unit B is a proton dissociative group having a pKa of 12 or less. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Further, the pKa of the acid group is preferably −5 or more.

Examples of the acid group in the structural unit B include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxy group, a sulfonylimide group and the like. Among the above, the acid group is preferably at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxy group.

The structural unit B can be introduced into the polymer A by a method of copolymerizing a monomer having an acid group or a method of copolymerizing a monomer having an acid anhydride structure and hydrolyzing the acid anhydride. Examples of the monomer having a carboxy group, which is an example of an acid group, include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like. Examples of the monomer having a phenolic hydroxy group, which is an example of an acid group, include p-hydroxystyrene and 4-hydroxyphenylmethacrylate. Examples of the monomer having an acid anhydride structure include maleic anhydride and the like.

The structural unit B is preferably a structural unit derived from a styrene compound having an acid group, or a structural unit derived from a vinyl compound having an acid group, and is a structural unit derived from a styrene compound having a phenolic hydroxy group, or a structural unit. It is more preferably a structural unit derived from a vinyl compound having a carboxy group, further preferably a structural unit derived from a vinyl compound having a carboxy group, and preferably a structural unit derived from (meth) acrylic acid. Especially preferable.

The structural unit B may be used alone or in combination of two or more.

The content of the structural unit B in the polymer A is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 15% by mass, based on the total mass of the polymer A. More preferably, it is 1% by mass to 10% by mass. By adjusting the content of the structural unit B in the polymer A within the above numerical range, the pattern forming property becomes better.
The content of the structural unit B in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-NMR measurement.}

(Other structural units: structural unit C)
In addition to the above-mentioned structural unit A and structural unit B, the polymer A may be other structural unit (hereinafter, may be referred to as “constituent unit C”) as long as the effect of the transfer material according to the present disclosure is not impaired. May be contained. Various characteristics of the polymer A can be adjusted by adjusting at least one of the type and the content of the structural unit C contained in the polymer A. In particular, the glass transition temperature (Tg) of the polymer A can be easily adjusted by appropriately using the structural unit C.

Examples of the monomer forming the structural unit C include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, and bicyclounsaturated compounds. , Maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated compounds with an aliphatic cyclic skeleton, and other known unsaturated Compounds and the like can be mentioned.

Examples of the constituent unit C include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, and (meth) acrylic acid. Methyl, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylate Examples thereof include structural units derived from benzyl, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetate acetate mono (meth) acrylate and the like. In addition, as the structural unit C, a structural unit derived from the compound described in paragraphs 0021 to 0024 of JP2004-246623A can be mentioned.

The structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton from the viewpoint of improving the electrical properties of the transfer material. Examples of the monomer forming the above-mentioned structural unit include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and , Benzyl (meth) acrylate and the like. Among the above, the structural unit C is preferably a structural unit derived from cyclohexyl (meth) acrylate.

The structural unit C is preferably a (meth) acrylic acid alkyl ester from the viewpoint of adhesion. Among the above, the structural unit C is more preferably a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms 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 polymer A contains, as the structural unit C, a structural unit having an ester of an acid group in the structural unit B from the viewpoint of optimizing the solubility and physical properties of the chemically amplified positive photosensitive resin layer in a developing solution. It is also preferable. Among the above, the polymer A preferably contains a structural unit having a carboxy group as the structural unit B, and further preferably contains a structural unit C containing a carboxylic acid ester group as a component, for example, (meth) acrylic. It is more preferable to contain a structural unit B derived from an acid and a structural unit C derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate.

The structural unit C may be used alone or in combination of two or more.

The content of the structural unit C in the polymer A is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 60% by mass or less, based on the total mass of the polymer A. Is more preferable, and 50% by mass or less is particularly preferable. The content of the structural unit C in the polymer A may be 0% by mass, preferably 1% by mass or more, and preferably 5% by mass or more, based on all the structural units constituting the polymer A. More preferred. By setting the content of the structural unit C in the polymer A within the above numerical range, the resolution and adhesion can be further improved.

Hereinafter, preferred examples of the polymer A 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.

The polymer A may be used alone or in combination of two or more.

The content of the polymer A in the chemically amplified positive photosensitive resin layer is 50% by mass with respect to the total solid content of the chemically amplified positive photosensitive resin layer from the viewpoint of exhibiting good adhesion to the substrate. It is preferably ~ 99.9% by mass, and more preferably 70% by mass to 98% by mass.

(Glass transition temperature of polymer A: Tg)
The glass transition temperature (Tg) of the polymer A is preferably 90 ° C. or lower, more preferably 20 ° C. to 60 ° C. from the viewpoint of transferability and adjusting the heating temperature in the heating step described later. , 30 ° C to 50 ° C is particularly preferable.

As a method of adjusting the glass transition temperature (Tg) of the polymer A within the above numerical range, for example, a method of adjusting the type and mass fraction of each structural unit contained in the polymer A by using the FOX equation as a guideline. Can be mentioned. By using the FOX formula, the glass transition temperature (Tg) of the polymer A is adjusted from the glass transition temperature (Tg) of the homopolymer of each structural unit contained in the polymer A and the mass fraction of each structural unit. can do. Further, the glass transition temperature (Tg) of the polymer A can be adjusted by adjusting the weight average molecular weight of the polymer A.

Hereinafter, the FOX formula will be described by taking a copolymer containing the first structural unit and the second structural unit as an example.
The glass transition temperature of the homopolymer of the first structural unit is Tg1, the mass fraction of the first structural unit contained in the copolymer is W1, and the glass transition temperature of the homopolymer of the second structural unit. Is Tg2, and when the mass fraction of the second constituent unit contained in the copolymer in the copolymer is W2, Tg0 of the copolymer containing the first constituent unit and the second constituent unit is taken as Tg0. (Unit: K) can be estimated according to the following formula. Therefore, a polymer having a desired glass transition temperature (Tg) can be obtained by adjusting the type and mass fraction of each structural unit contained in the target polymer using the FOX formula.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)

(Acid value of polymer A)
From the viewpoint of resolution, the acid value of the polymer A is preferably 0 mgKOH / g to 200 mgKOH / g, and more preferably 0 mgKOH / g to 100 mgKOH / g.

The acid value of the polymer represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer. Specifically, the measurement sample is dissolved in a mixed solvent of tetrahydrofuran and water (volume ratio: tetrahydrofuran / water = 9/1), and a potential difference titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.) is used. The obtained solution is neutralized and titrated with a 0.1 M aqueous sodium hydroxide solution at 25 ° C. The acid value is calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
Formula: 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: Titer 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: Mw)
The molecular weight of the polymer A is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight of the polymer A is 60,000 or less, the melt viscosity of the chemically amplified positive photosensitive resin layer is suppressed to a low level, and the polymer A 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 is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The weight average molecular weight of the polymer A can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device.
For the measurement of weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4. 6 mm ID x 15 cm, manufactured by Tosoh Corporation, Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), and Super HZ2000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation). Each one (manufactured by Tosoh Corporation) is connected in series, and THF (tetrahydrofuran) can be used as the eluent.
The measurement conditions are a sample concentration of 0.2% by mass, a flow velocity of 0.35 mL / min, a sample injection amount of 10 μL, a measurement temperature of 40 ° C., and a differential refractive index (RI) detector. Can be done.
The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A". It can be prepared using any of 7 samples of "-2500" and "A-1000".

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

(Method for producing polymer A)
The method for producing the polymer A (synthesis method) is not particularly limited, but for example, a polymerizable monomer for forming the constituent unit A, a polymerizable monomer for forming the constituent unit B, and if necessary, a polymerizable monomer. , The polymerizable monomer for forming the structural unit C can be synthesized by polymerizing in an organic solvent with a polymerization initiator. Further, the polymer A can also be synthesized by a so-called polymer reaction.

[Other polymers]
The chemically amplified positive photosensitive resin layer is a polymer that does not contain a structural unit having an acid group protected by an acid-degradable group in addition to the polymer A as long as the effect of the transfer material according to the present disclosure is not impaired. Hereinafter, it may be referred to as “another polymer”).

Examples of other polymers include polyhydroxystyrene and the like. Examples of polyhydroxystyrene include 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, ARUFON UC-3080 (all manufactured by Toagosei Co., Ltd.), and Jonclyl 690, Jonclyl 678, Jonclyl 67, and Jonclyl 586 (all manufactured by BASF). Goods can also be used.

The other polymers may be used alone or in combination of two or more.

When the chemically amplified positive photosensitive resin layer contains other polymers, the content of the other polymer in the chemically amplified positive photosensitive resin layer is 50% by mass or less with respect to the total mass of the polymer components. It is preferably 30% by mass or less, more preferably 20% by mass or less.

[Photoacid generator]
The chemically amplified positive photosensitive resin layer preferably contains a photoacid generator from the viewpoint of sensitivity and resolution. The photoacid generator is a compound capable of generating an acid by being irradiated with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

As the photoacid generator, 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. Further, a photoacid generator that is not directly sensitive to active light having a wavelength of 300 nm or more can be used as a sensitizer if it is a compound that is sensitive to active light having 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.

The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a pKa of 2 or less. A photoacid generator that generates an acid is particularly preferable. The lower limit of the pKa of the acid generated from the photoacid generator is not limited. The pKa of the acid generated from the photoacid generator is preferably -10 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 an onium salt compound and an oxime sulfonate compound, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity and resolution. ..

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Among the above, as the ionic photoacid generator, an onium salt compound is preferable, and diaryliodonium salts and triarylsulfonium salts are more 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.

Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds and the like. Among the above, as the nonionic photoacid generator, an oxime sulfonate compound is preferable from the viewpoint of sensitivity, resolution and adhesion. Specific examples of the trichloromethyl-s-triazines and the diazomethane derivative include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A.

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.

Any group of the compound having an oxime sulfonate structure represented by the formula (B1) may be substituted, and the ^{alkyl group at 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 in R 21} , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group in R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (for example, a bridge-type fat such as 7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a ring group, preferably a bicycloalkyl group or the like), or a halogen atom.

As ^{the aryl group in 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 in R ²¹ may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups and halogen atoms.

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.

The photoacid generator may be used alone or in combination of two or more.

The content of the photoacid generator in the chemically amplified positive photosensitive resin layer is 0.1% by mass to 10% by mass with respect to the total mass of the chemically amplified positive photosensitive resin layer from the viewpoint of sensitivity and resolution. It is preferably 0.5% by mass to 5% by mass, and more preferably 0.5% by mass to 5% by mass.

〔solvent〕
The chemically amplified positive photosensitive resin layer may contain a solvent.

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. Examples thereof include 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. Further, examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and these contents are incorporated in the present disclosure.

Further, in addition to the above 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-nonal. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.

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.

Examples of the solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), and propylene glycol methyl-n-butyl ether (boiling point 155 ° C.). And propylene glycol methyl-n-propyl ether (boiling point 131 ° C.) and the like can be mentioned.

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 of 176 ° C.), propylene glycol monomethyl ether propionate (boiling point of 160 ° C.), and dipropylene glycol methyl. Ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether Examples thereof include acetate (boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.).

Further, preferable examples of the solvent include esters, ethers, ketones and the like.

Examples of the esters include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, isopropyl acetate, n-butyl acetate and the like.

Examples of ethers include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolane, propylene glycol dimethyl ether, propylene glycol monoethyl ether and the like.

Examples of the ketones include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone and the like.

Further, as the solvent, toluene, acetonitrile, isopropanol, 2-butanol, isobutyl alcohol and the like can also be used.

The solvent may be used alone or in combination of two or more.

The content of the solvent in the chemically amplified positive photosensitive resin layer is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the chemically amplified positive photosensitive resin layer. It is particularly preferable that the content is 1% by mass or less.

[Other additives]
The chemically amplified positive photosensitive resin layer may contain other additives, if necessary, in addition to the polymer A and the photoacid generator.

(Basic compound)
The chemically amplified positive photosensitive resin layer preferably contains a basic compound. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of these include the compounds described in paragraphs 0204 to 0207 of JP2011-221494A, the contents of which are incorporated in the present disclosure.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexylamine. , Dicyclohexylmethylamine and the like.

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, 1,8-diazabicyclo [5.3.0] -7 -Undecene, N-cyclohexyl-N'-[2- (4-morpholinyl) ethyl] thiourea, 1,2,3-benzotriazole and the like can be mentioned.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide and the like.

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 basic compound may be used alone or in combination of two or more.

The content of the basic compound in the chemically amplified positive photosensitive resin layer is preferably 0.001% by mass to 5% by mass, based on the total mass of the chemically amplified positive photosensitive resin layer. More preferably, it is 005% by mass to 3% by mass.

(Surfactant)
The chemically amplified positive photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.

As the surfactant, any of anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants can be used, and nonionic surfactants are preferable. ..

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based surfactants, and fluorine-based surfactants. can. Specific examples of the nonionic surfactant include the nonionic surfactant described in paragraph 0120 of International Publication No. 2018/179640.

A preferable example of the nonionic surfactant is polystyrene measured by gel permeation chromatography containing the structural unit SA and the structural unit SB represented by the following formula I-1 and using tetrahydrofuran (THF) as a solvent. Examples thereof include copolymers having a converted weight average molecular weight (Mw) of 1,000 to 10,000.

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 to 4 carbon atoms, and R ⁴⁰⁴ is a hydrogen atom or a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10% by mass to 80% by mass. Represents a numerical value, q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and * represents a combination with other structures. Represents a part.

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 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable in terms of compatibility and wettability to the surface to be coated, and the alkyl group has 2 or 3 carbon atoms. Alkyl groups are more preferred.

In the formula I-1, 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 containing the structural unit SA and the structural unit SB represented by the formula I-1 is preferably 1,500 to 5,000.

As the surfactant, 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 content of the surfactant in the chemically amplified positive photosensitive resin layer is preferably 10% by mass or less, preferably 0.001% by mass to 10% by mass, based on the total mass of the chemically amplified positive photosensitive resin layer. It is more preferably mass%, and particularly preferably 0.01 mass% to 3 mass%.

(Plasticizer)
The chemically amplified positive photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity. The plasticizer is not limited, and a known plasticizer can be applied. Examples of the plasticizer include the plasticizers described in paragraphs 097 to 0103 of International Publication No. 2018/179640.

(Sensitizer)
The chemically amplified positive photosensitive resin layer can contain a sensitizer. As the sensitizer, a known sensitizer can be applied without limitation. Examples of the sensitizer include the sensitizers described in paragraphs 0104 to 0107 of International Publication No. 2018/179640.

(Heterocyclic compound)
The chemically amplified positive photosensitive resin layer can contain a heterocyclic compound. The heterocyclic compound is not limited, and known heterocyclic compounds can be applied. Examples of the heterocyclic compound include the heterocyclic compound described in paragraphs 011 to 0118 of International Publication No. 2018/179640.

(Alkoxysilane compound)
The chemically amplified positive photosensitive resin layer can contain an alkoxysilane compound. The alkoxysilane compound is not limited, and a known alkoxysilane compound can be applied. Examples of the alkoxysilane compound include the alkoxysilane compound described in paragraph 0119 of International Publication No. 2018/179640.

(Other ingredients)
The chemically amplified positive photosensitive resin layer contains metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorption. It may further contain known additives such as agents, thickeners, cross-linking agents, organic or inorganic anti-precipitation agents. Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP2014-85643, respectively, and the contents of this publication are incorporated in the present specification.

[Thickness of chemically amplified positive photosensitive resin layer]
The thickness of the chemically amplified positive photosensitive resin layer is preferably 1 μm to 15 μm, more preferably 1 μm to 10 μm, and 1 μm to 5 μm from the viewpoint of transferability and resolution. Especially preferable.

The thickness of the chemically amplified positive photosensitive resin layer can be measured by the following method.
In the cross-sectional observation image of the chemically amplified positive photosensitive resin layer in the thickness direction, the arithmetic mean value of the thickness of the chemically amplified positive photosensitive resin layer measured at 10 randomly selected points is obtained and obtained. Let be the thickness of the chemically amplified positive photosensitive resin layer. A cross-sectional observation image of the chemically amplified positive photosensitive resin layer in the thickness direction can be obtained by using a scanning electron microscope (SEM).

[Method of forming a chemically amplified positive photosensitive resin layer]
Examples of the method for forming the chemically amplified positive photosensitive resin layer include a method in which a positive photosensitive resin composition is applied onto a base material (for example, a temporary support) and then dried.

The coating method is not limited, and for example, known methods such as slit coating, spin coating, curtain coating, and inkjet coating can be applied.
It is also possible to apply a photosensitive resin layer on the temporary support on which another layer described later is formed.

Examples of the method for preparing the positive photosensitive resin composition include a method in which the above components and a solvent are mixed at an arbitrary ratio and dissolved by stirring. Further, a positive photosensitive resin composition can also be prepared by dissolving each of the above components in a solvent in advance to prepare a solution, and then mixing the obtained solutions in a predetermined ratio. As the solvent, the above-mentioned solvent can be used. The prepared positive photosensitive resin composition can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

The content of the solvent in the positive photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass with respect to 100 parts by mass of the total solid content in the positive photosensitive resin composition. It is more preferably parts by mass to 900 parts by mass.

[Middle layer]
The transfer material according to the present disclosure preferably has an intermediate layer containing a water-soluble resin between the temporary support and the chemically amplified positive photosensitive resin layer. Since the intermediate layer containing the water-soluble resin can absorb the substance generated by the acid decomposition reaction (that is, deprotection) of the group whose acid group is protected by the acid-degradable group, it is a chemically amplified positive photosensitive resin. The plasticization of the acid can be suppressed, and as a result, the excessive diffusion of the acid can be reduced. Therefore, by having an intermediate layer containing a water-soluble resin, it is possible to reduce the amount of change in the line width of the pattern with the passage of the standing time after exposure, and to improve the linearity of the pattern. You can also.

In the present disclosure, "water-soluble" means a property of dissolving 1 g or more in 100 g of water at 25 ° C.

(Water-soluble resin)
Examples of the water-soluble resin include cellulose resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, acrylamide resin, polyethylene oxide resin, gelatin, vinyl ether resin, polyamide resin, and copolymers thereof. Among the above, the water-soluble resin is preferably a cellulose resin, more preferably hydroxypropyl cellulose and hydroxypropyl methyl cellulose, and particularly preferably hydroxypropyl methyl cellulose.

The water-soluble resin may be used alone or in combination of two or more.

The content of the water-soluble resin in the intermediate layer is 20% by mass with respect to the total mass of the intermediate layer from the viewpoint of reducing the amount of change in the line width of the pattern with the passage of the standing time after exposure and the adhesion. It is preferably 50% by mass or more, and more preferably 50% by mass or more. The upper limit of the content of the water-soluble resin in the intermediate layer is not limited. The content of the water-soluble resin in the intermediate layer may be, for example, 100% by mass or less, or 98% by mass or less, based on the total mass of the intermediate layer.

(Surfactant)
The intermediate layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants can be used, but the preferred surfactant is nonionic. It is a system surfactant. The surfactant contained in the intermediate layer is not limited, and can be appropriately selected from known surfactants depending on the composition of the intermediate layer and the like.

The thickness of the intermediate layer is preferably 0.1 μm to 8 μm, preferably 0.1 μm to 5.0 μm, from the viewpoint of reducing the amount of change in the line width of the pattern with the lapse of the standing time after exposure. More preferably, it is more preferably 0.1 μm to 3.0 μm, and particularly preferably 0.1 μm to 2.0 μm.

The thickness of the intermediate layer can be measured by the following method.
In the cross-sectional observation image in the thickness direction of the intermediate layer, the arithmetic mean value of the thickness of the intermediate layer measured at 10 randomly selected points is obtained, and the obtained value is defined as the thickness of the intermediate layer. A cross-sectional observation image of the intermediate layer in the thickness direction can be obtained by using a scanning electron microscope (SEM).

The intermediate layer may be provided between the temporary support and the chemically amplified positive photosensitive resin layer, and between the temporary support and the chemically amplified positive photosensitive resin layer, the chemically amplified positive photosensitive resin layer may be provided. It is preferably provided in contact with the resin layer. By providing the intermediate layer in contact with the chemically amplified positive photosensitive resin layer, it becomes easier for the acid group to absorb the substance generated by the acid decomposition reaction of the group protected by the acid-degrading group, so that the substance is allowed to stand after exposure. The amount of change in the line width of the pattern with the passage of time can be further reduced.

Examples of the method for forming the intermediate layer include a method in which the composition for the intermediate layer is applied onto the temporary support and then dried. As the coating method, the method described in the above-mentioned "Method for forming a chemically amplified positive photosensitive resin layer" can be applied.

Examples of the method for preparing the composition for the intermediate layer include a method in which the above components and a solvent are mixed at an arbitrary ratio and dissolved by stirring. Further, a composition for an intermediate layer can also be prepared by dissolving each of the above components in a solvent in advance to prepare a solution, and then mixing the obtained solutions at a predetermined ratio. As the solvent, the above-mentioned solvent can be used. The prepared composition for an intermediate layer can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

[Other layers]
The transfer material according to the present disclosure may have a layer other than the positive photosensitive resin layer and the intermediate layer (hereinafter, may be referred to as “another layer”) as long as it does not deviate from the purpose of the present disclosure. good. Examples of other layers include an adhesion layer, a protective film, a contrast enhancement layer, a thermoplastic resin layer, and the like. Other layers include, for example, the layers described in paragraphs 0131 to 0134 of WO 2018/179640.

<Manufacturing method of resin pattern>
The method for producing a resin pattern according to the present disclosure is a step of bringing a substrate and the transfer material into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the substrate and the transfer material (hereinafter, "bonding step"). The step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support (hereinafter, referred to as "exposure step"). ), And a step of developing the chemically amplified positive photosensitive resin layer after the step of exposing the pattern to form a resin pattern (hereinafter, may be referred to as a "development step"). Since the method for producing a resin pattern according to the present disclosure includes the above steps, it is possible to reduce the amount of change in the line width of the pattern with the lapse of the standing time after exposure.

<Lasting process>
The method for producing a resin pattern according to the present disclosure includes a step of bringing a substrate and the transfer material into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the substrate and the transfer material.

An example of the bonding process is schematically shown in FIG. 2 (a). For example, in the step shown in FIG. 2A, the substrate 20 having the base material 22, the first conductive layer 24, and the second conductive layer 26 and the transfer material 100 are chemically amplified in the substrate 20 and the transfer material 100. The positive photosensitive resin layer 14 is brought into contact with each other and bonded together. When the protective film 16 is provided on the chemically amplified positive photosensitive resin layer 14 as in the transfer material 100 shown in FIG. 1, the substrate 20 is removed after the protective film 16 is removed from the transfer material 100. And the transfer material 100 are bonded together. It should be noted that the components shown by using the same reference numerals in FIG. 2 mean that they are the same components. Hereinafter, description of overlapping components and reference numerals in FIG. 2 may be omitted.

A known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator capable of further increasing productivity can be used for bonding the substrate and the transfer material. For bonding the substrate and the transfer material, it is preferable to stack the transfer material on the substrate and pressurize and heat it with a roll or the like.

[substrate]
The substrate itself may be a substrate such as glass, silicon, or film, and is a substrate in which an arbitrary layer such as a conductive layer is provided on the substrate such as glass, silicon, or film, if necessary. May be good. When the substrate further has a conductive layer, the substrate preferably has a conductive layer on the substrate.

The base material is preferably a glass base material or a film base material, more preferably a film base material, and particularly preferably a resin film.

The base material is preferably transparent. As the transparent base material, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used. The refractive index of the base material is preferably 1.50 to 1.52.

The base material may be composed of a translucent base material such as a glass base material, and tempered glass or the like represented by Corning's gorilla glass can be used.

When a film base material is used as the base material, it is more preferable to use a base material having a small optical strain and a base material having a high transparency, and it is particularly preferable to use a resin film.

Examples of the resin constituting the resin film include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer and the like.

Examples of the conductive layer include a metal layer and a conductive metal oxide layer. Here, "conductive" means that the volume resistivity is less than ^{1 × 10 6 Ωcm.} The volume resistivity is preferably less than ^{1 × 10 4 Ωcm.}

Examples of the metal constituting the metal layer include Al (aluminum), Zn (zinc), Cu (copper), Fe (iron), Ni (nickel), Cr (chromium), Mo (molybdenum) and the like. The metal constituting the metal layer may be a single metal composed of one kind of metal element, a metal containing two or more kinds of metal elements, or an alloy containing at least one kind of metal element. You may.

Examples of the conductive metal oxide constituting the conductive metal oxide layer include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), SiO _{2 and the} like.

From the viewpoint of conductivity and fine wire forming property, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer and a conductive metal oxide layer, and more preferably a metal layer. A copper layer is particularly preferable.

The conductive layer may be one layer or two or more layers. When the substrate has two or more conductive layers, the substrate preferably has conductive layers of different materials.

<Exposure process>
The method for producing a resin pattern according to the present disclosure includes a step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support.

An example of the exposure process is schematically shown in FIG. 2 (b). For example, in the step shown in FIG. 2B, the chemically amplified positive photosensitive resin layer 14 in the transfer material 100 is pattern-exposed via the temporary support 12. In FIG. 2B, as an example of the pattern exposure method, a mask 30 having a predetermined pattern is placed above the transfer material 100 arranged on the first conductive layer 24, and then the mask 30 is placed through the mask 30. To expose.

Examples of the pattern exposure method include exposure through a mask and digital exposure using a laser or the like.

The exposure light source may be appropriately selected from known light sources capable of irradiating light in a wavelength range (for example, 365 nm, 405 nm, etc.) in which the exposed portion of the chemically amplified positive photosensitive resin layer can be dissolved in a developing solution. can. Specific examples of the light source for exposure include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and the like.

The exposure amount is ^preferably from ^{5mJ / cm 2 ~200mJ / cm 2} , more preferably ^{10mJ / cm 2 ~100mJ / cm 2} .

The arrangement and size of the pattern are not limited and can be appropriately selected according to the purpose. For example, in the case of manufacturing a display device (for example, a touch panel) provided with an input device having circuit wiring, at least the pattern is at least from the viewpoint of improving the display quality of the display device and minimizing the area occupied by the take-out wiring. A part (particularly, the electrode pattern of the touch panel and the portion of the take-out wiring) is preferably a fine wire of 100 μm or less, and more preferably 70 μm or less.

<Development process>
The method for producing a resin pattern according to the present disclosure includes a step of developing the chemically amplified positive photosensitive resin layer after the step of exposing the pattern to form a resin pattern.

An example of the developing process is schematically shown in FIG. 2 (c). In the step shown in FIG. 2C, the temporary support 12 is peeled off from the chemically amplified positive photosensitive resin layer 14 after the exposure step, and then the chemically amplified positive photosensitive resin layer 14 after the exposure step is developed. The first resin pattern 14A is formed.

The pattern-exposed chemically amplified positive photosensitive resin layer can be developed using a developing solution. The developing solution is not limited as long as the exposed portion of the chemically amplified positive photosensitive resin layer can be removed, and for example, a known developing solution such as the developing solution described in JP-A-5-72724 can be used. can. The developer is preferably a developer in which the exposed portion of the chemically amplified positive photosensitive resin layer has a dissolution-type development behavior. The developer is preferably an alkaline aqueous solution-based developer containing, for example, a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may further contain an organic solvent, a surfactant, etc. that are miscible with water. 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 limited, and examples thereof include paddle development, shower development, shower and spin development, and dip development. Here, shower development will be described as an example of the development method. By spraying the developing solution on the chemically amplified positive photosensitive resin layer after exposure with a shower, the exposed portion of the chemically amplified positive photosensitive resin layer can be removed. Further, after the development, it is preferable to spray a cleaning agent or the like with a shower and rub 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.

The method for producing a resin pattern according to the present disclosure may include a post-baking step of heat-treating the resin pattern obtained by development.

Post-baking is preferably heated in an environment of 8.1 kPa to 121.6 kPa. The post-bake heating is more preferably performed in an environment of 114.6 kPa or less, and more preferably performed in an environment of 101.3 kPa or less.

The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.

The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.

Post-baking may be performed in an air environment or a nitrogen substitution environment.

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 preferably used in the present disclosure.

<Manufacturing method of circuit wiring>
The method for manufacturing a circuit wiring according to the present disclosure is a step of bringing a substrate having a conductive layer and the transfer material into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the substrate and the transfer material (hereinafter, "" (Sometimes referred to as a "bonding step") and a step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support (hereinafter, "exposure step"). Alternatively, it may be referred to as a "first exposure step") and a resin pattern (hereinafter, referred to as a "first resin pattern") obtained by developing the chemically amplified positive photosensitive resin layer after the pattern exposure step. A step of forming (hereinafter, may be referred to as a “development step” or a “first development step”) and a step of etching the conductive layer exposed in a region where the resin pattern is not formed (hereinafter, referred to as “development step”). It includes a "etching step" or a "first etching step") and a step of removing the resin pattern after the etching step (hereinafter, may be referred to as a "removal step"). Since the circuit wiring manufacturing method according to the present disclosure includes the above steps, it is possible to reduce the amount of change in the line width of the pattern with the lapse of the standing time after exposure.

The mode of each step of the bonding step, the exposure step (first exposure step), and the development step (first development step) in the circuit wiring manufacturing method according to the present disclosure is described in the above-mentioned "resin pattern manufacturing method". The embodiment of each step described in the section of the above can be applied, and the same applies to the preferred embodiment.

When a substrate having a plurality of conductive layers is used, it is preferable that at least one of the plurality of conductive layers contains a conductive metal oxide. Further, 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.

By repeatedly applying the circuit wiring manufacturing method according to the present disclosure to a substrate having a plurality of conductive layers, it is possible to manufacture a circuit wiring including a plurality of conductive layers having different patterns from each other. When a substrate having a plurality of conductive layers is used, the circuit wiring manufacturing method according to the present disclosure includes an etching step (first etching step), followed by a second exposure step, a second development step, and a second development step, which will be described later. By further including the etching step, it is possible to manufacture a circuit wiring including a plurality of conductive layers having different patterns from each other.

[Etching process (first etching process)]
The method for manufacturing a circuit wiring according to the present disclosure includes a step of etching the exposed conductive layer in a region where the resin pattern is not formed.

An example of the etching process is schematically shown in FIG. 2 (d). In the step shown in FIG. 2D, the first conductive layer 24 and the second conductive layer 26 that are exposed in the region where the first resin pattern 14A is not formed are etched. By etching, the first conductive layer 24A and the second conductive layer 26A having the same pattern as the first resin pattern 14A are formed.

In the etching step, it is sufficient that at least the conductive layer exposed in the region where the resin pattern is not formed can be etched, and the conductive layer is provided between the conductive layer exposed in the region where the resin pattern is not formed and the base material. Other conductive layers may also be etched.

As the etching method, for example, known methods such as those described in paragraphs 0048 to 0054 of JP2010-152155A, a known dry etching method such as plasma etching, and a wet etching method of immersing in an etching solution are known. The method can be applied.

As the etching solution used for wet etching, an acidic type etching solution or an alkaline type etching solution may be appropriately selected according to the etching target.

Examples of the acidic type etching solution include an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, and potassium permanganate. And so on. As the acidic component, a component in which a plurality of acidic components are combined may be used.

Examples of the alkaline type etching solution include an aqueous solution of an alkaline component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (for example, tetramethylammonium hydroxide), an alkaline component and a permanganate. Examples thereof include a mixed aqueous solution with a salt such as potassium. 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. The resin pattern used as the etching mask (etching pattern) in the present disclosure preferably exhibits particularly excellent resistance to an etching solution in a temperature range of 45 ° C. or lower. Therefore, the peeling of the chemically amplified positive photosensitive resin layer is prevented during the etching step, and the portion where the chemically amplified positive photosensitive resin layer does not exist is selectively etched.

After the etching step, a cleaning step and a drying step may be performed as necessary to prevent contamination of the process line.

As the cleaning liquid used in the cleaning step, for example, pure water or an aqueous solution obtained by mixing an organic solvent or a surfactant that is soluble in pure water can be used.

The boiling point of an organic solvent that can be dissolved in pure water (hereinafter, may be referred to as "water-soluble organic solvent") is preferably 50 ° C. to 250 ° C., preferably 55 ° C. to 250 ° C. from the viewpoint of solvent volatility. It is more preferably 200 ° C., and particularly preferably 60 ° C. to 150 ° C.

Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol and ethylene glycol, 2-acetoxy-2-phenylethanol, 3-methoxy-3-methylethanol and 3-methoxy-3-methyl. Alkoxy alcohols such as butanol and 2-butoxyethoxyethanol, ketones such as acetone and methyl ethyl ketone, glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether, tetrahydrofuran, acetonitrile, dimethylacetamide and dimethylformamide, Examples thereof include N-methylpyrrolidone, dimethylsulfoxide and 1,3-dioxolane.
Among the above, as the water-soluble organic solvent, methanol, ethanol, propanol, isopropanol, 3-methoxy-3-methylbutanol, 2-acetoxy-2-phenylethanol, tetrahydrofuran, and dimethylsulfoxide are preferable.

The content of the water-soluble organic solvent in the aqueous solution is preferably 0.01% by mass to 95% by mass, more preferably 0.01% by mass to 20% by mass, based on the total mass of the aqueous solution. It is more preferably 0.01% by mass to 10% by mass, and particularly preferably 0.01% by mass to 5% by mass.

The cleaning time in the cleaning step is not limited, and is preferably, for example, 10 seconds to 300 seconds.

In the drying step, for example using air blow, air blow pressure (preferably 0.1kg ^/ cm ² ~5kg ^/ cm 2 or so) may be performed to adjust to dry appropriately.

<Second exposure process>
The circuit wiring manufacturing method according to the present disclosure is a step of pattern-exposing a resin pattern (first resin pattern) after the etching step (first etching step) with a pattern different from the resin pattern (first resin pattern). (Hereinafter, it may be referred to as “second exposure step”).

An example of the second exposure step is schematically shown in FIG. 2 (e). For example, in the step shown in FIG. 2E, a mask 40 having a pattern different from that of the mask 30 used in the first exposure step is used, and the first resin pattern 14A after the first etching step is changed to the first resin pattern 14A. Pattern exposure is performed with a pattern different from that of.

In the second exposure step, for example, among the resin patterns (first resin patterns) remaining on the conductive layer after the etching step (first etching step), on the conductive layer removed in the second developing step described later. The remaining resin pattern (first resin pattern) is exposed.

For the pattern exposure in the second exposure step, the same method as the pattern exposure in the first exposure step can be applied except that a mask having a pattern different from that used in the first exposure step is used.

<Second development process>
In the method for manufacturing a circuit wiring according to the present disclosure, the chemically amplified positive photosensitive resin layer after the pattern exposure step (second exposure step) is developed, and the pattern is different from the resin pattern (first resin pattern). It may include a step of forming a different resin pattern (hereinafter, may be referred to as “second resin pattern”). In the second developing step, the portion of the resin pattern (first resin pattern) exposed in the second exposure step is removed.

An example of the second developing step is schematically shown in FIG. 2 (f). For example, in the step shown in FIG. 2 (f), the first resin pattern 14A after the second exposure step is developed to form the second resin pattern 14B.

The same method as the development in the first development step can be applied to the development in the second development step.

<Second etching process>
The method for manufacturing a circuit wiring according to the present disclosure may be referred to as a step of etching the exposed conductive layer in a region where the resin pattern (second resin pattern) is not formed (hereinafter, "second etching step"). ) May be included. By the second etching step, the exposed conductive layer can be removed in the region where the resin pattern (second resin pattern) is not formed.

An example of the second etching step is schematically shown in FIG. 2 (g). For example, in FIG. 2 (g), the first conductive layer 24A exposed in the region where the second resin pattern 14B is not formed is etched. After the second etching step, a circuit wiring including conductive layers 24B and 26A having different patterns is formed.

For the etching in the second etching step, the same method as the etching in the first etching step can be applied except that the etching solution is selected according to the conductive layer to be removed by etching.

In the second etching step, it is preferable to selectively etch a less conductive layer than in the first etching step according to a desired pattern. For example, as shown in FIG. 2, the first conductive layer 24B is etched by using an etching solution that selectively etches only the first conductive layer 24A exposed in the region where the first pattern 14A is not formed. Can be a pattern different from the pattern of the second conductive layer 26A.

<Full exposure process>
The circuit wiring manufacturing method according to the present disclosure is a step of fully exposing the chemically amplified positive photosensitive resin layer formed on the conductive layer after the etching step and before the removing step (hereinafter, "full exposure step"). It may include.). By providing the entire surface exposure step before the removing step, the removing property of the chemically amplified positive photosensitive resin layer in the removing step can be improved.

In the present disclosure, "exposing the entire surface of the chemically amplified positive photosensitive resin layer" means that all of the chemically amplified positive photosensitive resin layer formed on the conductive layer may be exposed, and the chemically amplified positive photosensitive resin layer may be exposed. The portion without the resin layer may or may not be exposed, but from the viewpoint of convenience, for example, the entire surface of the substrate on the side where the chemically amplified positive photosensitive resin layer is provided is exposed. Is preferable.

From the viewpoint of increasing the reaction rate of the photoacid generator and removing excess water, a step of heating the substrate before, during, or both of the full exposure may be included. The heating device is not particularly limited, and a known heating device can be used. Specifically, an IR (Infrared Ray) heater, warm air air drying, a hot blower, a convection oven and the like can be used.

Further, the method for manufacturing the circuit wiring according to the present disclosure preferably does not include a step of etching the conductive layer using the developed positive photosensitive resin layer as a mask after the entire exposure step.

<Heating process>
In the method for manufacturing a circuit wiring according to the present disclosure, the fully exposed chemically amplified positive photosensitive resin layer is subjected to the above-mentioned full-scale exposure step, after the full-face exposure step, or both, and before the removal step described later. It may include a step of heating (hereinafter, may be referred to as a “heating step”). By including the heating step, the reaction rate between the generated acid and the chemically amplified positive photosensitive resin layer can be improved, and as a result, the removal performance can be improved.

[Removal process]
The method for manufacturing a circuit wiring according to the present disclosure includes a step of removing the resin pattern after the etching step.

Removal in the removal step includes, for example, dissolution and dispersion of the chemically amplified positive photosensitive resin layer in the removing liquid.

An example of the removal step is schematically shown in FIG. 2 (h). In the step shown in FIG. 2H, after the second etching step, the second resin pattern 14B remaining on a part of the first conductive layer 24B is removed.

Examples of the method for removing the resin pattern include a method for removing the resin pattern by chemical treatment, and a method for removing the resin pattern with a removing liquid is preferable. As a specific example of the method for removing the resin pattern, the substrate having the resin pattern is immersed in the removing liquid being stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to 30 minutes. The method can be mentioned.

In the removal step, from the viewpoint of removability, it is preferable to use a removal liquid containing 30% by mass or more of water, more preferably to use a removal liquid containing 50% by mass or more of water, and 70% by mass or more of water. It is more preferable to use a removing liquid to be used.

Examples of the removing liquid include inorganic alkaline components such as sodium hydroxide and potassium hydroxide, or organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. It preferably contains a component. Among the above, the removing liquid is preferably a removing liquid containing an organic alkali component, and particularly preferably a removing liquid containing an amine compound, from the viewpoint of removability.

The content of the alkaline component may be appropriately selected from the viewpoint of basic strength, solubility, etc., but from the viewpoint of removability, 0.01% by mass to 20% by mass with respect to the total mass of the removal solution. It is preferably 0.1% by mass to 10% by mass, and more preferably 0.1% by mass to 10% by mass.

The removing liquid preferably contains a surfactant from the viewpoint of removability. As the surfactant, a known surfactant can be used. The content of the surfactant is preferably 0.1% by mass to 10% by mass with respect to the total mass of the removing liquid from the viewpoint of removability.

The removing liquid preferably contains a water-soluble organic solvent. Preferred examples of the water-soluble organic solvent include dimethyl sulfoxide and N-methylpyrrolidone.

As the removing step, a method of using a removing liquid and removing by a spray method, a shower method, a paddle method or the like is preferable.

<Roll-to-roll method>
The circuit wiring manufacturing method according to the present disclosure is preferably performed by a roll-to-roll method. The roll-to-roll method refers to a method in which at least one step (preferably all steps or all steps other than the heating step) is performed while transporting the substrate. The transfer of the substrate can be performed by combining the step of unwinding the substrate and the step of winding the substrate. The method of unwinding the substrate and the method of winding the substrate are not limited, and can be appropriately selected from the methods known in the roll-to-roll method.

<Manufacturing method of touch panel>
The method for manufacturing a touch panel according to the present disclosure is a step of bringing a substrate having a conductive layer and the transfer material into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the substrate and the transfer material (bonding step). A step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support (exposure step (first exposure step)) and a step of pattern-exposing the pattern. Later, a step of developing the chemically amplified positive photosensitive resin layer to form a resin pattern (first resin pattern) (development step (first development step)) and exposure in a region where the resin pattern is not formed. A step of etching the conductive layer (etching step (first etching step)) and a step of removing the resin pattern after the etching step (removal step) are included. Since the touch panel manufacturing method according to the present disclosure includes the above steps, it is possible to reduce the amount of change in the line width of the pattern with the lapse of the standing time after exposure.

Regarding the mode of each step of the bonding step, the exposure step (first exposure step), the development step (first development step), the etching step (first etching step), and the removal step in the touch panel manufacturing method according to the present disclosure. Can be applied to the aspects of each step described in the above-mentioned "Method for manufacturing circuit wiring", and the preferred embodiments are also the same. Further, the touch panel manufacturing method according to the present disclosure includes a second exposure step, a second development step, a second etching step, a full exposure step, a heating step and the like described in the above-mentioned "Circuit wiring manufacturing method" section. You may be.

FIG. 3 shows an example of a mask pattern used in the touch panel manufacturing method according to the present disclosure. In the pattern A shown in FIG. 3, 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. In the method for manufacturing a touch panel according to the present disclosure, for example, by exposing the chemically amplified positive photosensitive resin layer through a mask having the pattern A shown in FIG. 3, a pattern corresponding to the solid line portion SL and the gray portion G can be obtained. It is possible to manufacture a touch panel on which the circuit wiring to have is formed.

The touch panel according to the present disclosure is a touch panel having at least circuit wiring formed through the above steps. 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.
As the detection method in the touch panel according to the present disclosure, any known method such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among the above, the capacitance method is preferable as the detection method.
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-2012-517501), 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 FIGS. 1 and 5 of Japanese Patent Application Laid-Open No. 2012-89102), OGS (One Glass Solution) type, TOR (Touch-on-Lens) type (for example, Japanese Patent Application Laid-Open No. (The one described in FIG. 2 of 2013-54727), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), various out-selling types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.) can be mentioned.
The touch panels related to this disclosure include "Latest Touch Panel Technology" (July 6, 2009, published by Techno Times Co., Ltd.), supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (2004, 12). , FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. Unless otherwise specified, "parts" and "%" are based on mass.

<Example 1>
[Preparation of Chemically Amplified Positive Photosensitive Resin Composition 1]
A chemically amplified positive photosensitive resin composition 1 was prepared according to the following formulation.
-Polymer A (the following polymer 1): 9.64 parts-Photoacid generator (the following compound A-1): 0.25 parts-Surfactant (the following surfactant C): 0.01 parts-Addition Agent (Compound D below): 0.1 parts ・ Propylene glycol monomethyl ether acetate: 90.00 parts

Polymer 1: A polymer having the structure shown below (the glass transition temperature is 25 ° C., the weight average molecular weight is 25,000. The numerical values described in the following structural units mean mass%).

Compound A-1: Compound having the structure shown below

Surfactant C: Polymer with the structure shown below

Compound D: A compound having the structure shown below.

[Preparation of Composition 1 for Intermediate Layer]
The composition 1 for the intermediate layer was prepared according to the following formulation.
-Cellulose resin (Methanol (registered trademark) 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.): 3.5 parts-Surfactant (Megafuck (registered trademark) F444, manufactured by DIC Corporation): 0.1 parts-Pure Water: 33.7 parts, Methanol: 62.7 parts

[Preparation of transfer material 1]
2. The intermediate layer composition 1 is dried on a temporary support 1 (polyethylene terephthalate film having a thickness of 12 μm, Lumirror 12QS62, manufactured by Toray Industries, Inc., haze value 0.43%) using a slit-shaped nozzle. An intermediate layer was formed by applying in an amount of 0 μm and then drying. The chemically amplified positive photosensitive resin composition 1 is applied onto the intermediate layer in an amount such that the dry film thickness is 3.0 μm, and then dried with warm air at 90 ° C. to form a chemically amplified positive photosensitive resin layer. Formed. Finally, as a cover film, a polyethylene film (OSM-N manufactured by Toledeger) was pressure-bonded onto a chemically amplified positive photosensitive resin layer to prepare a transfer material 1.

[Preparation of substrate]
A copper layer having a thickness of 250 nm was formed on a PET (polyethylene terephthalate) film having a thickness of 200 μm by a sputtering method to prepare a substrate having the copper layer (that is, PET with a copper layer).

[Manufacturing of circuit wiring]
(Manufacture of substrate A having a resin pattern)
The cover film is peeled off from the transfer material 1 and transferred onto the copper layer of the above substrate (PET with a copper layer) under the conditions of a roll temperature of 90 ° C., a linear pressure of 0.6 MPa, and a linear velocity (lamination rate) of 3.6 m / min. Material 1 was pasted together.

As a photomask for patterning, a chrome mask provided with a line-and-space pattern of 10 μm was prepared. The surface of the temporary support of the transfer material 1 bonded on the substrate was brought into contact with the chromium mask, and the chemically amplified positive photosensitive resin layer was exposed at an exposure amount of ^{75 mJ / cm 2 using an ultrahigh pressure mercury lamp.} After the exposure, the substrate was allowed to stand for 3 hours in a 25 ° C. and 55% RH environment with the temporary support placed on the chemically amplified positive photosensitive resin layer. After standing, the temporary support was peeled off from the transfer material, and shower development was performed for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25 ° C., whereby the chemically amplified positive photosensitive patterned on the copper layer. A substrate A having a resin layer (resin pattern) was obtained.

[Manufacturing of circuit wiring A]
The copper layer was shower-etched for 60 seconds with a copper etching solution (Cu-02, manufactured by Kanto Chemical Co., Inc.) at 25 ° C. on the substrate A having a resin pattern on the copper layer. Then, a chemical amplification positive type photosensitive resin layer was removed by shower peeling for 2 minutes using a stripping solution at 60 ° C. (KP-301 manufactured by Kanto Chemical Co., Ltd.) to prepare a circuit wiring A.

[Manufacturing of substrate B and circuit wiring B having a resin pattern]
Substrate B and circuit wiring B having a resin pattern were produced by the same procedure as the method for producing substrate A and circuit wiring A, except that the standing time after exposure and before development was set to 24 hours.

[Evaluation of PED performance]
For each of the circuit wirings A and B, the line widths at 20 points of the line pattern portion are measured by observing with an optical microscope, and the arithmetic mean line width of the line pattern portion (hereinafter referred to as "average line width") is obtained. rice field. From the obtained average line width value, the line width change rate Δ with the standing time was calculated by the following formula, and the PED performance was evaluated according to the following criteria. The evaluation results are shown in Table 1. Of the following criteria, A, B and C are desirable for the performance of the transfer material.
Equation: Δ = [Average line width of circuit wiring B / Average line width of circuit wiring A]

(standard)
A: 0.97 <Δ≤1.00
B: 0.94 <Δ≤0.97
C: 0.90 <Δ≤0.94
D: 0.85 <Δ≤0.90
E: Δ≤0.85

[Evaluation of nip resistance performance]
The transfer material 1 bonded to the substrate (PET with a copper layer) under the above conditions was passed between the pair of nip rolls under the conditions of a roll temperature of 30 ° C., a linear pressure of 0.3 MPa, and a linear velocity of 1.0 m / min. Then, the surface of the sample was observed to confirm the presence or absence of peeling of the temporary support in the transfer material 1, and the nip resistance performance was evaluated according to the following criteria. The evaluation results are shown in Table 1.
(standard)
A: No peeling of the temporary support B: With peeling of the temporary support

<Example 2>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the chemically amplified positive photosensitive resin composition 2 prepared according to the following formulation was used. The evaluation results are shown in Table 1.

[Chemically amplified positive photosensitive resin composition 2]
・ Polymer A (polymer 2 below): 9.64 parts ・ Photoacid generator (compound A-2 below): 0.25 parts ・ Surface active agent (surfactant C): 0.01 parts ・ Additive (Compound D): 0.1 parts, propylene glycol monomethyl ether acetate: 90.00 parts

Polymer 2: A compound having the structure shown below (the glass transition temperature is 90 ° C., the weight average molecular weight is 20,000. The numerical value described in each of the following structural units means mass%).

Compound A-2: Compound having the structure shown below

<Example 3>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the chemically amplified positive photosensitive resin composition 3 prepared according to the following formulation was used. The evaluation results are shown in Table 1.

[Positive Photosensitive Resin Composition 3]
-Polymer A (polymer 3 below): 9.64 parts-Photoacid generator (Compound A-1): 0.25 parts-Surfactant (surfactant C): 0.01 parts-Additives ( Compound D): 0.1 part ・ Propylene glycol monomethyl ether acetate: 90.00 part

Polymer 3: A polymer having the structure shown below (the glass transition temperature is 26 ° C., the weight average molecular weight is 30,000, and the acid value is 27 mgKOH / g. , Means% by weight.)

<Example 4>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the chemically amplified positive photosensitive resin composition 4 prepared according to the following formulation was used. The evaluation results are shown in Table 1.

[Chemically amplified positive photosensitive resin composition 4]
-Polymer A (Polymer 1): 9.64 parts-Photoacid generator (Compound A-1): 0.25 parts-Surfactant (Surfactant C): 0.01 parts-Additive (Compound) D): 0.09 parts ・ Additive (Compound E below): 0.01 parts ・ Propylene glycol monomethyl ether acetate: 90.00 parts

Compound E: 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Example 5>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the temporary support 2 manufactured according to the following method was used. The evaluation results are shown in Table 1. The temporary support 2 in the transfer material produced in Example 5 has a coating layer on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided.

[Manufacturing of temporary support 2]
A temporary support 2 having a coating layer on one side of a polyethylene terephthalate film used as a base material was produced by the following method.

[Extrusion molding]
Pellets of polyethylene terephthalate using the titanium compound described in Japanese Patent No. 5575671 as a polymerization catalyst were dried to a water content of 50 ppm or less, and then charged into a hopper of a uniaxial kneading extruder having a diameter of 30 mm and melted at 280 ° C. Extruded. The melt was passed through a filter (pore diameter 3 μm) and then extruded from a die onto a cooling roll at 25 ° C. to obtain an unstretched film. The extruded melt was brought into close contact with the cooling roll by using an electrostatic application method.

[Stretching and coating]
A temporary support 2 having a base material (polyethylene terephthalate film) having a thickness of 10 μm and a coating layer having a thickness of 50 nm was obtained by applying a coating liquid for a coating layer to the obtained unstretched film and sequentially biaxially stretching the film. The coating liquid for the coating layer was applied after the unstretched film was uniaxially stretched in the process of sequentially biaxially stretching the unstretched film. The haze value of the temporary support 2 was 0.31%. The coating liquid for the coating layer was prepared according to the following formulation.

(Coating liquid for coating layer)
-Acrylic polymer (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass): 167 parts-Nonion-based surfactant (Naroacty (registered trademark) CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100 Mass%): 0.7 parts, anionic surfactant (Lapisol® A-90, manufactured by Chukyo Yushi Co., Ltd., solid content 1% by mass, diluted with water): 55.7 parts, carnauba wax dispersion (cellozole) (Registered trademark) 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 7 parts, carbodiimide compound (Carbodilite (registered trademark) V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., solid content 10% by mass, diluted with water) : 20.9 parts, matting agent (Snowtex (registered trademark) XL, manufactured by Nissan Chemical Co., Ltd., solid content 40% by mass): 2.8 parts, water: 743 parts

<Example 6>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the thickness of the intermediate layer was 5.0 μm. The evaluation results are shown in Table 1.

<Example 7>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the chemically amplified positive photosensitive resin composition 1 was directly applied onto the temporary support 1 without providing the intermediate layer. The evaluation results are shown in Table 1.

<Example 8>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the temporary support 3 (thickness 12 μm, haze value 0.68%) manufactured by the same procedure as the temporary support 2 was used. bottom. The evaluation results are shown in Table 1.

<Example 9>
PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that a temporary support 4 (polyethylene terephthalate film with a thickness of 16 μm, Lumirror 16QS62, manufactured by Toray Industries, Inc., haze value 0.46%) was used. bottom. The evaluation results are shown in Table 1.

<Comparative example 1>
The PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that the temporary support 5 (thickness 25 μm, haze value 0.35%) manufactured by the same procedure as the temporary support 2 was used. bottom. The evaluation results are shown in Table 1.

<Comparative example 2>
PED performance and nip resistance performance were evaluated in the same manner as in Example 1 except that a temporary support 6 (polyethylene terephthalate film having a thickness of 38 μm, Lumirror 38QS63, manufactured by Toray Industries, Inc., haze value 0.45%) was used. bottom. The evaluation results are shown in Table 1.

The temporary supports used in Examples 1 to 9 and Comparative Examples 1 and 2 have at least irregularities on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided.

From Table 1, a temporary support having a thickness of 7 μm to 18 μm and having at least irregularities on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided, and chemically amplified positive photosensitive. It was found that in the circuit wirings of Examples 1 to 9 produced by using the transfer material having the resin layer, the amount of change in the line width of the pattern with the lapse of the standing time after exposure was small. Furthermore, it was found that the transfer materials used in Examples 1 to 9 also had good nip resistance performance.

On the other hand, in the circuit wirings of Comparative Examples 1 and 2 produced by using a transfer material having a temporary support having a thickness of more than 18 μm, the amount of change in the line width of the pattern with the lapse of the standing time after exposure is large. became. Further, it was found that the nip resistance performance of the transfer materials used in Comparative Examples 1 and 2 was inferior to the nip resistance performance of the transfer materials used in Examples 1 to 9.

<Comparative example 3>
The temporary support 7 was manufactured in the same manner as the method for manufacturing the temporary support 2, except that a matting agent was not used in the manufacturing process of the temporary support 2. The temporary support 7 has no unevenness on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided. The PED performance was evaluated in the same manner as in Example 5 except that the obtained temporary support 7 was used. As a result, the PED evaluation was A, but it was planned because good slipperiness could not be obtained between the temporary support and the photomask and alignment could not be achieved (that is, alignment could not be performed). It was not possible to form a pattern at the above position.

The disclosure of Japanese Patent Application No. 2018-227711, filed December 4, 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 herein by reference.

Claims (10)

A temporary support with a thickness of 7 μm to 18 μm and
Chemically amplified positive photosensitive resin layer and
Have,
The temporary support is a transfer material having at least an uneven surface on the side opposite to the side on which the chemically amplified positive photosensitive resin layer is provided. The transfer material according to claim 1, wherein the temporary support contains particles and the haze value of the temporary support is 0.50% or less. The transfer material according to claim 1 or 2, wherein the temporary support has irregularities only on the surface opposite to the side on which the chemically amplified positive photosensitive resin layer is provided. Claims 1 to claim having an intermediate layer containing a water-soluble resin provided in contact with the chemically amplified positive photosensitive resin layer between the temporary support and the chemically amplified positive photosensitive resin layer. Item 3. The transfer material according to any one of Item 3. The transfer material according to claim 4, wherein the thickness of the intermediate layer is 0.1 μm to 3.0 μm. Any of claims 1 to 5, wherein the chemically amplified positive photosensitive resin layer contains a polymer containing a structural unit having a group in which an acid group is protected by an acid-degradable group, and an acid generator. The transfer material according to item 1. The polymer containing a structural unit having a group in which the acid group is protected by an acid-degradable group is derived from the structural unit represented by the formula A1, the structural unit represented by the formula A2, and the structural unit represented by the formula A3. The transfer material according to claim 6, which is a polymer containing at least one structural unit selected from the group.

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 Representing an alkyl or aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, where R ¹⁴ represents a hydrogen atom or methyl group and X ¹ is a single bond or It represents a 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 Representing an alkyl group or 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, or an alkoxy. It represents a group, an alkenyl group, 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, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is Representing an alkyl or aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, where R ³⁴ represents a hydrogen atom or methyl group and X ⁰ is a single bond or Represents a divalent linking group. A step of bringing the substrate and the transfer material according to any one of claims 1 to 7 into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the substrate and the transfer material.
A step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support.
A step of developing the chemically amplified positive photosensitive resin layer after the step of pattern exposure to form a resin pattern, and a step of forming a resin pattern.
A method for manufacturing a resin pattern including. A step of bringing a substrate having a conductive layer and the transfer material according to any one of claims 1 to 7 into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the transfer material. ,
A step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support.
A step of developing the chemically amplified positive photosensitive resin layer after the step of pattern exposure to form a resin pattern, and a step of forming a resin pattern.
A step of etching the conductive layer exposed in a region where the resin pattern is not formed, and a step of etching the conductive layer.
A step of removing the resin pattern after the etching step and a step of removing the resin pattern.
Manufacturing method of circuit wiring including. A step of bringing a substrate having a conductive layer and the transfer material according to any one of claims 1 to 7 into contact with each other and bonding the chemically amplified positive photosensitive resin layer in the transfer material. ,
A step of pattern-exposing the chemically amplified positive photosensitive resin layer in the transfer material after the bonding step via the temporary support.
A step of developing the chemically amplified positive photosensitive resin layer after the step of pattern exposure to form a resin pattern, and a step of forming a resin pattern.
A step of etching the conductive layer exposed in a region where the resin pattern is not formed, and a step of etching the conductive layer.
A step of removing the resin pattern after the etching step and a step of removing the resin pattern.
A method for manufacturing a touch panel including.

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