KR20230029956A - Method of forming a metal pattern, and method of manufacturing a metal mask for deposition - Google Patents

Abstract

A step of preparing a laminate having a negative photosensitive resin layer on a substrate, a component incident obliquely with respect to the thickness direction of the exposure mask from the side opposite to the side on which the substrate is provided in the negative photosensitive resin layer a step of irradiating light having a light and pattern-exposing the negative photosensitive resin layer through the exposure mask; a step of forming a resin pattern having a tapered shape by developing the pattern-exposed negative photosensitive resin layer; and A method of forming a metal pattern including a step of forming a tapered metal pattern corresponding to a shape of a resin pattern, and a method of manufacturing a metal mask for deposition having a metal pattern obtained by the method of forming the metal pattern.

Description

Method of forming a metal pattern, and method of manufacturing a metal mask for deposition

The present disclosure relates to a method of forming a metal pattern and a method of manufacturing a metal mask for deposition.

In a display device equipped with a touch panel such as a capacitive input device (an organic electroluminescence (EL) display device, a liquid crystal display device, etc.), an electrode pattern corresponding to a sensor in a visible unit, a peripheral wiring portion and conductive layer patterns such as wiring of the lead-out wiring portion are provided inside the touch panel.

In general, since the number of steps for obtaining the required pattern shape is small in the formation of a patterned layer, with respect to the layer of the photosensitive resin composition prepared on an arbitrary substrate using a photosensitive transfer member, the desired A method of developing after exposure through a mask having a pattern is widely used.

In addition, in the method of forming the pixels of the organic EL display device, after attaching a metal mask (deposition mask) including through holes to the base material for the organic EL display device, it is put into a vapor deposition device, and organic materials such as A method of forming a pixel by vapor deposition is known.

Moreover, as a manufacturing method of the conventional metal mask, the thing described in Unexamined-Japanese-Patent No. 2006-152396 or Unexamined-Japanese-Patent No. 2017-226918 is known.

In Japanese Laid-open Patent Publication No. 2006-152396, in a method for manufacturing a metal mask based on a mask original plate for electric pole, a plurality of similar transfer patterns formed in a predetermined shape on a first substrate coated with a resist After sequential exposure using a photomask, development is performed to form convex portions having an inclined sidewall on the first substrate, and to form a first conductive film on the entire surface of the first substrate on the side where the convex portions are formed. In addition, a metal is deposited on the upper surface of the first conductive film by plating, and the precipitated metal is separated from the first conductive film to manufacture a master original plate having a predetermined shape concave portion, and on the conductive upper surface of the second substrate. , Based on the concave portion of the predetermined shape of the master disc, a convex portion substantially identical to the convex portion of the predetermined shape is formed by resin, and the second substrate having the convex portion by the resin is separated from the master disc for the electric pole. A mask original plate is fabricated, and plating is performed on the second conductive film exposed to the mask original plate for electric pole to a thickness at which an opening having a sidewall substantially equal to an inclined sidewall of the concave portion of the predetermined shape of the mask original plate is provided. A method for manufacturing a metal mask is described, characterized in that a desired metal film is deposited and formed, and the metal film is produced by peeling from the mask original plate for electric pole.

Japanese Unexamined Patent Publication No. 2017-226918 discloses a method for manufacturing a fine metal mask, (a) preparing a carrier glass and depositing a sacrificial layer on the carrier glass, (b) electrode metal for electroforming plating A process of forming an electrode layer by depositing (c) a process of applying photoresist on the electrode layer, (d) a process of exposing and developing the photoresist using photolithography to pattern it, (e) patterning A step of forming an electroplating layer by electroforming the photoresist, (f) a step of forming a metal pattern by removing the photoresist, and (g) a mask by forming a pattern corresponding to the metal pattern on the electrode layer. A process of forming a pattern, (h) a process of heat treatment to increase the rigidity of the patterned electroformed plating layer and the electrode layer, (i) a process of inspecting the mask pattern formed on the electroformed plating layer and the electrode layer, (j) ) A method of manufacturing a fine metal mask using an electroforming method including a step of separating the electrode layer from the electroforming layer from the carrier glass is disclosed.

Moreover, as a conventional vapor deposition mask with a board|substrate, what was described in Unexamined-Japanese-Patent No. 2019-173181 is known.

Japanese Unexamined Patent Publication No. 2019-173181 discloses a plurality of plating layers composed of a glass substrate, a plating layer formed by plating on the substrate, and having a perforated region and a non-perforated region surrounding the perforated region. A deposition mask with a substrate is described, characterized in that a deposition mask is provided, and a plurality of deposition masks are arranged in a plurality of stages and in a plurality of columns.

An object to be solved by one embodiment of the present disclosure is to provide a method of forming a metal pattern having an excellent taper shape.

Another problem to be solved by another embodiment of the present disclosure is to provide a method of manufacturing a metal mask for deposition having an excellent taper shape.

The present disclosure includes the following aspects.

<1> step of preparing a laminate having a negative photosensitive resin layer on a substrate, incident on the negative photosensitive resin layer at an angle to the thickness direction of the exposure mask from the side opposite to the side on which the substrate is provided A step of irradiating light having a component that is, and pattern-exposing the negative photosensitive resin layer through the exposure mask, forming a resin pattern having a tapered shape by developing the pattern-exposed negative photosensitive resin layer, and forming a tapered metal pattern corresponding to the shape of the resin pattern.

<2> In the step of pattern exposure, a scattering layer having a diffuse transmittance of 5% or more and an exposure light source are arranged in this order on a side opposite to the negative photosensitive resin layer side of the exposure mask, and the exposure light source The method for forming a metal pattern according to <1>, in which scattered light is irradiated from the above through the scattering layer.

<3> The method of forming a metal pattern according to <2>, wherein the scattering layer contains a matrix material and particles present in the matrix material, and a difference in refractive index between the matrix material and the particles is 0.05 or more.

<4> The method of forming a metal pattern according to <2> or <3>, wherein the scattering layer contains a matrix material and particles present in the matrix material, and the particles have an average primary particle diameter of 0.3 µm or more.

<5> The method for forming a metal pattern according to any one of <2> to <4>, wherein the scattering layer has irregularities on at least one surface.

<6> The method for forming a metal pattern according to <5>, wherein the unevenness has a plurality of convex portions, and the distance between adjacent convex portions and tops of the convex portions is 10 μm to 50 μm.

<7> The method for forming a metal pattern according to any one of <2> to <6>, wherein the scattering layer and the exposure mask are disposed at a position where they do not contact each other.

<8> The metal pattern according to any one of <2> to <6>, wherein the scattering layer is in contact with the exposure mask and disposed on a side opposite to the negative photosensitive resin layer side in the exposure mask. method of formation.

<9> The method of forming a metal pattern according to any one of <2> to <6>, wherein the exposure mask is a scattering exposure mask in which the scattering layer is formed on a surface opposite to the surface on which the light-shielding pattern is formed.

<10> The preparing step is to transfer the negative photosensitive resin layer of the transfer material onto the substrate using a transfer material having a temporary support and a negative photosensitive resin layer disposed on the temporary support, The method for forming a metal pattern according to any one of <1> to <9>, including forming the laminate.

<11> The method for forming a metal pattern according to <10>, wherein the pattern exposure in the pattern exposure step is contact exposure in which the temporary support is brought into contact with the exposure mask to be exposed.

<12> The pattern exposure in the pattern exposure step is contact exposure in which the exposure mask is brought into contact with the laminate having the negative photosensitive resin layer to expose after the temporary support is peeled off. The method of forming the metal pattern described in >.

<13> The method for forming a metal pattern according to any one of <1> to <12>, wherein the substrate is a conductive substrate.

<14> The method for forming a metal pattern according to any one of <1> to <13>, wherein the metal pattern is a metal pattern formed by a plating method.

<15> The method for forming a metal pattern according to any one of <1> to <14>, further including a step of removing the resin pattern after the step of forming the metal pattern.

<16> The method for forming a metal pattern according to <15>, wherein the resin pattern is removed with a chemical solution.

<17> The method for forming a metal pattern according to any one of <1> to <16>, further including a step of removing the substrate from the metal pattern.

<18> The method for forming a metal pattern according to any one of <1> to <17>, wherein the resin pattern includes a pyramid shape or a cone shape resin pattern.

<19> The method for forming a metal pattern according to any one of <1> to <18>, wherein the negative photosensitive resin layer has a thickness of 10 µm or more.

<20> The method for forming a metal pattern according to any one of <1> to <19>, wherein the obtained metal pattern is a metal pattern for a metal mask for vapor deposition.

<21> A method for manufacturing a metal mask for vapor deposition, including forming a metal pattern by the method for forming a metal pattern according to any one of <1> to <20>.

According to one embodiment of the present disclosure, a method of forming a metal pattern having an excellent taper shape can be provided.

According to another embodiment of the present disclosure, a method for manufacturing a metal mask for deposition having an excellent taper shape can be provided.

1 is a schematic diagram showing a preferred example of a method for forming a metal pattern according to the present disclosure.
Fig. 2 is a schematic cross-sectional view showing a first aspect of the arrangement position of the scattering layer in light irradiation in the pattern exposure step.
Fig. 3 is a schematic cross-sectional view showing a second aspect of the arrangement position of the scattering layer in light irradiation in the pattern exposure step.
Fig. 4 is a schematic cross-sectional view showing an example of using a light scattering exposure mask as a third aspect of the arrangement position of the scattering layer in light irradiation in the pattern exposure step.
Fig. 5 is a schematic cross-sectional view showing the position of the length of each part in one example of one resin pattern.
Fig. 6 is a schematic cross-sectional view showing the position of the length of each part in one example of one metal pattern.
7 is a schematic view showing an example of the pattern shape of an exposure mask.

Hereinafter, the contents of the present disclosure will be described. In addition, although it demonstrates referring attached drawing, the code|symbol may be abbreviate|omitted.

In addition, the numerical range expressed using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in this specification, "(meth)acryl" represents both acryl and methacryl, or any one, and "(meth)acrylate" represents both acrylate and methacrylate, or either one. indicate

In the present specification, the amount of each component in the composition means the total amount of the plurality of substances corresponding to each component present in the composition, unless otherwise specified.

In this specification, the word "process" is included in the term as long as the intended purpose of the process is achieved even if it is not only an independent process but also a case that cannot be clearly distinguished from other processes.

In addition, in the notation of a group (atomic group) in this specification, the notation that does not describe substitution and unsubstitution includes those having a substituent as well as those having no substituent. For example, an "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 this specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, as light used for exposure, in general, active light rays (active energy rays) such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams are exemplified.

In addition, the chemical structural formula in this specification may be described as a simplified structural formula in which hydrogen atoms are omitted.

In the present disclosure, “mass%” and “weight%” have the same meaning, and “mass parts” and “weight parts” have the same meaning.

Moreover, in this indication, the combination of two or more preferable aspects is a more preferable aspect.

In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are, unless otherwise specified, using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names of Tosoh Corporation). It is a molecular weight obtained by using a gel permeation chromatography (GPC) analyzer, detecting with a solvent THF (tetrahydrofuran) and a differential refractometer, and converting using polystyrene as a standard substance.

(Method of forming metal pattern)

A method of forming a metal pattern according to the present disclosure includes a step of preparing a laminate having a negative photosensitive resin layer on a substrate, and an exposure mask from the side opposite to the side on which the substrate is provided in the negative photosensitive resin layer. A step of irradiating light having a component incident obliquely with respect to the thickness direction of and pattern-exposing the negative-type photosensitive resin layer through the exposure mask, developing the pattern-exposed negative-type photosensitive resin layer to form a tapered shape and a step of forming a resin pattern having a resin pattern, and a step of forming a tapered metal pattern corresponding to the shape of the resin pattern.

In a conventional method of forming a metal pattern, a metal pattern can be formed by forming a through hole in a metal plate by an etching method using a photolithography technique.

For example, after patterning a photoresist on a stainless steel (SUS) substrate having a thickness of 100 μm to 200 μm, the SUS substrate is etched into the shape of the opening to be realized using an etchant.

However, in the method of processing a metal sheet by etching with a chemical solution, since the metal sheet is etched not only in the thickness direction but also in the surface direction, so-called side etching occurs, there is a problem in the dimensional accuracy or stability of processing.

Therefore, as a method for producing a high-precision metal mask, a method for manufacturing a fine metal mask using an electroforming plating method has been proposed.

As an example of a method for manufacturing a metal mask by the electroforming method, first, a metal film (ie, a conductive film) is formed on one side of a base substrate made of a non-conductive material such as glass by sputtering or the like to impart conductivity, and then the conductive film is applied. A pattern of openings in a mask made of photoresist is transferred and formed with high precision. Next, on the conductive film exposed from the photoresist, a power supply is connected to this conductive film in a plating solution, and nickel or a nickel alloy is deposited to a required thickness. Finally, this precipitated metal film is peeled off to make a metal mask.

At this time, in order to manufacture a metal mask having a tapered aperture, the photoresist pattern needs to be a tapered pattern having an inclination on the sidewall.

In this way, the present inventors have found that there is a problem in the tapered shape in the conventional metal pattern formation method.

In the method for forming a metal pattern according to the present disclosure, light having a component incident obliquely with respect to the thickness direction of an exposure mask is irradiated from the side opposite to the side on which the substrate is provided in the negative photosensitive resin layer, By pattern-exposing the negative photosensitive resin layer, the exposure amount, particularly the exposure amount of the side surface of the formed resin pattern, is reduced along the length of the negative photosensitive resin layer in the thickness direction, and a tapered shape is generated in the obtained resin pattern . Moreover, by being the said aspect, the taper shape of the said resin pattern and the taper shape of the metal pattern obtained can fully be controlled. Therefore, it is assumed that a metal pattern having an excellent taper shape can be obtained.

The metal pattern produced by the method of forming a metal pattern according to the present disclosure is a metal pattern having a reverse taper shape or a forward taper shape when reversed, and can be suitably used as, for example, a metal mask for deposition, and can be used for organic EL displays. It can be more suitably used as a FMM (Fine Metal Mask) for device manufacturing, and can be particularly suitably used as an FMM for organic light emitting diode (OLED) manufacturing.

Moreover, as FIG. 1, the schematic diagram which shows a preferable example of the formation method of the metal pattern concerning this indication is shown.

Figure 1 consists of Figure 1 (a) to Figure 1 (e) according to the steps of each process. 1(a) to 1(e), in a part of the metal pattern to be formed, it is shown as a cross-sectional schematic diagram showing a cross section in a direction perpendicular to the surface direction of the base material.

As shown in Fig. 1 (a), in the step of preparing the laminate, a laminate 100 having a negative photosensitive resin layer 104a on a substrate 102 is prepared.

An exposure mask (not shown) thickness of the negative photosensitive resin layer 104a in the laminate 100 from the side opposite to the side on which the base material 102 is provided in the negative photosensitive resin layer 104a. Pattern exposure is performed by light having a component incident obliquely with respect to the direction, and further development is performed to form a resin pattern 104 having a tapered shape as shown in FIG. 1(b).

Next, as shown in FIG. 1(c), a reverse tapered metal pattern 106 corresponding to the shape of the resin pattern 104 is formed by a plating method or the like.

In addition, the taper angle of the resin pattern is θ1, and the taper angle of the metal pattern is θ2. In addition to Fig. 1(c), θ1 and θ2 are the same in Fig. 1(b), Fig. 1(d) and Fig. 1(e).

The resin pattern 104 is removed from the base material 102 having the resin pattern 104 and the metal pattern 106 by a chemical solution or the like, and as shown in FIG. 1(d), the metal pattern 106 is removed. A base material 102 having is obtained.

From the substrate 102 having the metal pattern 106, the substrate 102 may be further removed. By removing the substrate 102, only the metal pattern 106 can be obtained as shown in Fig. 1(e). In the case of removing the base material 102 as shown in FIG. 1(e), the metal pattern 106 is preferably a pattern in which all metal parts are bonded to each other in parts not shown.

<Preparation process>

The method for forming a metal pattern according to the present disclosure includes a step of preparing a laminate having a negative photosensitive resin layer on a substrate (also referred to as “preparation step”).

In addition, the preparation step uses a transfer material having a temporary support and a negative photosensitive resin layer disposed on the temporary support to transfer the negative photosensitive resin layer of the transfer material onto the base material, thereby forming the laminated layer. It is preferable to include forming a sieve.

The negative photosensitive resin layer used in this disclosure and the transfer material having the negative photosensitive resin layer will be described later.

The above laminate is a laminate having at least a base material and a negative photosensitive resin layer, and may have other layers such as a temporary support body and a release layer, but a laminate composed of a base material, a negative photosensitive resin layer, and a temporary support body, or A laminate made of a substrate and a negative photosensitive resin layer is preferable, and a laminate made of a substrate, a negative photosensitive resin layer, and a temporary support is more preferable.

The thickness of the negative photosensitive resin layer is not particularly limited and can be appropriately set according to the desired thickness of the resin pattern described later. From the viewpoint of the taper angle and dimensional stability of the metal pattern to be obtained, it is preferably 8 μm or more, and 10 μm. The above is more preferable, 15 μm or more is more preferable, 20 μm or more is particularly preferable, and 30 μm or more is most preferable. Moreover, it is preferable that the upper limit of the thickness of the said negative type photosensitive resin layer is 100 micrometers or less.

-write-

It is preferable that the said base material is a plate-shaped base material, and it is more preferable that it is a metal substrate.

In addition, the base material is preferably a conductive base material, that is, a conductive base material having conductivity at least on its surface, and the base material is a base material made of a conductive material, that is, the base material is a conductive base material having conductivity as a whole. it is more preferable

As the substrate, for example, a metal thin plate made of stainless steel or the like, or a material formed by electroless plating a conductive film of nickel on the upper surface of glass as an insulating material can be suitably used.

As said glass, alkali-free glass or soda glass can be used suitably.

As the conductive material used for the substrate, for example, nickel, chromium, tantalum, tungsten, indium tin oxide (ITO), etc. can be used. In addition, physical methods such as formation of a conductive film by electroless plating, sputtering, vacuum deposition, and ion plating can also be used for imparting conductivity to the base material. Moreover, as a material of the base material used as a base, a glass plate, a stainless steel plate, a silicon substrate, etc. are mentioned.

When using a substrate having a conductive layer on the surface, the thickness of the conductive layer is preferably smaller as long as it has conductivity required for the electrolytic plating process.

Moreover, it is preferable that the thickness of the said conductive layer is 0.5 micrometer - 5 micrometer specifically, for example.

The method for producing the laminate is not particularly limited, but examples include a method of forming a negative photosensitive resin layer on a substrate using a transfer material, a method of coating and drying a negative photosensitive resin composition on a substrate, and the like. and a method of bonding the negative photosensitive resin layer and the base material in the transfer material is preferably mentioned.

Moreover, when the said transfer material has a temporary support body, it is preferable to peel after the said bonding.

In addition, when the said transfer material has a cover film, after removing a cover film from the surface of a negative photosensitive resin layer, what is necessary is just to stick it together.

The method of bonding the base material and the transfer material (the negative photosensitive resin layer in the transfer material) is not particularly limited, and a known transfer method and a laminating method can be used.

The bonding is preferably performed by laminating a base material on the negative photosensitive resin layer side of the transfer material and pressurizing and heating using a means such as a roll. Moreover, well-known laminators, such as a laminator, a vacuum laminator, and an auto-cut laminator which can further increase productivity, can be used for the said bonding.

Moreover, it is preferable that the said bonding is performed by the roll-to-roll system.

Hereinafter, the roll-to-roll method will be described.

In the present disclosure, the roll-to-roll method includes a step of unwinding at least one of the base material and the transfer material using a base material capable of winding and unwinding (also referred to as “unwinding step”), and the laminate. including a step of winding (also referred to as a "winding step"), at least one step (preferably all steps, or all steps other than the heating step), at least one of the base material and the transfer material, and the above It refers to a method of bonding a base material and a transfer material together while conveying the laminate.

The unwinding method in the unwinding step and the winding method in the unwinding step are not particularly limited, and a known method may be used in the manufacturing method using a roll-to-roll method.

<Pattern exposure process>

In the method for forming a metal pattern according to the present disclosure, light having a component incident obliquely with respect to the thickness direction of an exposure mask is irradiated from the side opposite to the side on which the substrate is provided in the negative photosensitive resin layer, and a step of pattern-exposing the negative photosensitive resin layer through the exposure mask (also referred to as "pattern exposure step").

The method of irradiating light having a component obliquely incident with respect to the thickness direction of the exposure mask is not particularly limited, but a method of irradiating scattered light to the exposure mask, exposure of light with a wide irradiation angle using an optical member such as a lens The method of irradiating a mask, etc. are mentioned.

The method of forming the scattered light is not particularly limited, and a known method can be used. For example, a method of forming the scattered light by a scattering layer is preferably used.

The method for forming light with a wide irradiation angle is not particularly limited, and a known method can be used. For example, light emitted from an LED (light emitting diode) with a narrow irradiation angle passes through a wide-angle lens or a fisheye lens. and a method of widening the irradiation angle.

Among them, in the pattern exposure step, scattered light is irradiated to an exposure mask from the side opposite to the side on which the substrate is provided in the negative photosensitive resin layer, and the negative photosensitive resin layer is irradiated with light passing through the exposure mask. It is preferable that it is a process of pattern-exposing a stratum.

As a pattern exposure step, specifically, for example, scattered light is irradiated to the negative photosensitive resin layer through an exposure mask from an exposure light source disposed on a side opposite to the negative photosensitive resin layer side of the exposure mask. By doing, the process of carrying out pattern exposure is mentioned preferably.

Irradiation of the scattered light is carried out by arranging a scattering layer having a diffuse transmittance of 5% or more and an exposure light source in this order on the side opposite to the negative photosensitive resin layer side of the exposure mask, and scattering light from the exposure light source through the scattering layer. It is desirable to investigate

Note that pattern exposure in the present disclosure refers to exposure in a patterned form, that is, exposure in a form in which an exposed portion and an unexposed portion exist in a negative photosensitive resin layer.

In the pattern exposure step, the detailed arrangement and specific size of the patterns in the pattern exposure are not particularly limited. For example, what is necessary is just to select suitably according to the display device (for example, a touchscreen) manufactured.

In the pattern exposure, a mask (light shielding mask) for exposure in a desired shape is used as the exposure mask. There is no restriction|limiting in particular as said exposure mask, A mask made of a well-known material can be used.

-Exposure light source-

As an exposure light source in this indication, a well-known thing can be used.

An exposure light source can be appropriately selected and used as long as it is a light source that emits light (for example, 365 nm or 405 nm) of a wavelength capable of exposing the negative photosensitive resin layer. Specifically, ultra-high-pressure mercury-vapor lamps, high-pressure mercury-vapor lamps, metal halide lamps, and LEDs (Light Emitting Diodes) are exemplified.

The light in the exposure is not particularly limited as long as the negative photosensitive resin layer can be exposed, but is preferably light having a wavelength of 365 nm or 405 nm, more preferably light having a wavelength of 365 nm, and having a wavelength of 365 nm Light is particularly preferred.

The exposure amount is not particularly limited as long as the negative photosensitive resin layer can be exposed, but is preferably 5 mJ/cm ² to 1,000 mJ/cm ² and more preferably 10 mJ/cm ² to 500 mJ/cm ² .

In the case of using a transfer material having a temporary support and a negative photosensitive resin layer disposed on the temporary support, in the pattern exposure step, you may expose after peeling the temporary support from the negative photosensitive resin layer, or expose through the temporary support. After that, the temporary support may be peeled off.

In the peeling of the temporary support, for example, while conveying the laminate containing the negative photosensitive resin layer and the temporary support at a speed of 0.5 m/min to 4.0 m/min, the angle formed by the temporary support and the laminate is 10°. It can be done by stretching to ~180°. By peeling off the temporary support before exposure, the adverse effect of the foreign matter contained in the temporary support or the foreign matter adhering to the temporary support on the exposure can be avoided.

In order to prevent contamination of the negative photosensitive resin layer due to contact between the negative photosensitive resin layer and the exposure mask, and to avoid an influence on exposure due to foreign matter adhering to the exposure mask, exposure through a temporary support is preferable.

That is, it is preferable to have a temporary support on the negative photosensitive resin layer in the laminate, and to perform the exposure in the step of forming the resin pattern through the temporary support. It is more preferable that the pattern exposure in the step of pattern exposure is contact exposure in which the temporary support is brought into contact with the exposure mask to be exposed.

In addition, it is also preferable that the pattern exposure in the pattern exposure step is contact exposure in which the exposure mask is brought into contact with the laminate having the negative photosensitive resin layer to expose after the temporary support is peeled off. .

As an exposure method using an exposure mask, existing high-definition exposure means such as mask close contact exposure using a mask aligner, proximity exposure, or projection exposure can be used. When exposure is performed using a mask aligner, the distance (exposure proximity gap) between the exposure mask and the negative photosensitive resin layer can be set arbitrarily, but is preferably 0 μm to 500 μm, more preferably 10 μm to 300 μm, and 25 μm to 200 μm is particularly preferred.

Moreover, as an exposure mask, a binary mask, a gray mask, a halftone mask, etc. can be used.

-Scattering layer-

In the pattern exposure process, irradiation of light (preferably scattered light) having a component that is incident obliquely with respect to the thickness direction of the exposure mask is performed by a scattering layer (more preferably having a diffuse transmittance) disposed between the exposure light source and the exposure mask. It is preferable to carry out through a scattering layer of 5% or more).

The scattering layer may be provided independently, or a function as a scattering layer may be imparted to other layers of the laminate, for example, a material having scattering properties, such as a base material of an exposure mask, a temporary support in a dry film resist, and the like. .

From the viewpoint of the taper angles of the obtained resin pattern and metal pattern, an embodiment in which the scattering layer and the exposure mask are disposed at a position where they do not contact each other is preferable.

The distance between the scattering layer and the exposure mask may be, for example, 0 μm to 200 μm.

In addition, the scattering layer is preferably arranged on a side opposite to the negative photosensitive resin layer side in the exposure mask from the viewpoint of the taper angles of the obtained resin pattern and metal pattern.

The measurement of the diffuse transmittance uses an index of the light diffuse transmittance. The light diffuse transmittance refers to the transmittance of diffused light obtained by subtracting the parallel component from the total transmittance of light including both parallel and diffuse components among the light passing through the scattering layer after light is applied to the scattering layer.

The light diffuse transmittance can be obtained in accordance with JIS K 7136 (2000) "Plastics - How to determine the haze of a transparent material".

That is, haze represents a value represented by the following formula, and therefore, the diffuse transmittance of the scattering layer as the subject can be obtained by using a haze meter.

Immersion (haze)% = [diffuse transmittance (Td) / total light transmittance (Tt)] × 100

As a measuring device in this disclosure, the value using the Nippon Denshoku Kogyo Co., Ltd. haze meter NDH7000II is employ|adopted.

The diffuse transmittance of the scattering layer is preferably 5% or more, more preferably 50% or more, still more preferably 70% or more, and particularly preferably 90% or more.

The upper limit of the diffuse transmittance is not particularly limited, but may be, for example, 100%.

The scattering angle of the scattering layer is preferably 15° or more, more preferably 20° or more, still more preferably 20° or more and 80° or less, and particularly preferably 40° or more and 70° or less. Here, the scattering angle means the width (sum of plus and minus sides) up to an angle at which the intensity of light transmitted through the scattering layer is 0° in the vertical direction and the intensity is half of that. In some cases, it is expressed in terms of half-price full-width.

The scattering angle can be measured using a goniometer or the like.

The scattering characteristics of light are generally symmetrical on the plus and minus sides, but even when the plus and minus sides are asymmetric, the definition of the scattering angle does not change.

When the value of the scattering angle differs depending on the direction of the measurement plane, the largest value among them is taken as the scattering angle of the scattering layer.

The scattering layer is not particularly limited, but from the viewpoint of easy adjustment of the diffuse transmittance and easy availability, the scattering layer is a scattering layer containing a matrix material and particles present in the matrix material (hereinafter referred to as a matrix material and particles). can be referred to as a containing scattering layer), or a scattering layer having irregularities on at least one surface.

-Scattering Layer Containing Matrix Material and Particles-

As one aspect of the scattering layer used in the present disclosure, a matrix material and a layer containing particles present in the matrix material and imparting light scattering properties to the scattering layer (hereinafter sometimes referred to as specific particles) can be cited. .

The scattering layer containing the specific particles is preferably a layer in which the specific particles are dispersed and contained in a transparent matrix material.

As a matrix material, glass, quartz, resin material, etc. are mentioned.

When glass or quartz is used as the matrix material, specific particles may be kneaded into the glass or quartz and uniformly dispersed to form a scattering layer.

When a resin material is used as the matrix material, it is preferably a resin capable of forming an ultraviolet-transmitting resin layer, and examples thereof include acrylic resins, polycarbonate resins, polyester resins, polyethylene resins, polypropylene resins, epoxy resins, A urethane resin, a silicone resin, etc. are mentioned.

When a resin material is used as the matrix material, the scattering layer can be formed by a known method. For example, a plate-shaped scattering layer can be obtained by melt-kneading resin pellets and specific particles as a matrix material and injection molding. Alternatively, a resin composition containing a precursor monomer of a resin and specific particles may be cured to form a scattering layer, or a resin composition obtained by kneading specific particles in a mixture containing a resin material and a solvent as an optional component may be cured to form a scattering layer. You can do it. The method of forming the scattering layer is not limited to the above.

In order for specific particles to impart sufficient light scattering properties to the scattering layer, the scattering layer preferably contains a matrix material and particles present in the matrix material, and the difference in refractive index between the matrix material and the particles is preferably 0.05 or more, and 0.05 to 0.05 It is more preferably 1.0, and more preferably 0.05 to 0.6.

When the difference in refractive index between the matrix material and the specific particle is within the above range, the intensity of scattered light can be increased, and the decrease in energy imparted due to excessive reflection of incident light, which is a concern when the intensity of scattering height is excessively large, is suppressed. , it is possible to impart an amount of energy sufficient to cure the negative photosensitive resin layer.

Further, in order for specific particles to impart sufficient light scattering properties to the scattering layer, the scattering layer preferably contains a matrix material and particles present in the matrix material, and the average primary particle diameter of the particles is 0.3 μm or more. The average primary particle diameter of the specific particles is more preferably in the range of 0.3 μm to 2.0 μm, and particularly preferably in the range of 0.5 μm to 1.5 μm. When the average primary particle diameter is within the above range, Mie Scattering of ultraviolet rays occurs, the intensity of forward scattered light increases, and it is easy to impart an amount of energy sufficient to cure the negative photosensitive resin layer.

The average primary particle diameter of the specific particles is calculated by measuring the particle diameters of 200 arbitrary specific particles existing within the viewing angle using an electron microscope and arithmetic averaging the measured values.

In addition, when the shape of a particle is not spherical, the longest side is taken as a particle diameter.

Examples of specific particles include zirconium oxide particles (ZrO ₂ particles), niobium oxide particles (Nb ₂ O ₅ particles), titanium oxide particles (TiO ₂ particles), aluminum oxide particles (Al ₂ O ₃ particles), and dioxide dioxide. inorganic particles such as silicon particles (SiO ₂ particles), and organic particles such as crosslinked polymethyl methacrylate.

The scattering layer may contain only one type of specific particle, or may contain two or more types of specific particles.

The content of specific particles is not particularly limited, and it is preferable to achieve a desired diffuse transmittance or a desired scattering angle by adjusting the type, size, content, shape, refractive index, etc. of specific particles in the scattering layer.

As content of specific particle|grains, it can be set as 5 mass % - 50 mass % with respect to the total mass of a scattering layer, for example.

-A scattering layer having irregularities on at least one surface-

As another embodiment of the scattering layer, a scattering layer having irregularities on at least one surface is exemplified. By having irregularities on at least one surface of the scattering layer, light is scattered by the irregularities, and scattered light is irradiated to the negative photosensitive resin layer through the scattering layer.

As for the irregularities in the scattering layer, it is preferable that the distance between adjacent convex portions and tops of the convex portions is 10 μm to 50 μm.

As for the irregularities, adjacent convex portions and bottoms of the convex portions are in contact, and it is preferable from the viewpoint of light scattering that the adjacent convex portions and the convex portions are densely formed without gaps such as voids.

A desired diffuse transmittance or a desired scattering angle can be achieved by adjusting the size and shape of the convex portion, the formation density per unit area of the convex portion, and the like. There is no particular restriction on the shape of the convex portion, and a hemispherical shape, a conical shape, a pyramidal shape, a ridge shape, or the like is appropriately selected depending on the target diffusion transmittance, diffusion angle, and the like.

A commercial product may be used as the scattering layer having irregularities on at least one surface. Commercially available products include, for example, Lens Diffusion Plate (registered trademark) manufactured by Optical Solutions Co., Ltd., trade name: LSD5ACUVT10, LSD10ACUVT10, LSD20ACUVT10, LSD30ACUVT10, LSD40ACUVT10, LSD60ACUVT10, LSD80ACUVT10 (above, made of ultraviolet-transmitting acrylic resin) ),

Lens diffusion plate (registered trademark): LSD5AC10, LSD10AC10, LSD20AC10, LSD30AC10, LSD40AC10, LSD60AC10, LSD80AC10 (above, made of acrylic resin),

Lens diffusion plate (registered trademark): LSD5PC10, LSD10PC10, LSD20PC10, LSD30PC10, LSD40PC10, LSD60PC10, LSD80PC10, LSD60×10PC10, LSD60×1PC10, LSD40×1PC10, LSD30×5PC10 (above, made of polycarbonate),

Lens diffuser plate (registered trademark): LSD5U3PS (above, made of quartz glass) and the like.

As other scattering layers, fly eye lens FE10 manufactured by Tokushu Kogaku Jushi Co., Ltd., Diffuser manufactured by Pitt, SDXK-1FS, SDXK-AFS, SDXK-2FS manufactured by Suntec Opt Co., Ltd., Phil Light diffusion film MX manufactured by Plus Co., Ltd., acrylic diffusion plates ADF901, ADF852, ADF803, ADF754, ADF705, ADF656, ADF607, ADF558, ADF509, ADF451 manufactured by Shibuya Kogaku Co., Ltd., Nano manufactured by Oji Ftex Co., Ltd. Buckling (registered trademark), light diffusion film made by Lintec Co., Ltd. HDA060, HAA120, GBA110, DCB200, FCB200, IKA130, EDB200, Scorchcal (registered trademark) light diffusion diffuser film made by 3M Japan Co., Ltd. 3635-30 , 3635-70, light up (registered trademark) SDW, EKW, K2S, LDS, PBU, GM7, SXE, MXE, SP6F, Opt Saver (registered trademark) L-9, L-11, L made by Kimoto Co., Ltd. -19, L-20, L-35, L-52, L-57, STC3, STE3, chemical mat (registered trademark) 75PWX, 125PW, 75PBA, 75BLB, 75PBB, Oparus manufactured by Keiwa Co., Ltd. (registered trademark) trademark) PBS-689G, PBS-680G, PBS-689HF, PBS-680HG, PBS-670G, UDD-147D2, UDD-148D2, SHBS-227C1, SHBS-228C2, UDD-247D2, PBS-630L, PBS-630A, PBS-632A, BS-539, BS-530, BS-531, BS-910, BS-911, BS-912, Gurareje's Legenda (registered trademark) PC, CL, HC, OC, TR, MC, SQ, EL, OE, D120P, D121UPZ, D121UP, D261SIIIJ1, D261IVJ1, D263SIII, S263SIV, D171, D171S, D174S manufactured by Tsujiden Co., Ltd., etc. are mentioned.

The thickness of the scattering layer is preferably 2 mm or less, more preferably 1 mm or less, and even more preferably 100 μm or less.

The thickness of the scattering layer is preferably 0.5 μm or more, and more preferably 1 μm or more.

As the thickness of the scattering layer, the arithmetic average value of five arbitrary measured values measured by observing the cross section of the scattering layer with a scanning electron microscope (SEM) is adopted.

Irradiation of scattered light is not limited to light irradiation through an independent scattering layer.

For example, a scattering exposure mask in which layers other than the light-shielding portion in the exposure mask have light scattering properties can be suitably used. When a scattering exposure mask (also simply referred to as a "scattering exposure mask") is used, light passing through the exposure mask becomes scattered light.

Among them, from the viewpoint of the taper angles of the resin pattern and the metal pattern to be obtained, an aspect in which the exposure mask is a scattering exposure mask in which the scattering layer is formed on a surface opposite to the surface on which the light-shielding pattern is formed is preferable. .

In the irradiation of scattered light in the pattern exposure step, the arrangement position of the scattering layer is not particularly limited as long as it is between the exposure light source and the exposure mask.

For example, you may have an exposure mask, a scattering layer, and an exposure light source in this order on the side opposite to the side in which the said base material was provided in the said negative photosensitive resin layer.

An example of the arrangement position of the scattering layer in the case where scattered light (a preferable example of light having a component incident obliquely with respect to the thickness direction of the exposure mask) is irradiated through the scattering layer will be described with reference to the drawings.

Fig. 2 is a schematic cross-sectional view showing a first aspect of the arrangement position of the scattering layer in light irradiation in the pattern exposure step. The exposed laminate precursor shown in FIG. 2 includes a substrate 12, a negative photosensitive resin layer 16, a polyethylene terephthalate (PET) film serving as a temporary support 24, and an exposure mask 26 having a light-shielding region 26A. ), and on the exposure light source (not shown) side (opposite side of the negative photosensitive resin layer 16 to the side on which the substrate 12 is provided), a scattering layer 28 is provided, an exposure mask 26 and are disposed at positions not in contact with each other.

2 to 4, the optical path of the irradiated light is schematically indicated by an arrow.

As described in FIG. 2, since the scattered light passing through the scattering layer 28 is scattered at an angle to the normal direction of the negative photosensitive resin layer 16, the negative photosensitive resin layer The side surface of the pattern-shaped cured layer 16A formed by the cured region in (16) has a gentle inclination with respect to the surface direction of the base material. The side surface of the patterned cured layer 16A preferably has a taper angle of 50° or less with respect to the surface direction of the base material.

Fig. 3 is a schematic cross-sectional view showing a second aspect of the arrangement position of the scattering layer in light irradiation in the pattern exposure step. The exposed laminate precursor in FIG. 3 has the same layer structure as the exposed laminate precursor shown in FIG. 2 . In the second aspect shown in Fig. 3, the scattering layer 28 and the exposure mask 26 are placed in contact with each other.

The scattering layer 28 may be integrally formed on the surface of the exposure mask 26 on the light source side by coating, sticking, or the like.

Also in the second aspect shown in FIG. 3 , the scattered light that has passed through the scattering layer 28 and is scattered is incident as scattered light to a region of the exposure mask 26 that does not have the light-shielding region 26A, as shown in FIG. , The pattern-shaped cured layer 16A formed by the cured region in the negative photosensitive resin layer 16 has a gentle inclination with respect to the surface direction of the base material in a side view. The patterned cured layer 16A preferably has a taper angle of 50° or less with respect to the surface direction of the substrate in a cross section parallel to the normal direction of the substrate.

Fig. 4 is a schematic cross-sectional view showing an example of using a scattering exposure mask as a third aspect of the arrangement position of the scattering layer in light irradiation in the pattern exposure step.

In the third aspect shown in Fig. 4, a scattering exposure mask 32 having a diffuse transmittance of 5% or more is used as an exposure mask. The scattering exposure mask 32 is a scattering agent exposure mask 32 having a light blocking region 32A in a desired region of the scattering substrate. The diffuse transmittance of the scattering exposure mask is as described above.

In the third aspect shown in FIG. 4 , irradiated light irradiated by an exposure light source (not shown) arranged on the side opposite to the side on which the substrate 12 is provided in the negative photosensitive resin layer 16 has scattering properties. Since the scattered light that passes through the exposure mask 32 and is incident on the negative photosensitive resin layer 16 at an angle with respect to the normal direction of the substrate, as shown in FIG. 4, the negative photosensitive resin layer 16 ) The pattern-shaped cured layer 16A formed by the cured region in ) has a gentle inclination with respect to the surface direction of the base material in a side view. The patterned cured layer 16A preferably has a taper angle of 50° or less with respect to the surface direction of the substrate in a cross section parallel to the normal direction of the substrate.

In either aspect, in the metal pattern formation method of the present disclosure, scattered light is irradiated from an exposure light source to an exposure mask, and the negative photosensitive resin layer is exposed in a pattern through the exposure mask. For this reason, the side surface portion of the pattern-shaped cured layer formed by the cured region in the negative photosensitive resin layer has a gentle inclination with respect to the surface direction of the base material, and it is difficult to become a steeply inclined side surface. A laminate having various advantages as described above can be formed.

For the purpose of improving the linearity of the pattern after exposure, it is also preferable to perform heat treatment before the resin pattern forming step. It is possible to reduce the roughening of the pattern edge due to the standing wave generated in the negative photosensitive resin layer at the time of exposure by a process called so-called PEB (Post Exposure Bake).

<Resin pattern formation process>

The method for forming a metal pattern according to the present disclosure includes a step of forming a resin pattern having a tapered shape by developing the pattern-exposed negative photosensitive resin layer (also referred to as a "resin pattern forming step").

The thickness of the formed resin pattern can be appropriately selected from the relationship between hole pitch, aperture diameter, and deposition angle, but from the viewpoint of the taper angle and dimensional stability of the metal pattern obtained, 10 μm or more is preferable, and 15 μm or more is more preferable. 20 μm or more is more preferable, and 30 μm or more is particularly preferable. Moreover, it is preferable that an upper limit is 100 micrometers or less.

In the method for measuring the thickness of a resin pattern, a metal pattern, and each layer in the present disclosure, a cross section in a direction perpendicular to the plane direction of the transfer material or the laminate is observed with a scanning electron microscope (SEM), , to be measured. In addition, unless otherwise specified, the thickness value is an average value obtained by measuring 10 or more thicknesses.

In the present disclosure, "taper shape" in a resin pattern means the width W1 of the top of the resin pattern (opposite to the substrate side) and the width of the green portion (substrate side) of the resin pattern. When (W2) is measured, it refers to the case where the relationship is W1<W2. The taper angle refers to the angle formed by the side surface of the pattern with the base material, but may be approximated as an angle formed between the straight line and the surface of the base material when a straight line connects the top end and the green end of the resin pattern.

Although it can be appropriately selected from the relationship of the taper angle, hole pitch, aperture diameter, and deposition angle, 10° to 80° is preferable, 20° to 70° is more preferable, and 30° to 60° is particularly preferable.

Moreover, it is preferable that the taper shape with respect to the base material of the resin pattern in this indication is a forward taper shape.

In the present disclosure, the tapered shape of the resin pattern can be adjusted by, for example, selecting the angle and amount of light in a component obliquely incident on the exposure mask.

For example, when a scattering layer is used, adjusting the scattering angle and diffuse transmittance of the scattering layer, the amount of light of the exposure light source, and the like is exemplified.

The shape of the resin pattern is not particularly limited and may be appropriately selected according to the purpose, but the resin pattern preferably includes a truncated resin pattern from the viewpoint of more exerting the effect in the present disclosure, It is more preferable to include a resin pattern of a pyramidal object or a cone object.

In addition, the resin pattern preferably includes a resin pattern having a maximum diameter of 100 μm or less on the side opposite to the substrate side from the viewpoint of more exhibiting the effect in the present disclosure, and the side opposite to the substrate side It is more preferable to include a resin pattern having a maximum diameter of 50 μm or less on the surface, and more preferably to include a resin pattern having a maximum diameter of 0.1 μm or more and 20 μm or less on the side opposite to the substrate side, and on the side opposite to the substrate side. It is particularly preferable to include a resin pattern having a maximum diameter of 0.2 μm or more and 10 μm or less.

In addition, the resin pattern preferably includes a resin pattern having a surface area of 1,200 μm ² or less on the side opposite to the substrate side, from the viewpoint of more exhibiting the effect in the present disclosure, and the opposite side to the substrate side. It is more preferable to include a resin pattern having a surface area of 500 μm ² or less, and it is more preferable to include a resin pattern having an area of 0.1 μm ² or more and 250 μm ^{2 or} less on the side opposite to the substrate side, and It is particularly preferable to include a resin pattern having an area of 1 μm ² or more and 100 μm ² or less on the surface on the opposite side.

In the resin pattern forming step, the pattern-exposed negative photosensitive resin layer is developed to form a resin pattern having a tapered shape.

When the transfer material has an intermediate layer, in the resin pattern forming step, the intermediate layer of the unexposed portion is also removed along with the negative photosensitive resin layer of the unexposed portion. Further, in the resin pattern forming step, the middle layer of the exposed portion may also be removed in a form of being dissolved or dispersed in a developing solution.

Development of the exposed negative photosensitive resin layer in the resin pattern forming step can be performed using a developing solution.

The developer is not particularly limited as long as the non-image portion (non-exposed portion) of the negative photosensitive resin layer can be removed, and for example, a known developer such as the developer described in Japanese Unexamined Patent Publication No. 5-72724 can be used. .

As the developing solution, an alkaline aqueous solution-based developing solution containing a compound having pKa = 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter) is preferable. The developer may contain a water-soluble organic solvent and/or a surfactant. As a developer, the developer described in Paragraph 0194 of International Publication No. 2015/093271 is also preferable.

The development method is not particularly limited, and any of puddle development, shower development, shower and spin development, and dip development may be used. The shower development is a development treatment in which a non-exposed portion is removed by spraying a developing solution on the negative photosensitive resin layer after exposure by means of a shower.

After the resin pattern formation process, it is preferable to spray a cleaning agent by shower and remove development residues while rubbing with a brush.

The liquid temperature of the developing solution is not particularly limited, but is preferably 20°C to 40°C.

<Metal pattern forming process>

The method of forming a metal pattern according to the present disclosure includes a step of forming a tapered metal pattern corresponding to the shape of the resin pattern (also referred to as “metal pattern forming step”).

The thickness of the metal pattern to be formed is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 12 μm or more, from the viewpoint of strength and durability of the metal pattern to be obtained. And, 15 μm or more is particularly preferred. Moreover, it is preferable that it is 100 micrometers or less, and, as for an upper limit, it is more preferable that it is 50 micrometers or less.

In the present disclosure, the "taper shape corresponding to the shape of the resin pattern" in the metal pattern refers to the taper shape of the metal pattern formed according to the shape of the resin pattern having a taper shape. As described above, the resin pattern If there is a relationship of W1 < W2, when the width W3 of the top of the metal pattern (opposite to the base material side) and the width W4 of the green part (substrate side) of the metal pattern are measured, W3 > W4 For example, a metal pattern corresponding to a resin pattern formed in a forward tapered shape described later becomes a reverse tapered shape.

In addition, the taper angle in the taper shape of the metal pattern refers to the angle formed by the side surface of the metal pattern and the base material. You may approximate it as an angle.

The taper angle of the metal pattern can be appropriately selected, but is preferably 100° to 170°, more preferably 110° to 160°, and particularly preferably 120° to 150°.

It is preferable that the said metal pattern is a metal pattern provided with the opening part which has the said taper shape from a viewpoint of exhibiting more the effect in this indication.

The metal pattern preferably includes a resin pattern having a maximum diameter of 100 μm or less of an opening formed on at least one surface in a surface direction of the metal pattern, from the viewpoint of further exhibiting the effects of the present disclosure. It is more preferable to include a resin pattern in which the maximum diameter of the openings on at least one surface in the surface direction of the metal pattern is 50 μm or less, and the maximum diameter of the openings on at least one surface in the surface direction of the metal pattern is 0.1 μm. It is more preferable to include a resin pattern of 20 μm or less, and it is particularly preferable to include a resin pattern in which the maximum diameter of an opening on at least one surface in the plane direction of the metal pattern is 0.2 μm or more and 10 μm ^{2 or} less.

Further, from the viewpoint of further exhibiting the effects of the present disclosure, the metal pattern preferably includes a resin pattern in which an opening area of an opening provided on at least one surface in a plane direction of the metal pattern is 1,200 μm ² or less. And, it is more preferable to include a resin pattern in which the opening area of the opening on at least one surface in the surface direction of the metal pattern is 500 μm ² or less, and the opening provided on at least one surface in the surface direction of the metal pattern It is more preferable to include a resin pattern having an opening area of 0.1 μm ² or more and 250 μm ² or less, and the opening area of the opening provided on at least one surface in the surface direction of the metal pattern is 1 μm ^{2 or} more and 100 μm ^{2 or} less. is particularly preferred.

The method of forming the metal pattern in the metal pattern forming step is not particularly limited as long as it is a method capable of forming a metal pattern of a reverse tapered shape corresponding to the shape of the resin pattern, but a plating method (electroforming method) is preferable. can be heard

That is, it is preferable that the said metal pattern is a metal pattern formed by the plating method.

As a method of forming a metal pattern by the plating method, the following method is mentioned, for example.

A plating power supply is connected to a conductive portion of the base material on which the resin pattern is formed, and it is immersed in a plating bath for depositing a desired metal. Plating is deposited in the form of a film on a portion where the upper surface of the substrate is exposed, and plating metal is deposited in a range equal to or less than the thickness of the resin pattern to grow into a reverse tapered metal pattern.

Examples of the plating bath include a nickel sulfamate bath and a nickel-cobalt alloy bath obtained by adding cobalt thereto. In the plating process, the plating thickness is controlled by the voltage value and the energization or immersion time.

In addition, the composition of the plating bath, the plating treatment temperature, the total value at the time of the plating treatment, the plating treatment time, etc. are not particularly limited and can be appropriately selected according to the purpose.

In addition, it is not limited to electroplating, and you may deposit a metal by the electroless plating method.

In addition, the plating process can be performed in a range from room temperature (for example, 5°C to 30°C) to about 60°C.

A variety of metals such as nickel, a nickel-cobalt alloy, an iron-nickel alloy, and copper can be used as the metal in the metal pattern.

Among them, it is preferably an iron-nickel alloy containing 30% by mass or more and 45% by mass or less of nickel, and a metal whose main component is an alloy of 36% by mass of nickel and 64% by mass of iron, that is, more preferably Invar. do. When the material for forming the metal pattern is Invar, the coefficient of thermal expansion of the metal pattern is, for example, about 1.2×10 ^-6 /°C.

<Resin pattern removal process>

It is preferable that the method of forming a metal pattern according to the present disclosure further includes a step of removing the resin pattern (also referred to as a "resin pattern removal step") after the step of forming the metal pattern.

There is no particular restriction on the method for removing the resin pattern in the resin pattern removal step, but it is preferably performed with a chemical solution.

As a method of removing the resin pattern, a method of immersing a substrate having the resin pattern and the metal pattern in a chemical solution while stirring at preferably 30 ° C to 80 ° C, more preferably 50 ° C to 80 ° C for 1 minute to 30 minutes. can be heard

As the chemical solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound, A liquid dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof is exemplified.

Moreover, you may remove it by the spray method, the shower method, the puddle method, etc. using a chemical liquid.

<substrate removal process>

The method of forming a metal pattern according to the present disclosure preferably further includes a step of removing the substrate from the metal pattern after the step of forming the metal pattern.

The metal pattern from which the substrate has been removed has an aperture pattern having an inclined sidewall with an inverse taper shape complementary to the photoresist pattern, and can be suitably used as a thin-plate metal mask.

Although there is no particular limitation as a method of removing the substrate from the metal pattern in the substrate removal step, a method of separating the substrate and the metal pattern is preferably used.

Moreover, it is preferable that the said metal pattern is a pattern in which all metal parts are bonded.

The peeling is not particularly limited, but can be peeled, for example, by pulling the substrate in a folded state at 180°. The peeling speed is not particularly limited, but is preferably 1 mm/s to 50 mm/s.

<Other processes>

The method for forming a metal pattern according to the present disclosure may include optional steps (other steps) other than those described above. There is no restriction|limiting in particular as another process, A well-known process is mentioned.

Moreover, as an example of the resin pattern formation process and other processes in this indication, the method of Paragraph 0035 - Paragraph 0051 of Unexamined-Japanese-Patent No. 2006-23696 can be used suitably also in this indication.

Further, the method for forming a metal pattern according to the present disclosure may include a step of polishing the obtained metal pattern, a step of washing the obtained metal pattern, and the like.

<Usage of metal pattern>

The use of the metal pattern produced by the method for forming a metal pattern according to the present disclosure is not particularly limited, but the metal pattern can be suitably used as a metal pattern for a metal mask, and as a metal pattern for a metal mask for deposition. It can be used more suitably, and can be used particularly suitably as a metal pattern for a metal mask for depositing an organic light emitting material. Moreover, as said organic light emitting material, the red (R), green (G), or blue (B) organic light emitting material (RGB organic light emitting material) used for organic electroluminescent display devices is mentioned suitably, and organic electroluminescent light emitting diode RGB organic light emitting materials used for the above are particularly suitable.

In addition, the metal pattern produced by the method for forming a metal pattern according to the present disclosure can be particularly suitably used as a metal mask for deposition used in manufacturing an organic EL light emitting diode (OLED).

In addition, other uses of the metal pattern produced by the method of forming a metal pattern according to the present disclosure are not particularly limited, but for solder cream printing, dot printing for touch panels, phosphors of PDP (Plasma Display Panel: Plasma Display Panel) Printing etc. are also mentioned.

Hereinafter, the negative photosensitive resin layer used in the present disclosure and the transfer material having the negative photosensitive resin layer will be described in detail.

<<negative photosensitive resin layer>>

The transfer material used in this disclosure has at least a negative photosensitive resin layer.

The negative photosensitive resin layer may contain a polymerizable compound, a polymerization initiator, and other components.

-Polymeric compound-

It is preferable that a negative photosensitive resin layer contains a polymeric compound.

A polymerizable compound is a compound having a polymerizable group. As a polymerizable group, a radical polymerizable group and a cationic polymerizable group are mentioned, and a radical polymerizable group is preferable from a viewpoint that curing sensitivity is more favorable.

The polymerizable compound preferably includes a polymerizable compound having an ethylenically unsaturated group (hereinafter, simply referred to as "ethylenically unsaturated compound").

As an ethylenically unsaturated group, a (meth)acryloyl group is preferable.

It is preferable that the ethylenically unsaturated compound contains a bifunctional or higher functional ethylenically unsaturated compound. Here, the "difunctional or higher functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.

As an ethylenically unsaturated compound, a (meth)acrylate compound is preferable.

Examples of the ethylenically unsaturated compound include a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound ( Preferably, a trifunctional or higher functional (meth)acrylate compound) is preferably included.

As a bifunctional ethylenically unsaturated compound, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane diethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, for example ) acrylate, 1,10-decanedioldi(meth)acrylate, and 1,6-hexanedioldi(meth)acrylate.

As a commercial item of a bifunctional ethylenically unsaturated compound, for example, tricyclodecane dimethanol diacrylate [trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], tricyclodecane dimethanol dimetha acrylate [trade name: NK ester DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], 1,9-nonanediol diacrylate [trade name: NK ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], 1 ,10-decanediol diacrylate [trade name: NK ester A-DOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], and 1,6-hexanediol diacrylate [trade name: NK ester A- HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.].

Examples of trifunctional or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, and trimethylolpro Feint ly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and glycerin tri (meth) acrylate are exemplified.

Here, "(tri/tetra/penta/hexa)(meth)acrylate" means tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. is a concept that includes In addition, "(tri/tetra)(meth)acrylate" is a concept containing tri(meth)acrylate and tetra(meth)acrylate.

There is no particular restriction on the upper limit of the number of functional groups as the trifunctional or higher functional ethylenically unsaturated compound.

As a commercial item of a trifunctional or higher functional ethylenically unsaturated compound, dipentaerythritol hexaacrylate [brand name: KAYARAD DPHA, Shin-Nakamura Chemical Industry Co., Ltd.] is mentioned, for example.

The ethylenically unsaturated compound is 1,9-nonanedioldi(meth)acrylate or 1,10-decanedioldi(meth)acrylate and dipentaerythritol (tri/tetra/penta/hexa) It is more preferable that (meth)acrylate is included.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], ( Alkylene oxide modified compound of meth)acrylate compound [KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Allnex (registered trademark) 135, etc.], and ethoxylated glycerin triacrylates [such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.].

As an ethylenically unsaturated compound, a urethane (meth)acrylate compound is also mentioned. As the urethane (meth)acrylate compound, a trifunctional or higher functional urethane (meth)acrylate compound is preferable. Examples of the trifunctional or higher functional urethane (meth)acrylate compound include 8UX-015A [manufactured by Daisei Fine Chemical Co., Ltd.], NK Ester UA-32P [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], and NK Ester UA- 1100H [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.] is exemplified.

It is preferable that the ethylenically unsaturated compound contains the ethylenically unsaturated compound which has an acidic radical from the point of improving developability.

As an acid group, a phosphoric acid group, a sulfonic acid group, and a carboxy group are mentioned, for example. Among the above, as an acidic radical, a carboxyl group is preferable.

As the ethylenically unsaturated compound having an acid group, a trifunctional to tetrafunctional ethylenically unsaturated compound having an acid group [a compound in which a carboxy group is introduced into the skeleton of pentaerythritol tri and tetraacrylate (PETA) (acid value: 80 KOH/g to 120 mgKOH/ g)], and 5 to 6 functional ethylenically unsaturated compounds having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) compound having a carboxy group introduced into the skeleton [acid value: 25 KOH/g to 70 mg KOH/g)] can be heard A trifunctional or more than trifunctional ethylenically unsaturated compound having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

As the ethylenically unsaturated compound having an acid group, at least one compound selected from the group consisting of bifunctional or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one compound selected from the group consisting of bifunctional or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, developability and film strength are higher.

Examples of the difunctional or higher functional ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 [manufactured by Toagosei Co., Ltd.], Aronix (registered trademark) M-520 [manufactured by Toagosei Co., Ltd.], and Aronix (registered trademark). trademark) M-510 [manufactured by Toagosei Co., Ltd.].

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in Paragraphs 0025 to 0030 of Unexamined-Japanese-Patent No. 2004-239942 can be preferably used, and the content described in this publication is incorporated herein by reference. .

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

Among the ethylenically unsaturated compounds, the content of the ethylenically unsaturated compounds having a molecular weight of 300 or less is preferably 30% by mass or less, and more preferably 25% by mass or less, with respect to the content of all ethylenically unsaturated compounds contained in the negative photosensitive resin layer. It is preferable, and 20 mass % or less is more preferable.

The negative photosensitive resin layer may contain a single ethylenically unsaturated compound or may contain two or more ethylenically unsaturated compounds.

The content of the ethylenically unsaturated compound is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and 20% by mass to 60% by mass with respect to the total mass of the negative photosensitive resin layer. It is more preferable, and 20 mass % - 50 mass % are especially preferable.

When the negative photosensitive resin layer contains a bifunctional or higher functional ethylenically unsaturated compound, it may further contain a monofunctional ethylenically unsaturated compound.

When the negative photosensitive resin layer contains a bifunctional or higher functional ethylenically unsaturated compound, the bifunctional or higher functional ethylenically unsaturated compound is preferably a main component in the ethylenically unsaturated compound contained in the negative photosensitive resin layer.

When the negative photosensitive resin layer contains a bifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional or higher functional ethylenically unsaturated compound is 60% by mass relative to the content of all the ethylenically unsaturated compounds contained in the negative photosensitive resin layer. -100 mass % is preferable, 80 mass % - 100 mass % is more preferable, and 90 mass % - 100 mass % is still more preferable.

When the negative photosensitive resin layer contains an ethylenically unsaturated compound having an acid group (preferably, a difunctional or higher functional ethylenically unsaturated compound having a carboxy group or a carboxylic acid anhydride thereof), the content of the ethylenically unsaturated compound having an acid group is negative. 1 mass % - 50 mass % are preferable with respect to the total mass of a mold photosensitive resin layer, 1 mass % - 20 mass % are more preferable, and 1 mass % - 10 mass % are still more preferable.

-Polymerization initiator-

It is preferable that the negative photosensitive resin layer contains a polymerization initiator.

As a polymerization initiator, a thermal polymerization initiator and a photoinitiator are mentioned, A photoinitiator is preferable.

As the photopolymerization initiator, for example, a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as "oxime photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter referred to as "α-aminoalkylphenone photopolymerization initiator") Also referred to as "initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter referred to as " Also referred to as "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as "N-phenylglycine-based photopolymerization initiator").

The photopolymerization initiator includes at least one selected from the group consisting of oxime photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators. Preferably, it is more preferable to include at least one kind selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

Moreover, as a photoinitiator, you may use Paragraph 0031 of Unexamined-Japanese-Patent No. 2011-095716 - 0042, and Paragraph 0064 of Unexamined-Japanese-Patent No. 2015-014783 - the polymerization initiator of 0081, for example.

As a commercially available photopolymerization initiator, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE- 01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carboxyl][2-(2,2, 3,3-tetrafluoropropoxy)phenyl]methanol-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-03, manufactured by BASF], 1-[4-[4-(2-benzofuranyl) carbonyl)phenyl]thio]phenyl]-4-methyl-1-pentanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-04, manufactured by BASF], 2-(dimethylamino) )-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl- 1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF], 2-hydroxy-1-{4-[4-(2) -Hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: IRGACURE (registered trademark) 127, manufactured by BASF], 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl) butanone-1 [trade name: IRGACURE (registered trademark) 369, manufactured by BASF], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: IRGACURE (registered trademark)] 1173, manufactured by BASF], 1-hydroxycyclohexylphenyl ketone [trade name: IRGACURE (registered trademark) 184, manufactured by BASF], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: IRGACURE 651, manufactured by BASF], and an oxime ester compound [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropane -1-one [trade name APi-307 (registered trademark), Shenzhen UV- ChemTECH LTD], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) [trade name: TR-PBG-305, Chang Manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.], 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3 -yl] -1,2-propanediol-2-(O-acetyloxime) [trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.], 3-cyclohexyl-1-(6-(2) -(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)propane-1,2-dione-2-(O-benzoyloxime) [trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.].

The negative photosensitive resin layer may contain a single polymerization initiator or may contain two or more polymerization initiators.

0.1 mass % or more is preferable with respect to the total mass of a negative photosensitive resin layer, and, as for content of a polymerization initiator, 0.5 mass % or more is more preferable. Moreover, 10 mass % or less is preferable with respect to the total mass of a negative photosensitive resin layer, and, as for the upper limit of content of a polymerization initiator, 5 mass % or less is more preferable.

-Alkali-soluble acrylic resin-

The negative photosensitive resin layer may contain an alkali-soluble acrylic resin.

When the negative photosensitive resin layer contains an alkali-soluble acrylic resin, the solubility of the negative photosensitive resin layer (non-exposed portion) in a developing solution is improved.

In the present disclosure, "alkali-soluble" means that the dissolution rate determined by the following method is 0.01 µm/sec or more.

A coating film of the compound (for example, resin) by applying a propylene glycol monomethyl ether acetate solution having a concentration of 25% by mass on a glass substrate and then heating in an oven at 100 ° C. for 3 minutes ( thickness of 2.0 μm). The dissolution rate (µm/sec) of the coating film is determined by immersing the coating film in a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 30°C).

In addition, when the target compound is insoluble in propylene glycol monomethyl ether acetate, an organic solvent with a boiling point of less than 200 ° C. other than propylene glycol monomethyl ether acetate (for example, tetrahydrofuran, toluene, or ethanol) to dissolve the target compound.

The alkali-soluble acrylic resin is not limited as long as it is an acrylic resin having alkali solubility described above. Here, "acrylic resin" means a resin containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylic acid ester.

30 mol% or more is preferable, and, as for the total ratio of the structural unit derived from (meth)acrylic acid in alkali-soluble acrylic resin, and the structural unit derived from (meth)acrylic acid ester, 50 mol% or more is more preferable.

In the present disclosure, when the content of a "structural unit" is defined by mole fraction (molar ratio), the term "structural unit" is synonymous with "monomer unit" unless otherwise specified. In addition, in this indication, when resin or a polymer has 2 or more types of specific structural units, content of the said specific structural unit shall show the total content of the said 2 or more types of specific structural units unless there is particular explanation.

It is preferable that the alkali-soluble acrylic resin has a carboxy group in terms of developability. As a method for introducing a carboxy group into an alkali-soluble acrylic resin, a method of synthesizing an alkali-soluble acrylic resin using a monomer having a carboxy group is exemplified. By the above method, the monomer having a carboxy group is introduced into the alkali-soluble acrylic resin as a structural unit having a carboxy group. As a monomer which has a carboxy group, acrylic acid and methacrylic acid are mentioned, for example.

Alkali-soluble acrylic resin may have one carboxy group, and may have two or more carboxy groups. Moreover, single 1 type may be sufficient as the structural unit which has a carboxy group in alkali-soluble acrylic resin, and 2 or more types may be sufficient as it.

The content of the structural unit having a carboxyl group is preferably 5 mol% to 50 mol%, more preferably 5 mol% to 40 mol%, and more preferably 10 mol% to 30 mol% with respect to the total amount of the alkali-soluble acrylic resin. desirable.

It is preferable that an alkali-soluble acrylic resin has a structural unit which has an aromatic ring from the point of the water vapor transmission rate and intensity|strength after hardening. As a structural unit which has an aromatic ring, it is preferable that it is a structural unit derived from a styrene compound.

As a monomer which forms the structural unit which has an aromatic ring, the monomer which forms the structural unit derived from a styrene compound, and benzyl (meth)acrylate are mentioned, for example.

Examples of the monomer forming the structural unit derived from the styrene compound include styrene, p-methylstyrene, α-methylstyrene, α,p-dimethylstyrene, p-ethylstyrene, and p-t- butyl styrene, t-butoxy styrene, and 1,1-diphenyl ethylene, styrene or α-methyl styrene is preferred, and styrene is more preferred.

1 type may be sufficient as the structural unit which has an aromatic ring in alkali-soluble acrylic resin, and 2 or more types may be sufficient as it.

When the alkali-soluble acrylic resin has a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5 mol% to 90 mol%, and 10 mol% to 90 mol% with respect to the total amount of the alkali-soluble acrylic resin. mol% is more preferable, and 15 mol% - 90 mol% are still more preferable.

It is preferable that an alkali-soluble acrylic resin contains the structural unit which has an alicyclic frame|skeleton from the point of adhesiveness and the intensity|strength after hardening.

As an aliphatic ring in an alicyclic frame|skeleton, a dicyclopentane ring, a cyclohexane ring, an isophorone ring, and a tricyclodecane ring are mentioned, for example. Among the above, as an aliphatic ring in an aliphatic cyclic frame|skeleton, a tricyclodecane ring is preferable.

As a monomer which forms the structural unit which has an alicyclic backbone, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate are mentioned, for example.

1 type may be sufficient as the structural unit which has an alicyclic skeleton in alkali-soluble acrylic resin, and 2 or more types may be sufficient as it.

When the alkali-soluble acrylic resin has a structural unit having an aliphatic cyclic skeleton, the content of the structural unit having an aliphatic cyclic skeleton is preferably 5 mol% to 90 mol%, relative to the total amount of the alkali-soluble acrylic resin, and 10 mol% -80 mol% is more preferable, and 10 mol% - 70 mol% is still more preferable.

It is preferable that alkali-soluble acrylic resin has a reactive group from the point of adhesiveness and the intensity|strength after hardening.

As the reactive group, a radical polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. Moreover, when alkali-soluble acrylic resin has an ethylenically unsaturated group, it is preferable that alkali-soluble acrylic resin has a structural unit which has an ethylenically unsaturated group in a side chain.

In the present disclosure, "main chain" refers to a relatively longest bonded chain among molecules of a polymer compound constituting the resin, and "side chain" refers to an atomic group branched from the main chain.

As an ethylenically unsaturated group, a (meth)acrylic group or a (meth)acryloxy group is preferable, and a (meth)acryloxy group is more preferable.

1 type may be sufficient as the structural unit which has an ethylenically unsaturated group in alkali-soluble acrylic resin, and 2 or more types may be sufficient as it.

When the alkali-soluble acrylic resin has a structural unit having an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group is preferably 5 mol% to 70 mol%, relative to the total amount of the alkali-soluble acrylic resin, and 10 mol% -50 mol% is more preferable, and 15 mol% - 40 mol% is still more preferable.

As a means for introducing a reactive group into an alkali-soluble acrylic resin, a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, etc., an epoxy compound, a block isocyanate compound, iso A method of reacting a cyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride, and the like is exemplified.

As a preferred example of a means for introducing a reactive group into an alkali-soluble acrylic resin, after synthesizing an alkali-soluble acrylic resin having a carboxy group by a polymerization reaction, a part of the carboxy group of the alkali-soluble acrylic resin is glycidyl (meth) by a polymer reaction. ) A means for introducing a (meth)acryloxy group into an alkali-soluble acrylic resin by reacting an acrylate is exemplified. By the above means, an alkali-soluble acrylic resin having a (meth)acryloxy group in the side chain can be obtained.

The polymerization reaction is preferably carried out under temperature conditions of 70°C to 100°C, more preferably under temperature conditions of 80°C to 90°C. As the polymerization initiator used in the polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferable. Moreover, it is preferable to perform the said polymer reaction under temperature conditions of 80 degreeC - 110 degreeC. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

10,000 or more are preferable, as for the weight average molecular weight (Mw) of alkali-soluble acrylic resin, 10,000-100,000 are more preferable, and 15,000-50,000 are still more preferable.

From the viewpoint of developability, the acid value of the alkali-soluble acrylic resin is preferably 50 mgKOH/g or more, more preferably 60 mgKOH/g or more, more preferably 70 mgKOH/g or more, and particularly preferably 80 mgKOH/g or more. In the present disclosure, the acid value of the alkali-soluble acrylic resin is a value measured according to the method described in JIS K0070:1992.

The upper limit of the acid value of the alkali-soluble acrylic resin is preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less, from the viewpoint of suppressing dissolution of the exposed negative photosensitive resin layer (exposure portion) in the developing solution.

Specific examples of alkali-soluble acrylic resins are shown below. In addition, the content ratio (molar ratio) of each structural unit in the following alkali-soluble acrylic resin can be suitably set within the said preferable range of Mw according to a purpose.

[Formula 1]

[Formula 2]

[Formula 3]

The negative photosensitive resin layer may contain a single alkali-soluble acrylic resin, or may contain two or more alkali-soluble acrylic resins.

The content of the alkali-soluble acrylic resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and 25% by mass with respect to the total mass of the negative photosensitive resin layer from the point of developability. -70% by mass is more preferred.

-Polymer containing structural units having a carboxylic acid anhydride structure-

The negative photosensitive resin layer may further contain, as a binder, a polymer (hereinafter, also referred to as “polymer B”) containing a structural unit having a carboxylic acid anhydride structure. When the negative photosensitive resin layer contains the polymer B, developability and strength after curing can be improved.

The carboxylic acid anhydride structure may be any of a chain carboxylic acid anhydride structure and a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.

As the ring of the cyclic carboxylic acid anhydride structure, a 5-membered ring to a 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is still more preferable.

The structural unit having a carboxylic acid anhydride structure is a structural unit containing in the main chain a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or one hydrogen atom from a compound represented by the following formula P-1 It is preferable that the monovalent group removed is a structural unit bonded to the main chain directly or through a divalent linking group.

[Formula 4]

In formula P-1, R ^A1a represents a substituent, n ^1a pieces of R ^A1a may be the same or different, and Z ^1a represents a ring containing -C(=O)-OC(=O)- represents a divalent group to be formed, and n ^1a represents an integer of 0 or greater.

As a substituent represented by R ^A1a , an alkyl group is mentioned, for example.

As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is still more preferable.

n ^1a represents an integer greater than or equal to 0. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

When n ^1a represents an integer of 2 or greater, a plurality of R ^{A1a '} s may be the same or different. Further, a plurality of R ^{A1a '} s may be bonded to each other to form a ring, but it is preferable not to bond to each other to form a ring.

The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, and more preferably a structural unit derived from an unsaturated aliphatic carboxylic acid anhydride, Structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and constituent units derived from maleic anhydride are most preferred.

1 type of structural unit which has a carboxylic acid anhydride structure in the polymer B may be sufficient as it, and 2 or more types may be sufficient as it.

The content of the structural unit having a carboxylic acid anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and further 10 mol% to 35 mol% with respect to the total amount of the polymer B. desirable.

The negative photosensitive resin layer may contain 1 type of single polymer B, and may contain 2 or more types of polymer B.

When the negative photosensitive resin layer contains the polymer B, the content of the polymer B is preferably 0.1% by mass to 30% by mass with respect to the total mass of the negative photosensitive resin layer from the viewpoint of developability and strength after curing. , 0.2 mass % - 20 mass % are more preferable, 0.5 mass % - 20 mass % are still more preferable, and 1 mass % - 20 mass % are especially preferable.

-Surfactants-

The negative photosensitive resin layer may contain a surfactant.

As surfactant, Paragraph 0017 of Unexamined-Japanese-Patent No. 4502784, and Paragraph 0060 of Unexamined-Japanese-Patent No. 2009-237362 - surfactant of 0071 are mentioned, for example.

Examples of the surfactant include fluorochemical surfactants, silicon surfactants (also referred to as silicone surfactants), nonionic surfactants, and the like, and fluorochemical surfactants or silicone surfactants are preferable.

As commercially available products of fluorine-based surfactants, for example, Megafac (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F -144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557 , F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41 -LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Corporation), Fluorad (registered trademark) FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Suffron (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC- 1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Co., Ltd.), PolyFox (registered trademark) PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Futergent (registered trademark) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (above, made by NEOS Co., Ltd.), etc. are mentioned.

As the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom and in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heated is also preferably used. As such a fluorine-based surfactant, DIC Corporation's Megafac (registered trademark) DS series (Gagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shinbun (February 23, 2016)), for example An example is Megafac (registered trademark) DS-21.

As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

A block polymer can also be used for a fluorochemical surfactant. The fluorine-based surfactant is a (meth)acrylate compound having 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group). ) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used.

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Megafac (registered trademark) RS-101, RS-102, RS-718K, RS-72-K (above, manufactured by DIC Corporation) and the like.

Examples of the silicone surfactant include straight-chain polymers formed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains and terminals.

Specifically, commercially available silicone surfactants include DOWSIL (registered trademark) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, and Toray Silicone SH30PA. , Toray Silicon SH8400 (above, manufactured by Toray Dow Corning Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (above, Shin-Etsu Chemical High School Co., Ltd.) ), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (above, manufactured by Big Chemistry), etc. can

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , Sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (above, manufactured by BASF), Tetronic (registered trademark) 304, 701, 704, 901, 904, 150R1 (above, manufactured by BASF), Solsperse (registered trademark) 20000 (above, manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (above, manufactured by Fujifilm Wako Junyaku Co., Ltd.) ), Pionin (registered trademark) D-6112, D-6112-W, D-6315 (above, Takemoto Yushi Co., Ltd.), Allfin E1010, Surfynol 104, 400, 440 (above, Nissin Kagaku High School (above) Note) and the like.

The negative photosensitive resin layer may contain a single surfactant or may contain two or more surfactants.

When the negative photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass with respect to the total mass of the negative photosensitive resin layer. And, 0.1% by mass to 0.8% by mass is more preferable.

-Other Ingredients-

The negative photosensitive resin layer may contain components (hereinafter, also referred to as "other components") other than the components described above. Examples of other components include heterocyclic compounds, aliphatic thiol compounds, block isocyanate compounds, hydrogen-donating compounds, particles (eg, metal oxide particles), and colorants.

Moreover, as another component, the thermal polymerization inhibitor of Paragraph 0018 of Unexamined-Japanese-Patent No. 4502784, and Paragraph 0058 of Unexamined-Japanese-Patent No. 2000-310706 - the other additives of 0071 are also mentioned, for example.

A negative photosensitive resin layer can be formed by drying the coating layer made of the coating liquid for forming the negative photosensitive resin layer described above. Formation of the negative photosensitive resin layer is described in detail in the section on transfer materials.

-Impurities in the negative photosensitive resin layer-

From the viewpoint of improving reliability and patterning properties, it is preferable that the content of impurities in the negative photosensitive resin layer is small.

Specific examples of the impurity include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof, and halide ions (chloride ions, bromide ions) Minide ion, iodide ion, etc.) etc. are mentioned. Among them, since sodium ions, potassium ions, and chloride ions are easily mixed as impurities, it is particularly preferable to set them as the following contents.

The content of impurities in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less, on a mass basis. The lower limit can be 0.01 ppm or more on a mass basis, and can be 0.1 ppm or more.

Methods for reducing the impurities to the above range include selecting materials that do not contain impurities in the raw materials of each layer, preventing impurities from entering during layer formation, and removing them by washing. By such a method, the impurity amount can be made within the above range.

Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectroscopy, and ion chromatography, for example.

In addition, benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide in the negative photosensitive resin layer , It is preferable that there is little content of compounds, such as hexane. The content of these compounds in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less, on a mass basis. Although the lower limit is not particularly set, it may be 10 ppb or more, or 100 ppb or more, on a mass basis, from the viewpoint of the limit that can be reduced practically and the measurement limit.

The content of the impurities in the compound can be suppressed in the same way as for the metal impurities described above. Moreover, it can quantify by a well-known measuring method.

Although the negative photosensitive resin layer has been described above, it is preferable to set the same impurity amount also to the resin pattern formed from the negative photosensitive resin layer.

-Thickness of negative photosensitive resin layer

Although the thickness of the negative photosensitive resin layer can be selected appropriately, 10 μm or more is preferable, 15 μm or more is more preferable, 20 μm or more is still more preferable, and 30 μm or more is particularly preferable. Moreover, it is preferable that an upper limit is 100 micrometers or less.

-Formation method of negative photosensitive resin layer-

The negative photosensitive resin layer can be formed by preparing a negative photosensitive resin composition containing a component used for formation of the negative photosensitive resin layer and a solvent, followed by application and drying. After using each component as a solution previously dissolved in a solvent, respectively, the obtained solution may be mixed in a predetermined ratio to prepare a composition. The composition prepared as described above may be filtered using, for example, a filter having a pore diameter of 0.2 μm to 30 μm.

A negative photosensitive resin layer can be formed by apply|coating a negative photosensitive resin composition on a temporary support body or a cover film, and drying it.

The coating method is not particularly limited, and can be applied by a known method such as slit coating, spin coating, curtain coating, die coating, or inkjet coating.

Moreover, after forming the intermediate|middle layer mentioned later or other layers on a temporary support body or a cover film, you may form a negative photosensitive resin layer.

-Negative photosensitive resin composition-

It is preferable that a negative photosensitive resin composition contains the component used for formation of a negative photosensitive resin layer, and a solvent. A negative photosensitive resin layer can be suitably formed by containing a solvent in each component, adjusting the viscosity, applying and drying.

It is preferable that the negative photosensitive resin composition contains a solvent.

As a solvent, an organic solvent is preferable. As the organic solvent, for example, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol. As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.

As a solvent, the solvent of Paragraph 0054 of US Patent Application Publication No. 2005/282073 and 0055 can also be used, The content of this specification is integrated in this specification by reference.

Moreover, as a solvent, the organic solvent (high boiling point solvent) with a boiling point of 180 degreeC - 250 degreeC can also be used as needed.

The negative photosensitive resin composition may contain the solvent of single 1 type, and may contain 2 or more types of solvents.

When the negative photosensitive resin composition contains a solvent, the total solid content of the negative photosensitive resin composition is preferably 5% by mass to 80% by mass, and 5% by mass to 40% by mass with respect to the total mass of the negative photosensitive resin composition. Mass % is more preferable, and 5 mass % - 30 mass % are still more preferable.

When the negative photosensitive resin composition contains a solvent, the viscosity at 25°C of the negative photosensitive resin composition is preferably 1 mPa·s to 50 mPa·s, and 2 mPa·s to 50 mPa·s, for example, from the viewpoint of applicability. 40 mPa·s is more preferable, and 3 mPa·s to 30 mPa·s are still more preferable. Viscosity is measured using a viscometer. As a viscometer, the Toki Sangyo Co., Ltd. viscometer (brand name: VISCOMETER TV-22) can be used suitably, for example. However, the viscometer is not limited to the viscometer described above.

When the negative photosensitive resin composition contains a solvent, the surface tension of the negative photosensitive resin composition at 25°C is preferably 5 mN/m to 100 mN/m, for example, from the viewpoint of applicability, 10 mN/m ~ 80 mN/m is more preferable, and 15 mN/m - 40 mN/m is even more preferable.

Surface tension is measured using a surface tensiometer. As a surface tensiometer, a surface tensiometer (trade name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Science and Technology Co., Ltd. can be suitably used, for example. However, the surface tensiometer is not limited to the surface tensiometer described above.

<<Transcription Materials>>

It is preferable that the transfer material used in this indication has at least a negative photosensitive resin layer, and has at least a temporary support body and a negative photosensitive resin layer.

-Temporary support-

The transfer material used in the present disclosure preferably has a temporary support body.

The temporary support is a support that supports the negative photosensitive resin layer and can be peeled off.

When exposing the negative photosensitive resin layer, the temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the negative photosensitive resin layer can be exposed through the temporary support.

Having light transmittance means that the transmittance of the dominant wavelength of light used for pattern exposure is 50% or more, and the transmittance of the dominant wavelength of light used for pattern exposure is preferably 60% or more from the viewpoint of improving exposure sensitivity. , 70% or more is more preferable. As a method of measuring the transmittance, a method of measuring using Otsuka Electronics Co., Ltd. MCPD Series is exemplified.

As a temporary support body, a glass substrate, a resin film, paper, etc. are mentioned, From viewpoints of strength, flexibility, etc., a resin film is especially preferable. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferred.

The thickness of the temporary support is not particularly limited, and is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm in view of ease of handling, versatility, and the like.

The thickness of the temporary support may be selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a base material, light transmittance required during exposure, and the like.

About the preferable aspect of a temporary support body, Paragraph 0017 of Unexamined-Japanese-Patent No. 2014-85643 - Paragraph 0018 have description, and the content of this gazette is integrated in this indication, for example.

-Cover film-

It is preferable that the transfer material used in this disclosure has a cover film on the surface opposite to the surface on the side where the temporary support body in the transfer material is provided.

As a cover film, a resin film, paper, etc. are mentioned, From viewpoints of strength, flexibility, etc., a resin film is especially preferable. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Especially, a polyethylene film, a polypropylene film, and a polyethylene terephthalate film are preferable.

The average thickness of the cover film is not particularly limited, and is preferably 1 μm to 2 mm, for example.

-middle layer-

The transfer material or the laminate used in the present disclosure may have an intermediate layer (for example, a water-soluble resin layer).

It is preferable that an intermediate|middle layer contains the polymer mentioned later.

〔polymer〕

The intermediate layer may contain a polymer.

As the polymer used for the intermediate layer, a water-soluble resin or an alkali-soluble resin is preferable. In the present disclosure, “water-soluble” means that the solubility in 100 g of water at pH 7.0 at 22° C. is 0.1 g or more, and “alkali-soluble” means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22° C. It means that the solubility is 0.1 g or more.

In addition, either water-soluble or alkali-soluble may be sufficient as the said "water-soluble or alkali-soluble", and water-soluble and alkali-soluble may be sufficient as it.

Moreover, it is preferable that the solubility with respect to 100 g of water of pH 7.0 in 22 degreeC of a polymer is 1 g or more, and it is more preferable that it is 5 g or more.

Examples of water-soluble resins include cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and these and resins such as copolymers of Especially, it is preferable that it is a cellulose resin, and it is more preferable that it is at least 1 sort(s) of resin selected from the group which consists of hydroxypropyl cellulose and hydroxypropyl methyl cellulose.

As the alkali-soluble resin, an alkali-soluble acrylic resin is preferable, and an acrylic resin having an acid group that may form a salt is more preferable.

An intermediate|middle layer may contain a polymer individually by 1 type, and may contain 2 or more types.

It is preferable that it is 20 mass % - 100 mass % with respect to the total mass of an intermediate|middle layer, and, as for content of a polymer, it is more preferable that it is 50 mass % - 100 mass %, from an adhesive viewpoint.

[Ultraviolet rays absorber]

The intermediate layer may have a UV absorber for the purpose of controlling absorption. The ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays with a wavelength of 400 nm or less.

Examples of the ultraviolet absorber include ultraviolet absorbing materials such as benzophenone compounds, benzotriazole compounds, benzoate compounds, salicylate compounds, triazine compounds, and cyanoacrylate compounds.

Specifically, for example, as a benzotriazole compound, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4-6- Bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H- Benzotriazol-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, etc. Mixtures, modified products, polymers, derivatives and the like thereof may be mentioned.

For example, as a triazine compound, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol, 2-[4- [(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[ 4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 ,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, etc., mixtures, modified products, polymers, derivatives, etc. thereof; there is.

These may be used independently, and may mix and use plurality again.

The content of the ultraviolet absorbing material is not particularly limited, and may be appropriately set as an amount that makes the optical density of the photosensitive resin layer a desired value.

〔Surfactants〕

In the middle layer, it is preferable to contain a surfactant from the viewpoint of thickness uniformity. As the surfactant, any of a surfactant having a fluorine atom, a surfactant having a silicon atom, and a surfactant having neither a fluorine atom nor a silicon atom can be used. Among them, the surfactant is preferably a surfactant having a fluorine atom, from the viewpoint of suppression of generation of streaks in the negative photosensitive resin layer and the intermediate layer and adhesiveness, and having a perfluoroalkyl group and a polyalkyleneoxy group. It is more preferable that it is a surfactant.

Moreover, although anionic, cationic, nonionic (nonionic) or amphoteric any can be used as surfactant, a preferable surfactant is a nonionic surfactant.

The surfactant preferably has a solubility of 1 g or more in 100 g of water at 25°C from the viewpoint of suppressing precipitation of the surfactant.

The intermediate layer may contain the surfactant alone or in combination of two or more.

It is preferable that content of the surfactant in the said intermediate|middle layer is 0.05 mass % - 2.0 mass % with respect to the total mass of an intermediate|middle layer from the viewpoint of suppression of generation|occurrence|production of a stripe in a negative photosensitive resin layer and an intermediate|middle layer, and adhesiveness. And, it is more preferable that it is 0.1 mass % - 1.0 mass %, and it is especially preferable that it is 0.2 mass % - 0.5 mass %.

[Inorganic filler]

An inorganic filler may be included in the intermediate layer. The inorganic filler in the present disclosure is not particularly limited. A silica particle, an aluminum oxide particle, a zirconium oxide particle, etc. are mentioned, A silica particle is more preferable. From the viewpoint of transparency, particles having a small particle diameter are preferable, and particles having an average particle diameter of 100 nm or less are more preferable. For example, if it is a commercial product, Snowtex (registered trademark) is used suitably.

The volume fraction of the particles in the middle layer (volume ratio occupied by the particles in the middle layer) is 5% to 90% with respect to the total volume of the middle layer from the viewpoint of adhesion between the middle layer and the negative photosensitive resin layer. It is preferable, it is more preferable that it is 10% - 80%, and it is more preferable that it is 20% - 60%.

[pH adjuster]

The intermediate layer may contain a pH adjusting agent. By including a pH adjuster, the color development state or the discoloration state of the pigment in the intermediate layer can be maintained more stably, and the adhesion between the negative photosensitive resin layer and the intermediate layer is further improved.

The pH adjuster in the present disclosure is not particularly limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, and organic ammonium salts. Sodium hydroxide is preferred from the standpoint of water solubility. From the viewpoint of adhesion between the negative photosensitive resin layer and the intermediate layer, an organic ammonium salt is preferable.

[thickness of the middle layer]

The thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2 μm, from the viewpoint of adhesion between the negative photosensitive resin layer and the intermediate layer and pattern formation.

Moreover, it is preferable that the thickness of an intermediate|middle layer is thinner than the thickness of a negative photosensitive resin layer.

The intermediate layer may have two or more layers.

When the intermediate layer has two or more layers, the thickness of each layer is not particularly limited as long as it is within the above range, but among the two or more layers in the intermediate layer, the thickness of the layer closest to the negative photosensitive resin layer is the intermediate layer and the negative photosensitive resin layer. From the viewpoint of the adhesiveness of the photosensitive resin layer and pattern formation, 0.3 μm to 10 μm is preferable, 0.3 μm to 5 μm is more preferable, and 0.3 μm to 2 μm is particularly preferable.

[Method of Forming Intermediate Layer]

The intermediate layer in the present disclosure can be formed by preparing a composition for forming an intermediate layer containing components used for forming the intermediate layer and a water-soluble solvent, applying and drying the intermediate layer. After using each component as a solution previously dissolved in a solvent, respectively, the resulting solution may be mixed in a predetermined ratio to prepare a composition. The composition prepared as described above may be filtered using a filter having a pore diameter of 3.0 µm or the like.

An intermediate layer can be formed on the temporary support by applying the composition for forming the intermediate layer to the temporary support and drying it. The coating method is not particularly limited, and can be applied by a known method such as slit coating, spin coating, curtain coating, or inkjet coating.

The intermediate layer-forming composition preferably contains a component used for forming the intermediate layer and a water-soluble solvent. An intermediate layer can be suitably formed by incorporating a water-soluble solvent into each component to adjust the viscosity, coating, and drying.

As the water-soluble solvent, a known water-soluble solvent can be used, and examples thereof include water, alcohol having 1 to 6 carbon atoms, and the like, and water is preferably included. As a C1-C6 alcohol, methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol are mentioned specifically,. Among them, it is preferable to use at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.

-Other floors-

The transfer material according to the present disclosure may have layers other than those described above (hereinafter, also referred to as "other layers"). As another layer, a thermoplastic resin layer etc. are mentioned.

Regarding the preferred aspect of the thermoplastic resin layer, paragraphs 0189 to 0193 of Japanese Unexamined Patent Publication No. 2014-85643, and further preferred aspects of other layers are described in paragraphs 0194 to 0196 of Japanese Unexamined Patent Publication No. 2014-85643, respectively. , the content of this publication is incorporated herein by reference.

-Manufacturing method of transfer material-

The manufacturing method of the transfer material used in the present disclosure is not particularly limited, and a known manufacturing method such as a known method of forming each layer can be used.

Moreover, it is preferable that the manufacturing method of a transcription|transfer material further includes the process of providing a cover film on the said negative photosensitive resin layer, after forming a negative photosensitive resin layer on a temporary support body.

In addition, after manufacturing the transfer material, you may manufacture and store the transfer material in the form of a roll by winding the transfer material. The transfer material in the form of a roll can be provided in a form as it is bonded to a base material in a roll-to-roll method.

(Method of manufacturing metal mask for vapor deposition)

A method for manufacturing a metal mask for deposition according to the present disclosure is a method for manufacturing a metal mask for deposition including forming a metal pattern by the method for forming a metal pattern according to the present disclosure.

Further, a method for manufacturing a metal mask for vapor deposition according to the present disclosure includes a step of preparing a laminate having a negative photosensitive resin layer on a base material, and a side of the negative photosensitive resin layer opposite to the side on which the base material is provided. a step of irradiating light having a component obliquely incident with respect to the thickness direction of the exposure mask from the exposure mask, pattern-exposing the negative-type photosensitive resin layer through the exposure mask, and developing the pattern-exposed negative-type photosensitive resin layer. It is preferable to include a step of forming a tapered resin pattern by doing so, and a step of forming a tapered metal pattern corresponding to the shape of the resin pattern.

Further, the method for manufacturing a metal mask for vapor deposition according to the present disclosure may include each step in the above-described method for forming a metal pattern according to the present disclosure, and the preferred embodiments are also the same.

In addition, the metal mask for vapor deposition manufactured by the method for manufacturing a metal mask for vapor deposition according to the present disclosure may have other members in addition to the metal pattern.

The other members are not particularly limited, and known members used for metal masks for deposition can be used.

(Manufacturing method of organic light emitting diode, and manufacturing method of organic EL display device)

The method for manufacturing an organic light emitting diode according to the present disclosure or the method for manufacturing an organic EL display device according to the present disclosure uses a metal pattern obtained by the method for forming a metal pattern according to the present disclosure.

In addition, the method for manufacturing an organic light emitting diode according to the present disclosure or the method for manufacturing an organic EL display device according to the present disclosure is a step of using a metal pattern obtained by the method for forming a metal pattern according to the present disclosure as a metal mask for deposition. It is preferable to include, and it is more preferable to include a step of depositing the organic light emitting material on a substrate or the like by using the metal pattern obtained by the method of forming a metal pattern according to the present disclosure as a metal mask for depositing the organic light emitting material.

Examples of the organic light emitting material include red (R), green (G), and blue (B) organic light emitting materials.

Further, the method for manufacturing an organic light emitting diode according to the present disclosure or the method for manufacturing an organic EL display device according to the present disclosure may include each step in the above-described method for forming a metal pattern according to the present disclosure, A preferable aspect is also the same.

Further, the manufacturing method of the organic light emitting diode according to the present disclosure or the method of manufacturing the organic EL display device according to the present disclosure may include known steps other than those described above.

Example

Examples are given below to further specifically describe embodiments of the present invention. Materials, amount of use, ratio, processing content, processing procedure, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, "part" and "%" are based on mass unless there is particular notice.

<Measurement of Scattering Angle of Scattering Layer>

Using a goniophotometer GP-200 manufactured by Murakami Shikisai Kijutsu Genkyusho Co., Ltd., light was incident perpendicularly to the scattering layer, and the intensity of the transmitted light was measured in an angular range from plus 90° to minus 90° did. With respect to the intensity of 0°, the entire angular width at which the intensity was 1/2 was taken as the scattering angle.

<Preparation of negative photosensitive resin compositions 1 and 2>

After mixing so that it might become the composition of following Table 1, by adding methyl ethyl ketone, the negative photosensitive resin compositions 1 and 2 (it describes as compositions 1 and 2 in Table 1. Solid content concentration: 25 mass %) were prepared, respectively.

[Table 1]

Moreover, the detail of the compound of Table 1 is shown below.

BPE-500: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

BPE-200: 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

M-270: polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.

A-TMPT: trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

SR-454: ethoxylated (3) trimethylolpropane triacrylate, manufactured by Sartomer

SR-502: ethoxylated (9) trimethylolpropane triacrylate, manufactured by Sartomer

A-9300-CL1: ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

B-CIM: Photoradical generator (photopolymerization initiator), manufactured by Hampford, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer

SB-PI 701: sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Boeki Co., Ltd.

CBT-1: rust inhibitor, carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.

TDP-G: Polymerization inhibitor, phenothiazine, Kawaguchi Chemical Industry Co., Ltd. product

Irganox245: hindered phenolic polymerization inhibitor, manufactured by BASF

F-552: Fluorine-based surfactant, Megafac F552, manufactured by DIC Co., Ltd.

<Production of transfer material A>

On a temporary support, which is a polyethylene terephthalate film (16KS40: trade name, Toray Co., Ltd.) having a thickness of 16 μm, using a bar coater, the negative photosensitive resin composition 1 was prepared so that the thickness of the negative photosensitive resin layer after drying was 10 μm. After adjusting the application amount and applying the negative photosensitive resin composition 1, it was made to dry in an 80 degreeC oven and the negative photosensitive resin layer was formed. Next, polyethylene terephthalate (16KS40: trade name, Toray Industries, Ltd.) having a thickness of 16 μm was crimped onto the surface of the negative photosensitive resin layer as a cover film to prepare transfer material A.

<Production of transfer material B>

On a temporary support, which is a polyethylene terephthalate film (16KS40: trade name, Toray Co., Ltd.) with a thickness of 16 μm, the following water-soluble resin composition was applied using a bar coater so that the thickness after drying was 1 μm, and it was heated in an oven at 90 ° C. It was made to dry, and the water-soluble resin layer was formed as an intermediate|middle layer. Then, on the water-soluble resin layer, using a bar coater, the coating amount of the negative photosensitive resin composition 2 was adjusted so that the thickness of the negative photosensitive resin layer after drying was 10 μm, and the negative photosensitive resin composition 2 was applied. Then, it was made to dry in an 80 degreeC oven, and the negative photosensitive resin layer was formed. Next, as a cover film, polyethylene terephthalate (16KS40: trade name, Toray Industries, Ltd.) having a thickness of 16 μm was crimped onto the surface of the negative photosensitive resin layer to prepare transfer material B.

-Composition of water-soluble resin composition-

・Number of exchanged ions: 38.12 parts

・Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts

・Kuraray Poval PVA-205 (polyvinyl alcohol, Kuraray Co., Ltd.): 3.22 parts

・Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts

Megafac F-444 (fluorine-based nonionic surfactant, manufactured by DIC Co., Ltd.): 0.0015 part

<Preparation of transfer material C>

Transfer material C was produced in the same manner as in production of transfer material A except that the thickness of the negative photosensitive resin layer after drying was 8 µm.

<Production of transfer material D>

Transfer material D was produced in the same manner as in production of transfer material A except that the thickness of the negative photosensitive resin layer after drying was 20 µm.

(Example 1)

<Formation of Laminate>

The cover film of the transfer material A prepared above is peeled off, and the surface of the exposed negative photosensitive resin layer is plated with Ni (thickness: 100 nm) on glass. Lamination was performed under the conditions to obtain a laminate (preparation step).

-Laminating conditions-

Temperature of substrate: 80°C

Temperature of rubber roller: 110℃

Line pressure: 3N/cm

Conveying speed: 2m/min

<Formation of resin pattern>

Next, an exposure mask (line/space = 20 µm/20 µm, line length 100 µm) was adhered to the surface of the temporary support body of the obtained laminate.

Then, on the exposure mask, as a scattering layer, a lens diffusion plate (registered trademark) LSD60ACUVT30 (scattering angle: 60°, diffuse transmittance: 95%, material: ultraviolet ray-transmitting acrylic resin) manufactured by Optical Solutions Co., Ltd. was disposed. The exposure mask and the scattering layer were placed without contacting each other. In Table 2, the scattering layer used in Example 1 was described as "a resin layer having irregularities".

Light was irradiated through the temporary support using a high-pressure mercury lamp exposure machine (manufactured by Dainippon Kakensho Co., Ltd. MAP-1200L, dominant wavelength: 365 nm), and the negative photosensitive resin layer was pattern-exposed at 150 mJ/cm ² (pattern exposure process). After the temporary support was peeled off, a resin pattern having a tapered shape was formed by shower development for 50 seconds using an aqueous solution of sodium carbonate having a liquid temperature of 25°C (resin pattern forming step).

<Observation of cross-sectional shape of resin pattern (taper shape evaluation)>

The cross-sectional shape of the obtained resin pattern was observed with an electron microscope (SEM) at 10 arbitrary locations on the substrate surface, and as shown in FIG. 5, the width W1 of the pattern top and half of the layer thickness of the pattern The width (W2), the width (W3) of the green part of the pattern, and the layer thickness (W4) were measured, and the value of tan(W4/((W3-W1)/2)) was calculated using the respective average values. Evaluation criteria are shown below.

A: W3>W2>W1 is satisfied, and the value is less than 5.67.

B: W3>W2>W1 is satisfied, and the value is 5.67 or more.

C: Does not satisfy W3>W2>W1.

<Formation of metal pattern>

Electrolytic plating using the conductive substrate as an electrode was performed as follows, and an electrodeposited material (metal pattern) having a thickness of about 7 μm was deposited in a region on the conductive substrate where the resin pattern was not formed.

A plating solution was placed in a plating bath heated to 50°C, a conductive base material prepared as a cathode was placed, and a nickel plate was placed as an anode, respectively, and a power supply was connected. Next, a power source was operated and an electric current was passed between the conductive substrate and the nickel plate for about 60 minutes, respectively. A nickel plating layer (metal pattern) was formed in a region on the surface of the conductive substrate where no resin pattern was formed (metal pattern forming step).

<Removal of resin pattern>

Subsequently, the resin pattern was removed by immersing in a 5% by mass aqueous solution of triethylamine (boiling point: 89°C) adjusted to 40°C for 60 seconds to form a tapered metal pattern on the substrate.

<Separation of base material>

The conductive substrate on which the metal pattern was formed in the above was peeled off by being stretched in a folded state at 180 degrees at 50 mm/s, thereby obtaining a metal mask having a metal pattern.

<Observation of cross-sectional shape (taper shape evaluation)>

The cross-sectional shape of the obtained metal pattern was observed with an electron microscope (SEM) at 10 arbitrary locations on the substrate surface, and as shown in FIG. The width (W6), the width (W7) of the green part of the pattern, and the layer thickness (W8) were measured, and the value of tan(W8/((W5-W7)/2)) was calculated using the respective average values. Evaluation criteria are shown below.

A: W5>W6>W7 is satisfied, and the value is less than 5.67.

B: W5>W6>W7 is satisfied, and the value is 5.67 or more.

C: Does not satisfy W5>W6>W7.

<Exposure margin>

The cross-sectional shape of the resin pattern obtained in the same manner as in the formation of the resin pattern was observed in the same manner as above, except that the exposure was changed by varying the exposure amount by ±5%, and as shown in FIG. 5, the width W1 of the pattern top and , the width (W2) of half of the film thickness of the pattern, the width (W3) of the green part of the pattern, and the film thickness (W4) are measured, and tan(W4/((W3-W1)/ 2)) was calculated.

In the above case, evaluation was performed in the same way as the observation of the cross-sectional shape of the resin pattern (taper shape evaluation).

A: The resin pattern produced by exposure at an exposure amount varied by ±5% satisfies W3 > W2 > W1, and the value is less than 5.67.

B: The resin pattern produced by exposure at an exposure amount varied by ±5% satisfies W3 > W2 > W1, and the value is 5.67 or more.

C: The resin pattern produced by exposure with the exposure amount changed by ±5% does not satisfy W3>W2>W1.

(Examples 2 to 9, and Comparative Examples 1 and 2)

As described in Table 2, resin patterns and metal patterns were formed in the same manner as in Example 1 except for changing the exposure method and transfer material, and evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.

More specifically, it is as follows.

In Example 2, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that the scattering layer used in Example 1 was changed to another scattering layer containing a specific resin.

In the specific resin-containing layer in Example 2, silica particles having an average primary particle size of 1.5 μm (Nippon Shokubai Co., Ltd. Seahorse KE- P150, refractive index of 1.43) is a layer having a thickness of 30 μm and containing 15% by mass as a solid content with respect to the total amount of the specific resin-containing layer. In the scattering layer of Example 2, the difference in refractive index between the matrix material and the specific particles was 0.07, and the difference in refractive index was 0.05 or more. In addition, the scattering angle of the scattering layer of Example 2 was 30°, and the diffuse transmittance was 90%.

In Example 2, a scattering layer was formed by spin coating a specific resin-containing layer on the surface opposite to the surface of the exposure mask on which the chromium pattern (shading pattern) was formed.

In Example 3, a resin pattern and a metal pattern were formed in the same manner as in Example 1 except that the temporary support was peeled off and the exposure mask was brought into contact with the negative photosensitive resin layer for pattern exposure.

In Example 4, a resin pattern and a metal pattern were formed in the same manner as in Example 3, except that transfer material B was used.

In Example 5, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that transfer material C was used.

In Example 6, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that the transfer material D was used.

In Example 7, it is the same as in Example 1 except that light-up LDS (manufactured by Kimoto Co., Ltd., scattering angle: 30°, light-diffusing polymer film, resin layer with concavo-convex, thickness 115 μm) was used as the scattering layer. Thus, a resin pattern and a metal pattern were formed.

In Example 8, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that an exposure mask (line/space = 5 μm/20 μm, line length 100 μm) was used.

In Example 9, as an exposure mask, square space portions (openings) SP having a side of 3 μm shown in FIG. 7 are arranged in a two-dimensional arrangement at intervals of 25 μm vertically and horizontally (in addition, in FIG. 7, a 3 × 3 space portion only is schematically shown), and a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that a mask having a light-shielding portion was used in a portion other than the space portion.

In Comparative Example 1, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that the scattering layer was not provided.

In Comparative Example 2, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that transfer material B was used and no scattering layer was provided.

[Table 2]

As shown in Table 2, the metal pattern formation method of Examples 1 to 9 is superior to the metal pattern formation method of Comparative Example 1 or 2 in the tapered shape of the obtained metal pattern.

12: Substrate
16: negative photosensitive resin layer
16A: pattern-shaped cured layer (resin pattern)
24: branch support
26: exposure mask
26A: light blocking area of exposure mask
28: scattering layer
32: scattering exposure mask
32A: shading area of scattering exposure mask
100: laminate
102: registration
104: resin pattern
104a: negative photosensitive resin layer
106: metal pattern
θ1: taper angle of resin pattern
θ2: taper angle of metal pattern
W1: the width of the top of the resin pattern
W2: Width of a portion of half of the layer thickness of the resin pattern
W3: width of resin pattern green
W4: layer thickness of resin pattern
W5: width of metal pattern government
W6: Width of a portion of half of the layer thickness of the metal pattern
W7: width of metal pattern rust
W8: layer thickness of metal pattern
SP: space part
As for the indication of Japanese Patent Application No. 2020-130530 for which it applied on July 31, 2020, the whole is used in this specification by reference. All documents, patent applications, and technical specifications described in this specification are incorporated by reference in this specification to the same extent as when each individual document, patent application, and technical specification is specifically incorporated by reference and is individually described. do.

Claims (21)

A step of preparing a laminate having a negative photosensitive resin layer on a substrate;
The negative photosensitive resin layer is irradiated with light having a component incident obliquely with respect to the thickness direction of the exposure mask from the side opposite to the side on which the substrate is provided in the negative photosensitive resin layer, and passes through the exposure mask. a process of pattern exposure;
A step of forming a resin pattern having a tapered shape by developing the pattern-exposed negative photosensitive resin layer; and
A method of forming a metal pattern comprising a step of forming a tapered metal pattern corresponding to the shape of the resin pattern. The method of claim 1,
In the step of pattern exposure, a scattering layer having a diffuse transmittance of 5% or more and an exposure light source are arranged in this order on a side of the exposure mask opposite to the negative photosensitive resin layer side, and the exposure light source emits light from the scattering layer. A method of forming a metal pattern by irradiating scattered light through a layer. The method of claim 2,
The method of forming a metal pattern according to claim 1 , wherein the scattering layer contains a matrix material and particles present in the matrix material, and a difference in refractive index between the matrix material and the particles is 0.05 or more. According to claim 2 or claim 3,
The method of forming a metal pattern according to claim 1 , wherein the scattering layer contains a matrix material and particles present in the matrix material, and the particles have an average primary particle diameter of 0.3 µm or more. The method according to any one of claims 2 to 4,
A method of forming a metal pattern in which the scattering layer has irregularities on at least one surface. The method of claim 5,
The method of forming a metal pattern in which the unevenness has a plurality of convex portions, and the distance between adjacent convex portions and the top of the convex portion is 10 μm to 50 μm. The method according to any one of claims 2 to 6,
The method of forming a metal pattern in which the scattering layer and the exposure mask are disposed at a position where they do not contact each other. The method according to any one of claims 2 to 7,
The method of forming a metal pattern according to claim 1 , wherein the scattering layer is in contact with the exposure mask and disposed on a side opposite to the negative photosensitive resin layer side in the exposure mask. The method according to any one of claims 2 to 6,
The method of forming a metal pattern according to claim 1 , wherein the exposure mask is a scattering exposure mask in which the scattering layer is formed on a surface opposite to the surface on which the light-shielding pattern is formed. The method according to any one of claims 1 to 9,
In the preparing step, using a transfer material having a temporary support and a negative photosensitive resin layer disposed on the temporary support, the negative photosensitive resin layer of the transfer material is transferred onto the substrate to form the layered product. A method of forming a metal pattern comprising forming a. The method of claim 10,
The method for forming a metal pattern according to claim 1 , wherein the pattern exposure in the pattern exposure step is contact exposure in which the temporary support is brought into contact with the exposure mask and exposed. The method of claim 10,
The pattern exposure in the pattern exposure step is contact exposure in which the exposure mask is brought into contact with the laminated body having the negative photosensitive resin layer to expose after the temporary support is peeled off, a method for forming a metal pattern. . According to any one of claims 1 or 12,
A method of forming a metal pattern in which the substrate is a conductive substrate. The method according to any one of claims 1 to 13,
A method of forming a metal pattern, wherein the metal pattern is a metal pattern formed by a plating method. According to any one of claims 1 to 14,
The method of forming a metal pattern further comprising a step of removing the resin pattern after the step of forming the metal pattern. The method of claim 15
A method of forming a metal pattern in which the removal of the resin pattern is performed with a chemical solution. The method according to any one of claims 1 to 16,
The method of forming a metal pattern further comprising a step of removing the substrate from the metal pattern. The method according to any one of claims 1 to 17,
The method of forming a metal pattern in which the resin pattern includes a resin pattern of a pyramid shape or a cone shape. The method according to any one of claims 1 to 18,
The method of forming a metal pattern in which the thickness of the negative photosensitive resin layer is 10 μm or more. According to any one of claims 1 to 19,
A method of forming a metal pattern in which the obtained metal pattern is a metal pattern for a metal mask for vapor deposition. A method for manufacturing a metal mask for deposition, comprising forming a metal pattern by the method of forming a metal pattern according to any one of claims 1 to 20.

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