CN114930250A

CN114930250A - Method for manufacturing resin pattern, method for manufacturing circuit wiring, method for manufacturing touch panel, and photosensitive transfer member

Info

Publication number: CN114930250A
Application number: CN202180007980.6A
Authority: CN
Inventors: 石坂壮二
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-02-05
Filing date: 2021-02-01
Publication date: 2022-08-19
Also published as: WO2021157525A1; JPWO2021157525A1

Abstract

The invention provides a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, a method for manufacturing a touch panel, and a photosensitive transfer member, the method for manufacturing a resin pattern uses a photosensitive transfer member having a temporary support and a photosensitive resin layer to form a resin pattern on a substrate, wherein the pattern width of the resin pattern in a portion in contact with the substrate is larger than the pattern width at a position 90% of the maximum height of the resin pattern by 0.2 μm or more, the photosensitive transfer member comprises a temporary support and a photosensitive resin layer, wherein, in the case of forming the resin pattern A having a pattern width of 6 μm at a position of 90% of the maximum height on the substrate, the pattern width of the resin pattern A at the part contacting with the substrate is more than 6.2 μm in the cross section of the resin pattern A in the width direction.

Description

Method for manufacturing resin pattern, method for manufacturing circuit wiring, method for manufacturing touch panel, and photosensitive transfer member

Technical Field

The present invention relates to a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, a method for manufacturing a touch panel, and a photosensitive transfer member.

Background

In a display device including a touch panel such as a capacitive input device (an organic Electroluminescence (EL) display device, a liquid crystal display device, or the like), a conductive layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition unit, a peripheral wiring portion, and a wiring for drawing out the wiring portion is provided inside the touch panel.

In general, since the number of steps for obtaining a desired pattern shape is small when a patterned layer is formed, a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer member through a mask having a desired pattern and then developing the layer is widely used.

Further, as conventional photosensitive resin compositions, photosensitive resin compositions described in japanese patent application laid-open nos. 2014-209173 and 2011-209426 are known.

Japanese patent application laid-open No. 2014-209173 discloses a photosensitive resin composition characterized by containing (A) an acid-modified photosensitive epoxy resin and (B) a non-photosensitive carboxylic acid resin having a styrene skeleton and a weight average molecular weight of 10000 to 50000.

Jp 2011-209426 a describes a photosensitive resin composition containing an alkali-soluble resin, a compound having a quinone diazide structure, and a nitrogen-containing heterocyclic compound having at least one structure selected from a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, an indole structure, a quinoline structure, and an isoquinoline structure.

Disclosure of Invention

Technical problem to be solved by the invention

An object of one embodiment of the present invention is to provide a method for producing a resin pattern having excellent resolution.

Another object of another embodiment of the present invention is to provide a method for manufacturing a circuit wiring having excellent resolution and a method for manufacturing a touch panel.

Further, another object of the present invention is to provide a photosensitive transfer member having excellent resolution.

Means for solving the technical problem

The means for solving the above problems include the following means.

< 1 > a method for producing a resin pattern, which comprises forming a resin pattern on a substrate using a photosensitive transfer member comprising a temporary support and a photosensitive resin layer, wherein the pattern width of a portion of the resin pattern in contact with the substrate is larger than the pattern width of the resin pattern at a position 90% of the maximum height of the substrate by 0.2 [ mu ] m or more.

< 2 > the method for producing a resin pattern according to < 1 >, wherein the thickness of the photosensitive resin layer is 8 μm or less.

< 3 > the method for producing a resin pattern according to < 1 > or < 2 >, wherein the thickness of the temporary support is 25 μm or less.

< 4 > the method for manufacturing a resin pattern according to any one of < 1 > to < 3 >, wherein a value obtained by subtracting a pattern width at a position 90% of a maximum height of the resin pattern from a pattern width of a portion of the resin pattern in contact with the substrate is 0.2 μm or more and 2.4 μm or less.

< 5 > the method for producing a resin pattern according to any one of < 1 > to < 4 >, wherein the photosensitive resin layer contains a polymerizable compound and a binder polymer.

< 6 > the method for producing a resin pattern < 5 > wherein the ratio Mm/Mb of the content Mm of the polymerizable compound to the content Mb of the binder polymer in the photosensitive resin layer is 0.9 or less.

< 7 > the method for producing a resin pattern according to < 5 > or < 6 >, wherein the polymerizable compound in the photosensitive resin layer contains a (meth) acrylic compound, and the content of the acrylic compound is 60% by mass or less based on the total mass of the (meth) acrylic compound contained in the photosensitive resin layer.

< 8 > the method of manufacturing a resin pattern according to any one of < 1 > to < 7 >, wherein the resin pattern to be manufactured includes a resin pattern having a pattern width of 6 μm or less.

< 9 > a method for manufacturing a circuit wiring, comprising the steps of: in the laminate having the resin pattern on the substrate manufactured by the method for manufacturing a resin pattern according to any one of < 1 > to < 8 >, the substrate has a conductive layer on a surface on a side where the resin pattern is formed, and the conductive layer located in a region where the resin pattern is not arranged is etched to form a circuit wiring.

< 10 > a method for manufacturing a touch panel, comprising a step of forming wiring for a touch panel by etching the conductive layer located in a region where the resin pattern is not arranged, in a laminate having the resin pattern on the substrate manufactured by the method for manufacturing a resin pattern according to any one of < 1 > to < 8 >, wherein the substrate has a conductive layer on a surface on a side where the resin pattern is formed.

< 11 > a photosensitive transfer member comprising a temporary support and a photosensitive resin layer, wherein when a resin pattern A having a pattern width of 6 μm at a position 90% from the maximum height of a substrate is formed on the substrate by the photosensitive transfer member, the pattern width of the resin pattern A at a portion contacting the substrate in a cross section in the width direction of the resin pattern A is 6.2 μm or more.

Effects of the invention

According to an embodiment of the present invention, a method for manufacturing a resin pattern with excellent resolution can be provided.

Further, according to another embodiment of the present invention, a method for manufacturing a circuit wiring having excellent resolution and a method for manufacturing a touch panel can be provided.

Further, according to another embodiment of the present invention, a photosensitive transfer member having excellent resolution can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view in the width direction of a resin pattern formed in the method for manufacturing a resin pattern according to the present invention.

Fig. 2 is a schematic view showing an example of the layer structure of the photosensitive transfer member used in the present invention.

Fig. 3 is a schematic view showing pattern a.

Fig. 4 is a schematic view showing pattern B.

Detailed Description

The present invention will be described below. Note that, although the description will be made with reference to the drawings, reference numerals may be omitted.

In the present specification, the numerical range expressed by the term "to" means a range including the numerical values before and after the term "to" as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acrylate" represents both or either of acrylate and methacrylate.

In the present specification, when a plurality of substances corresponding to respective components are present in a composition, the amount of each component in the composition indicates the total amount of the corresponding plurality of substances present in the composition unless otherwise specified.

In the present specification, the term "step" includes not only an independent step but also a step that can achieve a desired purpose even when it is not clearly distinguished from other steps.

In the expression of a group (atomic group) in the present specification, the expression that substitution and non-substitution are not described includes both a group having no substituent and a group having a substituent. For example, "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, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. The light used for exposure is usually an active ray (active energy ray) such as a bright line spectrum of a mercury lamp, a far ultraviolet ray typified by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, or an electron beam.

In addition, the chemical structural formula in the present specification may be described as a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights calculated by using THF (tetrahydrofuran) as a solvent and a differential refractometer to detect in a Gel Permeation Chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by TOSOH CORPORATION), and using polystyrene as a standard substance.

[ method for producing resin Pattern ]

The method for producing a resin pattern according to the present invention is a method for producing a resin pattern in which a resin pattern is formed on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer, wherein, in a cross section of the resin pattern in a width direction, a pattern width of the resin pattern in a portion in contact with the substrate is larger than a pattern width of the resin pattern at a position 90% of a maximum height of the substrate by 0.2 μm or more.

In order to improve the fineness of the photosensitive resin composition, reduction of the film thickness is being studied.

In the case of a thin film resist, if a process such as development or etching is performed under the same conditions as in a conventional thick film resist, there is a possibility that a preferable form (undercut, peeling, uneven shape, or the like) cannot be obtained due to excessive development or etching.

In particular, if the etching is excessive, there are problems as follows: etching is performed deep into the lower portion of the resist (so-called side etching), or the resist layer itself is damaged to cause the loss of the wiring, and the like, and it is difficult to miniaturize the resin pattern.

On the other hand, in general, in order to make the etching linearity and the linear shape uniform, it is required that the resist has a rectangular shape, and further, it is designed to obtain good linearity by extending the etching time or the like.

However, when the resist is thinned as described above, it is difficult to perform the process for a long etching time.

The present inventors have found that the resolution is not sufficient in the conventional method for producing a resin pattern having a cross-sectional shape of a pattern.

As a result of intensive studies, the present inventors have found that a manufacturing method of a resin pattern by using the above-described structure may have excellent resolution.

The mechanism for the detailed presentation of the above effects is not clear, but it is presumed that: in the cross section of the resin pattern in the width direction, by making the pattern width of the resin pattern in the portion in contact with the substrate larger than the pattern width at a position 90% of the maximum height of the substrate by 0.2 μm or more, when etching using the resin pattern is performed, the width of the resin pattern in the portion in contact with the substrate is large, so that the progress of side etching can be slowed down, and even in an etching pattern having a small width, the occurrence of etching defects such as pattern thinning and disconnection can be suppressed, and the resolution (also simply referred to as "resolution") of the obtained etching pattern is excellent.

In general, in order to prevent etching failure, the resist is required to have a rectangular shape free from residue and curl.

On the other hand, in the method for manufacturing a resin pattern according to the present invention, the shape of the resist after development is intentionally designed to be a curled shape to reduce the etching rate and to prevent excessive etching.

That is, the method for producing a resin pattern according to the present invention is an invention having a technical idea opposite to the design of a conventional negative resist.

The method for producing a resin pattern according to the present invention is a method for producing a resin pattern in which a resin pattern is formed on a substrate using a photosensitive transfer member having a temporary support and a photosensitive resin layer.

A preferred embodiment of the photosensitive transfer member used in the present invention will be described below.

The photosensitive transfer member used in the method for producing a resin pattern according to the present invention is preferably a negative photosensitive transfer member.

The resin pattern produced by the method for producing a resin pattern according to the present invention can be preferably used as a resist.

In the method for manufacturing a resin pattern according to the present invention, in a cross section of the resin pattern in the width direction, a pattern width of the resin pattern in a portion in contact with the substrate is larger than a pattern width of the resin pattern at a position 90% of a maximum height of the substrate by 0.2 μm or more. If the thickness is 0.2 μm or more, the progress at the edge during etching can be slowed, and the resolution is excellent.

In the method for producing a resin pattern according to the present invention, in terms of resolution and linearity, in a cross section of the resin pattern in the width direction, a value obtained by subtracting the pattern width at a position 90% of the maximum height of the resin pattern from the pattern width of the resin pattern in a portion in contact with the substrate (a value of the pattern width at a position 90% of the maximum height of the resin pattern from the pattern width of the resin pattern in a portion in contact with the substrate) is preferably 0.2 μm or more and 3.0 μm or less, more preferably 0.2 μm or more and 2.4 μm or less, even more preferably 0.3 μm or more and 2.0 μm or less, and particularly preferably 0.4 μm or more and 2.0 μm or less.

In the method for measuring the pattern width at a position 90% of the maximum height of the resin pattern from the substrate and the pattern width of the resin pattern at a portion in contact with the substrate in the cross section of the resin pattern in the width direction of the resin pattern according to the present invention, the substrate having the resin pattern is cut along the width direction of the resin pattern, and the cut resin pattern and substrate are observed from the cut surface side with a scanning electron microscope to measure the respective pattern widths. In addition, the pattern width at a position 90% of the maximum height of the resin pattern and the pattern width of the resin pattern at a portion in contact with the substrate are averaged to 10 measured values.

In the present invention, the "cross section in the width direction of the resin pattern" refers to a cross section on a plane parallel to the width direction and the thickness direction of the substrate, and for example, refers to a cross section on a plane perpendicular to the line direction of the resin pattern which is a line and a space.

In the present invention, the "position of X% of the maximum height of the resin pattern in the cross section of the resin pattern in the width direction" means a position of X% of the height of the resin pattern from the maximum height of the resin pattern of the substrate in the cross section of the resin pattern in the width direction.

Further, in the present invention, the resin pattern is preferably higher in hardness than the uncured photosensitive resin layer.

The resin pattern 4 on the substrate 2 shown in fig. 1 has curled portions 4a at both sides of the resin pattern 4 in the vicinity of a portion in contact with the substrate 2. In fig. 1, the height of the resin pattern 4 from 90% of the maximum height of the substrate 2 is H90, the pattern width at the position of 90% of the maximum height of the resin pattern 4 is L1, and the pattern width of the resin pattern 4 at the portion in contact with the substrate 2 is L2.

In the method for producing a resin pattern according to the present invention, when a resin pattern a having a pattern width of 6 μm is formed on a substrate at a position 90% away from the maximum height of the substrate, the pattern width of the resin pattern a in a portion contacting the substrate in a cross section of the resin pattern a in the width direction is preferably 6.2 μm or more, more preferably 6.2 μm or more and 9.0 μm or less, further preferably 6.2 μm or more and 8.4 μm or less, particularly preferably 6.3 μm or more and 8.0 μm or less, and most preferably 6.4 μm or more and 8.0 μm or less, from the viewpoint of resolution and linearity.

In the method of manufacturing a resin pattern according to the present invention, all the resin patterns may not be resin patterns in which the pattern width of a portion in contact with the substrate in a cross section in the width direction of the resin pattern is larger by 0.2 μm or more than the pattern width at a position 90% of the maximum height of the substrate, and the ratio of the resin pattern in which the pattern width of the portion in contact with the substrate in a cross section in the width direction of the resin pattern in the resin pattern manufactured by the photosensitive transfer member is larger by 0.2 μm or more than the pattern width at a position 90% of the maximum height of the resin pattern in a cross section in the width direction of the resin pattern in the resin pattern manufactured by the photosensitive transfer member as viewed in a direction perpendicular to the surface direction of the substrate is preferably 50 area% or more, more preferably 80 area% or more, and particularly preferably 90 area% or more.

In the method for producing a resin pattern according to the present invention, in terms of resolution and linearity, in a cross section of the resin pattern in the width direction, a value of a pattern width at a position of 90% of the maximum height of the resin pattern to a pattern width at a position of 50% of the maximum height of the resin pattern is preferably-0.5 μm or more and 1.0 μm or less, more preferably-0.2 μm or more and 0.5 μm or less, still more preferably-0.2 μm or more and 0.2 μm or less, and particularly preferably-0.1 μm or more and 0.1 μm or less.

From the viewpoint of resolution and linearity, the resin pattern produced by the resin pattern production method according to the present invention is more preferably a resin pattern in which the pattern width is gradually increased from a position of 5% to 40% of the maximum height of the resin pattern toward the substrate in a cross section of the resin pattern in the width direction, more preferably a resin pattern in which the pattern width is gradually increased from a position of 10% to 30% of the maximum height of the resin pattern toward the substrate, and particularly preferably a resin pattern in which the pattern width is gradually increased from a position of 15% to 25% of the maximum height of the resin pattern toward the substrate.

In the method for producing a resin pattern according to the present invention, in terms of resolution and linearity, in a cross section of the resin pattern in the width direction, a value of a pattern width at a position 90% of the maximum height of the substrate of the resin pattern to a pattern width at a position 5% of the maximum height of the substrate of the resin pattern is preferably 0.1 μm or more and 2.5 μm or less, more preferably 0.1 μm or more and 2.0 μm or less, still more preferably 0.15 μm or more and 1.8 μm or less, and particularly preferably 0.2 μm or more and 1.5 μm or less.

From the viewpoint of further exhibiting the effects of the present invention, the resin pattern produced by the method for producing a resin pattern according to the present invention preferably includes a resin pattern having a pattern width of 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less, and particularly preferably 1 μm or more and 6 μm or less.

In addition, from the viewpoint of further exhibiting the effects of the present invention, the resin pattern produced by the method for producing a resin pattern according to the present invention preferably has a line-and-space pattern.

Further, from the viewpoint of further exhibiting the effects of the present invention, the resin pattern produced by the method for producing a resin pattern according to the present invention is preferably a resist pattern for wiring formation, more preferably a resist pattern for circuit wiring, and particularly preferably a resist pattern for circuit wiring including wiring having a width of 6 μm or less.

The maximum height of the resin pattern produced by the method for producing a resin pattern according to the present invention is also related to the thickness of the photosensitive resin layer described later, and is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less, from the viewpoint of further exhibiting the effects of the present invention.

The resin pattern produced by the method for producing a resin pattern according to the present invention preferably includes a resin pattern having a pattern width at a position 90% of the maximum height of the substrate of the resin pattern/the maximum height of the resin pattern within the following numerical range.

From the viewpoint of further exhibiting the effects of the present invention, the value of the pattern width at a position 90% of the maximum height of the substrate of the resin pattern/the maximum height of the resin pattern is preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.5 or more and 0.8 or less.

As the method for producing the resin pattern, a method including a step of bonding the photosensitive transfer member and the substrate (hereinafter, also referred to as "bonding step") so that the substrate (preferably, a substrate having conductivity) is in contact with the 2 nd surface of the photosensitive resin layer (i.e., the surface on the side not facing the temporary support), a step of pattern-exposing the photosensitive resin layer (hereinafter, also referred to as "exposure step"), and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, also referred to as "developing step") in this order is preferable.

< bonding Process >

The method for producing a resin pattern preferably includes a bonding step.

In the bonding step, the substrate (when a conductive layer is provided on the surface of the substrate, the conductive layer) is preferably brought into contact with the 2 nd surface of the photosensitive resin layer, thereby pressure-bonding the photosensitive transfer member and the substrate. In the above aspect, the adhesion between the 2 nd surface of the photosensitive resin layer and the substrate is improved, and therefore, the photosensitive resin layer can be preferably used as a resist in etching, exposure, and development of a conductive layer of a photosensitive resin layer having a pattern formed thereon.

In the case where the photosensitive transfer member includes the cover film, the cover film may be removed from the surface of the photosensitive resin layer and then bonded.

In the case where the photosensitive transfer member further includes a layer other than the cover film (for example, a high refractive index layer and/or a low refractive index layer) on the surface of the photosensitive resin layer on the side not facing the temporary support, the bonding step is a method of bonding the surface of the photosensitive resin layer on the side not having the temporary support and the substrate via the layer.

The method for pressure-bonding the substrate and the photosensitive transfer member is not particularly limited, and a known transfer method and lamination method can be used.

The photosensitive transfer member is preferably bonded to the substrate by laminating the substrate on the 2 nd surface side of the photosensitive resin layer and applying pressure and heat using a mechanism such as a roller. In the bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving productivity can be used.

The method for manufacturing the resin pattern and the method for manufacturing the circuit wiring including the bonding step are preferably performed by a roll-to-roll method.

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

The roll-to-roll method is as follows: the substrate that can be wound and unwound is used as the substrate, and includes a step of unwinding the substrate or the structure including the substrate before any one of the steps included in the resin pattern manufacturing method or the circuit wiring manufacturing method (also referred to as an "unwinding step"), and a step of winding the substrate or the structure including the substrate after any one of the steps (also referred to as a "winding step"), and at least any one of the steps is performed while conveying the substrate or the structure including the substrate (preferably, all of the steps or all of the steps other than the heating step).

The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method can be used for a manufacturing method to which the roll-to-roll method is applied.

< substrate >

As the substrate used in the method for producing a resin pattern according to the present invention, a known substrate can be used, but a substrate having a conductive layer is preferable, and a conductive layer is more preferable on the surface of the substrate.

The substrate may have any layer other than the conductive layer as necessary.

Examples of the substrate constituting the substrate include glass, silicon, and a thin film.

The base material constituting the substrate is preferably transparent. In the present specification, "transparent" means that the transmittance of light having a wavelength of 400nm to 700nm is 80% or more.

The refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

Examples of the transparent glass substrate include strengthened glass typified by gorilla glass produced by Corning Incorporated. Further, as the transparent glass substrate, materials used in japanese patent application laid-open nos. 2010-86684, 2010-152809 and 2010-257492 can be used.

When a film substrate is used as the substrate, a film substrate having low optical distortion and/or high transparency is preferably used. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

When the substrate is manufactured in a roll-to-roll manner, a film substrate is preferable as the substrate. When the circuit wiring for a touch panel is manufactured by a roll-to-roll method, the substrate is preferably a sheet-like resin composition.

Examples of the conductive layer included in the substrate include conductive layers used for general circuit wiring and touch panel wiring.

The conductive layer is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer, from the viewpoint of conductivity and thin line formability.

The substrate may have 1 conductive layer alone or 2 or more conductive layers. When the conductive layer has 2 or more layers, the conductive layers are preferably different in material.

Examples of the material of the conductive layer include a metal and a conductive metal oxide.

Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.

Examples of the conductive metal Oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO (silicon Oxide) ₂ 。

In the present specification, "conductive" means that the volume resistivity is less than 1 × 10 ⁶ Omega cm. The volume resistivity of the conductive metal oxide is preferably less than 1X 10 ⁴ Ωcm。

In the case of manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

The conductive layer is preferably an electrode pattern of a sensor corresponding to a viewing portion used in the capacitive touch panel or a wiring of a peripheral lead portion.

< Exposure Process >

The method for producing a resin pattern preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.

The detailed arrangement and specific dimensions of the pattern when performing pattern exposure are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wirings manufactured by a method for manufacturing circuit wirings and to reduce the area occupied by lead-out wirings, at least a part of the pattern (preferably, an electrode pattern of the touch panel and/or a part of the lead-out wirings) preferably includes a thin line having a width of 20 μm or less, and more preferably, includes a thin line having a width of 10 μm or less.

The light source used for exposure may be appropriately selected and used as long as it is a light source that irradiates light of a wavelength (for example, 365nm or 405nm) that can expose the photosensitive resin layer. Specific examples thereof include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

The exposure amount is preferably 5mJ/cm ² ～200mJ/cm ² More preferably 10mJ/cm ² ～100mJ/cm ² 。

In the exposure step, pattern exposure may be performed after the temporary support is peeled from the photosensitive resin layer, or the temporary support may be peeled after pattern exposure is performed via the temporary support. In order to prevent contamination of the photosensitive resin layer due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on exposure, it is preferable to perform pattern exposure through the temporary support. The pattern exposure may be exposure through a mask or may be direct exposure using an exposure system such as a laser.

< developing Process >

The method for producing a resin pattern preferably includes a step (developing step) of developing the exposed photosensitive resin layer to form a resin pattern after the exposure step.

In the case where the photosensitive transfer member includes the thermoplastic resin and the intermediate layer, the thermoplastic resin layer and the intermediate layer in the unexposed portion are also removed together with the photosensitive resin layer in the unexposed portion in the developing step. In the developing step, the thermoplastic resin layer and the intermediate layer in the exposed portion may be removed in the form of being dissolved or dispersed in a developing solution.

The development of the exposed photosensitive resin layer in the development step can be performed using a developer.

The developing solution is not particularly limited as long as it can remove the non-image portion (non-exposed portion) of the photosensitive resin layer, and a known developing solution such as the developing solution described in japanese patent application laid-open No. 5-72724 can be used.

The developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5mol/L (liter). The developer may also contain a water-soluble organic solvent and/or a surfactant. The developer described in section 0194 of international publication No. 2015/093271 is also preferable as the developer.

The development method is not particularly limited, and may be any of spin-on immersion development, shower and spin development, and immersion development. The shower development refers to a development treatment in which a developing solution is sprayed to the exposed photosensitive resin layer with a shower to remove unexposed portions.

After the developing step, it is preferable to remove the development residue while spraying a cleaning agent with a shower and wiping with a brush.

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

< Process for peeling off cover film >

When the photosensitive transfer member includes the cover film, the method for producing the resin pattern preferably includes a step of peeling the cover film from the photosensitive transfer member. The method for peeling the cover film is not limited, and a known method can be applied.

< other working procedures >

The method for manufacturing the resin pattern may include any step (other step) other than the above-described steps. Examples thereof include, but are not limited to, the following steps.

The photosensitive transfer member used in the present invention will be described in detail below.

< photosensitive transfer Member >

The photosensitive transfer member used in the present invention includes at least a temporary support and a photosensitive resin layer.

The photosensitive transfer member may be formed by directly laminating the temporary support and the photosensitive resin layer without using another layer, or by laminating the temporary support and the photosensitive resin layer with another layer. Further, another layer may be laminated on the surface of the photosensitive resin layer opposite to the surface facing the temporary support.

Examples of the other layers than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, and a cover film.

[ temporary support body ]

The photosensitive transfer member used in the present invention includes a temporary support.

The temporary support is a support which can be peeled off and supports a laminate including a photosensitive resin layer or a photosensitive resin layer.

The temporary support preferably has light-transmitting properties from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure. In the present specification, "having light transmittance" means that the transmittance of light of a wavelength used for pattern exposure is 50% or more.

From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of the temporary support to light of a wavelength used for pattern exposure (more preferably, a wavelength of 365nm) is preferably 60% or more, and more preferably 70% or more.

The transmittance of the layer provided in the photosensitive transfer member is a ratio of the intensity of the emitted light emitted through the layer when light is incident in a direction (thickness direction) perpendicular to the main surface of the layer to the intensity of the incident light, and is measured by MCPD Series manufactured by OTSUKA ELECTRONICS co.

Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and the resin film is preferable from the viewpoint of strength, flexibility, and light transmittance.

Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.

The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of the strength of the support, the flexibility required for bonding the temporary support to the circuit wiring forming substrate, and the light transmittance required in the first exposure step.

The thickness of the temporary support is preferably within a range from 5 μm to 100 μm, more preferably within a range from 10 μm to 50 μm, still more preferably within a range from 10 μm to 20 μm, and particularly preferably within a range from 10 μm to 16 μm, from the viewpoint of easy handling and versatility.

In addition, the thickness of the temporary support is preferably 50 μm or less, and more preferably 25 μm or less, from the viewpoint of resolution and linearity in exposure through the temporary support.

The film used as the temporary support is preferably free from deformation such as wrinkles, scratches, defects, and the like.

From the viewpoint of pattern formability in pattern exposure via the temporary support and transparency of the temporary support, the smaller the number of fine particles, foreign substances, defects, precipitates, and the like contained in the temporary support, the more preferable it is. The number of particles, foreign matters or defects having a diameter of 1 μm or more is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, more preferably 3/10 mm ² The average particle size is preferably 0/10 mm ² 。

Preferable examples of the temporary support include paragraphs 0017 to 0018 in Japanese patent laid-open publication No. 2014-85643, paragraphs 0019 to 0026 in Japanese patent laid-open publication No. 2016-27363, paragraphs 0041 to 0057 in International publication No. 2012/081680, paragraphs 0029 to 0040 in International publication No. 2018/179370, and paragraphs 0012 to 0032 in Japanese patent laid-open publication No. 2019-101405, the contents of which are incorporated herein.

[ photosensitive resin layer ]

The photosensitive transfer member used in the present invention includes a photosensitive resin layer.

The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of an exposed portion in a developer is reduced by exposure and an unexposed portion is removed by development. However, the photosensitive resin layer is not limited to the negative photosensitive resin layer, and may be a positive photosensitive resin layer in which the exposed portion is exposed to light to improve the solubility of the exposed portion in a developer and is removed by development.

The photosensitive resin layer preferably contains a polymerizable compound and a binder polymer, more preferably contains a polymerizable compound, a binder polymer, and a photopolymerization initiator, and particularly preferably contains a polymer a, a polymerizable compound, and a photopolymerization initiator. The photosensitive resin layer preferably contains 10 to 90 mass% of a binder polymer, 5 to 70 mass% of a polymerizable compound, and 0.01 to 20 mass% of a photopolymerization initiator, based on the total mass of the photosensitive resin layer.

Hereinafter, each component will be described in order.

[ adhesive Polymer ]

The photosensitive resin layer preferably contains a binder polymer.

The binder polymer is not particularly limited, and for example, a known binder polymer used for a resist is preferably used.

The binder polymer may be an alkali-soluble polymer.

As the alkali-soluble polymer, an alkali-soluble polymer having an acid group is preferable.

Among them, the binder polymer is preferably the polymer a described later.

Polymer A-

The binder polymer preferably contains a polymer a.

The polymer a is preferably an alkali-soluble polymer. The alkali-soluble polymer contains a polymer which is easily soluble in an alkali substance.

The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably 200mgKOH/g, and even more preferably 190mgKOH/g, from the viewpoint of suppressing swelling of the photosensitive resin layer by the developer to further improve the resolution.

The lower limit of the acid value of the polymer a is not particularly limited, but from the viewpoint of further improving the developability, it is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, and particularly preferably 170mgKOH/g or more.

The acid value is the mass [ mg ] of potassium hydroxide required to neutralize 1g of the sample, and the unit is referred to as mgKOH/g in the present specification. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The acid value of the polymer A can be adjusted depending on the kind of the constituent unit constituting the polymer A and the content of the constituent unit containing an acid group.

The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the development aggregates and the properties of the unexposed film such as the edge fusibility and the cutting property in the production of the photosensitive resin laminate, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge-fusion property is a degree to which the photosensitive resin layer is likely to protrude from an end face of a roll when the photosensitive transfer member is wound in a roll. The swarf property is a degree at which swarf is easily scattered when an unexposed film is cut by a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, they are transferred to a mask in a subsequent exposure step or the like, which causes defective products. The degree of dispersion of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, even more preferably 1.0 to 3.0. In the present invention, the molecular weight is a value determined using gel permeation chromatography. And, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing the coarsening of the line width and the deterioration of the resolution at the time of the shift of the focal position at the time of exposure, the photosensitive resin layer preferably contains a polymer of a monomer component having an aromatic hydrocarbon group as the polymer a. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content ratio of the monomer component having an aromatic hydrocarbon group in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more, based on the total mass of all the monomer components. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. The content ratio of the monomer component having an aromatic hydrocarbon group in the case of containing a plurality of polymers A is determined as a weight average value.

Examples of the monomer having the aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer a is styrene, the content ratio of the styrene monomer component is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, even more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of all the monomer components.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.

Examples of the monomer having a benzyl group include a (meth) acrylate having a benzyl group (for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate), and a vinyl monomer having a benzyl group (for example, vinylbenzyl chloride, vinylbenzyl alcohol, etc.). Among them, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer a is benzyl (meth) acrylate, the content ratio of the benzyl (meth) acrylate monomer component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, even more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of all the monomer components.

The polymer a containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group and at least one of the 1 st monomers described later and/or at least one of the 2 nd monomers described later.

The polymer a containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the 1 st monomers described later, and more preferably by copolymerizing at least one of the 1 st monomers and at least one of the 2 nd monomers described later.

The 1 st monomer is a monomer having a carboxyl group in the molecule. Examples of the 1 st monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among them, (meth) acrylic acid is preferable.

The content of the 1 st monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass, based on the total mass of all the monomer components.

In addition, in the present specification, "(meth) acrylic acid" represents acrylic acid or methacrylic acid, "(meth) acryloyl group" represents acryloyl group or methacryloyl group, and "(meth) acrylate" represents "acrylate" or "methacrylate".

The copolymerization ratio of the 1 st monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. From the viewpoint of exhibiting good developability, controlling edge-bleed property, and the like, the copolymerization ratio is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The copolymerization ratio is preferably 50% by mass or less from the viewpoint of the high resolution and the edge shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern, and from these viewpoints, is more preferably 35% by mass or less, still more preferably 30% by mass or less, and particularly preferably 27% by mass or less.

The 2 nd monomer is a monomer having a non-acidic property and having at least 1 polymerizable unsaturated group in the molecule. Examples of the 2 nd monomer include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile, and the like. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable.

The content of the 2 nd monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and still more preferably 20 to 45% by mass, based on the total mass of all the monomer components.

From the viewpoint of suppressing the coarsening of the line width and the deterioration of the resolution at the time of the shift of the focus position in the exposure, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, and the like are preferable.

In one aspect, the polymer a is preferably a polymer containing 25 to 40 mass% of a monomer component having an aromatic hydrocarbon group, 20 to 35 mass% of the 1 st monomer component, and 30 to 45 mass% of the 2 nd monomer component. In another embodiment, the polymer preferably contains 70 to 90 mass% of the monomer component having an aromatic hydrocarbon group and 10 to 25 mass% of the 1 st monomer component.

The polymer a may have any one of a linear structure, a branched structure and an alicyclic structure in a side chain. By using a monomer having a group having a branched structure in a side chain or a monomer having a group having an alicyclic structure in a side chain, a branched structure or an alicyclic structure can be introduced into a side chain of the polymer a. The group having an alicyclic structure may be monocyclic or polycyclic.

Specific examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, tert-octyl (meth) acrylate, and the like. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate and tert-butyl methacrylate are more preferable.

Specific examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Also disclosed is a (meth) acrylate containing an alicyclic hydrocarbon group having 5-20 carbon atoms. More specific examples thereof include (bicyclo [ 2.2.1] heptyl-2) acrylate, (meth) acrylic acid 1-adamantyl ester, (meth) acrylic acid 2-adamantyl ester, (meth) acrylic acid 3-methyl-1-adamantyl ester, (meth) acrylic acid 3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid 3-ethyl adamantyl ester, (meth) acrylic acid 3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid 3,5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid 3, 5-dimethyl-8-ethyl-1-adamantyl ester, and mixtures thereof, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-menthylindenyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 3-hydroxy-2, 6, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl (meth) acrylate, 3,7, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl (meth) acrylate, (meth) acrylate (norbornyl (meth) acrylate, Isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Among these (meth) acrylates, cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate, or tricyclodecyl (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, or tricyclodecyl (meth) acrylate is more preferable.

The polymer a may be used alone or in combination of two or more. When two or more kinds of polymers are used in combination, it is preferable to use two kinds of polymers a containing monomer components having aromatic hydrocarbon groups in combination or use a polymer a containing monomer components having aromatic hydrocarbon groups in combination with a polymer a not containing monomer components having aromatic hydrocarbon groups in combination. In the latter case, the proportion of the polymer a containing a monomer component having an aromatic hydrocarbon group to be used is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the polymer a.

The synthesis of polymer a is preferably carried out by: an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is added to a solution obtained by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropyl alcohol, and the mixture is heated and stirred. Sometimes, the synthesis is carried out while a part of the mixture is added dropwise to the reaction solution. After the reaction is completed, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The glass transition temperature Tg of the polymer A is preferably from 30 ℃ to 135 ℃. By using the polymer a having a Tg of 135 ℃ or less in the photosensitive resin layer, coarse line width and deterioration in resolution can be suppressed when the focus position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130 ℃ or lower, still more preferably 120 ℃ or lower, and particularly preferably 110 ℃ or lower. From the viewpoint of improving the edge fusion resistance, it is preferable to use the polymer a having a Tg of 30 ℃ or higher. From this viewpoint, the Tg of the polymer a is more preferably 40 ℃ or higher, still more preferably 50 ℃ or higher, particularly preferably 60 ℃ or higher, and most preferably 70 ℃ or higher.

The photosensitive resin layer may contain a resin other than the polymer a.

Examples of the resin other than the polymer a include acrylic resins, styrene-acrylic copolymers (in which the styrene content is 40% by mass or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

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

The proportion of the binder polymer to the total mass of the photosensitive resin layer is preferably within a range of 10 to 90 mass%, more preferably 30 to 70 mass%, and still more preferably 40 to 60 mass%. From the viewpoint of controlling the development time, the ratio of the binder polymer to the photosensitive resin layer is preferably 90% by mass or less. On the other hand, from the viewpoint of improving the edge fusion resistance, the ratio of the binder polymer to the photosensitive resin layer is preferably 10% by mass or more.

(polymerizable Compound)

The photosensitive resin layer preferably contains a polymerizable compound.

In the present specification, the "polymerizable compound" means a compound other than the above-mentioned binder polymer, which is polymerized by the action of a polymerization initiator described later.

As the polymerizable compound, an ethylenically unsaturated compound is preferable.

The ethylenically unsaturated compound is a component contributing to the photosensitivity (i.e., photocurability) of the negative photosensitive resin layer and the strength of the cured film.

And the ethylenically unsaturated compound is a compound having 1 or more ethylenically unsaturated groups.

The photosensitive resin layer preferably contains an ethylenically unsaturated compound having 2 or more functions as the ethylenically unsaturated compound.

Here, the ethylenically unsaturated compound having 2 or more functions means a compound having 2 or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group, (meth) acryloyl group is more preferable.

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

The photosensitive resin layer preferably contains a polymerizable compound having a polymerizable group.

The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and a group having a cationically polymerizable group such as an epoxy group and an oxetanyl group.

The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups (ethylenically unsaturated compound), and more preferably a compound having 2 or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound), from the viewpoint of further improving the photosensitivity of the photosensitive resin layer.

In addition, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less, from the viewpoint of further improving resolution and peelability.

From the viewpoint of making the balance between the photosensitivity, the resolution, and the releasability of the photosensitive resin layer more excellent, the photosensitive resin layer preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in one molecule, and more preferably contains a 2-functional ethylenically unsaturated compound having 2 ethylenically unsaturated groups in one molecule.

From the viewpoint of excellent peelability, the content of the 2-functional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60% by mass or more, more preferably more than 70% by mass, and even more preferably 90% by mass or more, relative to the content of the polymerizable compound. The upper limit is not particularly limited, and may be 100 mass%. That is, the polymerizable compounds contained in the photosensitive resin layer may all be 2-functional ethylenically unsaturated compounds.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group.

Polymerizable compound B1-

The photosensitive resin layer preferably contains a polymerizable compound B1 having an aromatic ring and 2 ethylenically unsaturated groups. The polymerizable compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in one molecule of the polymerizable compound.

In the photosensitive resin layer, the mass ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of further improving the resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.

Examples of the aromatic ring included in the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. The aromatic ring may have a substituent.

The polymerizable compound B1 may have only 1 aromatic ring, or may have 2 or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive resin layer by the developer.

Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and the bisphenol a structure is preferred.

Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.

The bisphenol structure may have 2 polymerizable groups bonded to both ends thereof directly or through 1 or more alkyleneoxy groups. As the alkyleneoxy group attached to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated herein by reference.

The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloyloxyalkyl) phenyl) propane.

Examples of the 2, 2-bis (4- ((meth) acryloyloxyalkylpolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (BPE-500, Shin-Nakamura Chemical Co., manufactured by Ltd.), 2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, Hitachi Chemical Co., manufactured by Ltd.), 2-bis (4- (methacryloyloxypentadecaethoxyphenyl) propane (BPE-1300, 2-bis (4- (methacryloyloxypentadecaethoxyphenyl) propane, 2-bis (4- (methacryloyloxypentadecaethoxyphenyl) propane (BPE-1300, 2-bis (4-methacryloyloxydiethoxy) phenyl) propane, and the like, Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.), 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (BPE-200, Shin-Nakamura Chemical Co., manufactured by Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK ESTETR A-BPE-10, Shin-Nakamura Chemical Co., manufactured by Ltd.).

As the polymerizable compound B1, a compound represented by the following general formula (I) can be used.

[ chemical formula 1]

{ formula (II) wherein R ₁ And R ₂ Each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ B is C ₃ H ₆ ，n ₁ And n ₃ Each independently is an integer of 1 to 39, and n ₁ +n ₃ N2 and n4 are each independently an integer of 0 to 29, and n2+ n ₄ The repeating units of- (A-O) -and- (B-O) -may be arranged randomly or in blocks, and each may be an integer of 0 to 30. In the case of a block, either one of- (A-O) -and- (B-O) -may be on the biphenyl group side. }

In a mode, n ₁ +n ₂ +n ₃ +n ₄ Preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. And, n ₂ +n ₄ Preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.

The polymerizable compound B1 may be used alone or in combination of two or more.

From the viewpoint of further improving the resolution, the content of the polymerizable compound B1 in the photosensitive resin layer is preferably 10 mass% or more, and more preferably 20 mass% or more, with respect to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 70% by mass or less, and more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin bleeds out from the end of the transfer member).

The photosensitive resin layer may contain a polymerizable compound other than the polymerizable compound B1.

The polymerizable compound other than the polymerizable compound B1 is not particularly limited, and can be appropriately selected from known compounds. Examples thereof include a compound having 1 ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., manufactured by Ltd.), ethylene glycol dimethacrylate, 1, 10-decanediol diacrylate and neopentyl glycol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di (meth) acrylate.

Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (TAISEI FINE CHEMICAL CO, manufactured by LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., manufactured by Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., manufactured by Ltd.).

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide-modified products thereof.

Here, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate. In one aspect, the photosensitive resin layer preferably contains the polymerizable compound B1 and an ethylenically unsaturated compound having 3 or more functional groups, and more preferably contains the polymerizable compound B1 and two or more ethylenically unsaturated compounds having 3 or more functional groups. In this case, the mass ratio of the polymerizable compound B1 to the 3-or more-functional ethylenically unsaturated compound is preferably (total mass of the polymerizable compound B1): (total mass of the 3-or more-functional ethylenically unsaturated compound) 1:1 to 5:1, more preferably 1.2:1 to 4:1, and still more preferably 1.5:1 to 3: 1.

In one embodiment, the photosensitive resin layer preferably contains the polymerizable compound B1 and two or more 3-functional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functional groups include caprolactone-modified (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., Kayarad (registered trademark) DPCA-20 manufactured by Ltd., Shin-Nakamura Chemical Co., Ltd., A-9300-1CL manufactured by Ltd.), alkylene oxide-modified (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd. KAYARAD RP-1040 manufactured by Ltd., Shin-Nakamura Chemical Co., Ltd., ATM-35E and A-9300 manufactured by Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD.), and ethoxyglycerol triacrylate (e.g., Shin-Nakamura Chemical Co., Ltd., A-GLY-9E manufactured by Ltd.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), ARONIX M-520 (manufactured by TOAGOSEI co., ltd.), and ARONIX M-510 (manufactured by TOAGOSEI co., ltd.).

As the polymerizable compound other than the polymerizable compound B1, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese patent application laid-open No. 2004-239942 can be used.

From the viewpoint of resolution and linearity, the value of the ratio Mm/Mb of the content Mm of the polymerizable compound to the content Mb of the binder polymer in the photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.

From the viewpoint of curability and resolution, the polymerizable compound in the photosensitive resin layer preferably contains a (meth) acrylic compound.

Further, from the viewpoint of curability, resolution, and linearity, the polymerizable compound in the photosensitive resin layer more preferably contains a (meth) acrylic compound, and the content of the acrylic compound with respect to the total mass of the (meth) acrylic compound contained in the photosensitive resin layer is 60 mass% or less. The lower limit of the content of the acrylic compound is not particularly limited, and is, for example, 0.1 mass%.

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

The content of the polymerizable compound in the photosensitive resin layer is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, and still more preferably 20 to 50 mass% with respect to the total mass of the photosensitive resin layer.

The weight average molecular weight (Mw) of the polymerizable compound containing the polymerizable compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.

[ other ingredients ]

The photosensitive resin layer may contain components other than the binder polymer and the polymerizable compound.

Photopolymerization initiators

The photosensitive resin layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that initiates polymerization of the polymerizable compound upon receiving an active light such as ultraviolet light, visible light, and X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

Examples of the photo radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylphenone structure, a photopolymerization initiator having an α -hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

In addition, from the viewpoint of the photosensitivity, the visibility of exposed portions and unexposed portions, and the resolution, the photosensitive resin layer preferably contains at least one selected from 2,4, 5-triarylimidazole dimers and derivatives thereof as a photo radical polymerization initiator. In addition, the two 2,4, 5-triarylimidazole dimers and the derivatives thereof, in which the structures of the two 2,4, 5-triarylimidazole may be the same or different, may be used.

Examples of the derivatives of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

As the photo radical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-95716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-14783 can be used.

Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CASNO.10287-53-3), benzoin methyl ether, anisyl (p, p ' -dimethoxybenzyl), TAZ-110 (trade name: Midori Kagaku Co., manufactured by Ltd.), benzophenone, TAZ-111 (trade name: Midori Kagaku Co., manufactured by Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF Co., Ltd.), Omnirad651 and 369 (trade name: IGM Resins B.V., manufactured by Ltd.), and 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole (Tokyo, Co., Ltd.).

Examples of commercially available products of the photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trade name) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (trade name: Omnirad 379EG, Manufactured by IGM Resins b.v.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: omnirad 907, manufactured by IGM Resins b.v.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (trade name: omnirad 127, manufactured by IGM Resins b.v.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: omnirad 369, manufactured by IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173, IGM Resins b.v.), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184, manufactured by IGM Resins b.v.), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad651, manufactured by IGM Resins b.v.), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad TPO H, by IGM Resins b.v.), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819 manufactured by IGM Resins b.v.), an oxime ester photopolymerization initiator (trade name: lunar6, manufactured by DKSH Management ltd.), 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM manufactured by Hampford corporation) and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry co., ltd).

Further, 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) can be used (trade name: B-IMD, KUROGANE KASEICo., manufactured by Ltd.).

In the present specification, 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbisimidazol (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer is described as B-CIM or B-IMD.

The photo cation polymerization initiator (photoacid generator) is a compound that receives activating light to generate an acid. The photo cation polymerization initiator is preferably a compound which generates an acid by being sensitive to an activating light having a wavelength of 300nm or more, preferably 300 to 450nm, but the chemical structure thereof is not limited. The photo cation polymerization initiator that is not directly sensitive to the activation light having a wavelength of 300nm or more may be used in combination with a sensitizer as long as it is a compound that generates an acid by being sensitive to the activation light having a wavelength of 300nm or more.

As the photo cation polymerization initiator, a photo cation polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photo cation polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photo cation polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of pKa is not particularly limited, but is preferably at least-10.0, for example.

Examples of the photo cation polymerization initiator include ionic photo cation polymerization initiators and nonionic photo cation polymerization initiators.

Examples of the ionic photo-cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

As the ionic photo-cationic polymerization initiator, the ionic photo-cationic polymerization initiators described in paragraphs 0114 to 0133 of Japanese patent application laid-open No. 2014-85643 can be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl s-triazine, diazomethane compound and imide sulfonate compound, the compounds described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494 can be used. Further, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be used.

The photosensitive resin layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from 2,4, 5-triarylimidazole dimer and derivatives thereof.

The photosensitive resin layer may contain one kind of photopolymerization initiator alone, or may contain two or more kinds of photopolymerization initiators.

The content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less, with respect to the total mass of the photosensitive resin layer.

-pigments-

From the viewpoint of visibility of exposed portions and non-exposed portions, pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye (also simply referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical. Although the detailed mechanism is not clear, when the pigment N is contained, the adhesion between the pigment N and the adjacent layers (for example, the temporary support and the intermediate layer) is improved, and the resolution is further improved.

In the present specification, the "change in the maximum absorption wavelength of a dye by an acid, an alkali, or a radical" may mean any of a method in which a dye in a colored state is decolorized by an acid, an alkali, or a radical, a method in which a dye in a decolorized state is colored by an acid, an alkali, or a radical, and a method in which a dye in a colored state is changed to a colored state of another color.

Specifically, the dye N may be a compound that develops color by changing from a decolored state by exposure to light, or may be a compound that develops color by changing from a colored state by exposure to light. In this case, the dye may be one that generates an acid, a base, or a radical in the photosensitive resin layer by exposure and acts to change the state of coloration or decoloration, or may be one that changes the state (for example, pH) in the photosensitive resin layer by a change in the acid, the base, or the radical. Further, the dye may be one which changes in color development or decoloration by being directly stimulated by an acid, an alkali, or a radical without exposure.

Among them, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.

From the viewpoint of visibility and resolution of the exposed portion and the unexposed portion, the photosensitive resin layer preferably contains both a dye (as dye N) whose maximum absorption wavelength changes by a radical and a photo radical polymerization initiator.

The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, from the viewpoint of visibility of the exposed portion and the unexposed portion.

Examples of the color developing mechanism of the dye N in the present invention include the following: a method in which a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator), or a photo base generator is added to a photosensitive resin layer, and a radical reactive dye, an acid reactive dye, or a base reactive dye (for example, leuco dye) is developed by a radical, an acid, or a base generated from the photo radical polymerization initiator, the photo cation polymerization initiator, or the photo base generator after exposure.

From the viewpoint of visibility of the exposed portion and the unexposed portion, the dye N preferably has a maximum absorption wavelength of 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm in a wavelength range of 400nm to 780nm during color development.

The dye N may have only 1 maximum absorption wavelength in the wavelength range of 400nm to 780nm in the case of color development, or may have 2 or more maximum absorption wavelengths. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm when developing color, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the pigment N was determined by using a spectrophotometer under an atmospheric atmosphere: UV3100 (manufactured by SHIMADZU CORPORATION) is obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature 25 ℃) in the range of 400 to 780nm and detecting the wavelength (maximum absorption wavelength) at which the light intensity becomes minimum.

Examples of the dye that develops color or decolors by exposure include colorless compounds.

Examples of the dye decolorized by exposure to light include a leuco compound, a diarylmethane dye, an oxazine dye, a xanthene dye, an iminonaphthoquinone dye, an azomethine dye, and an anthraquinone dye.

The dye N is preferably a colorless compound from the viewpoint of visibility of an exposed portion and a non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), a leuco compound having a fluoran skeleton (fluoran-based dye), a leuco compound having a diarylmethane skeleton (diarylmethane-based dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide-based dye), and a leuco compound having a leucoauramine skeleton (leucoauranilide-based dye).

Among these, triarylmethane-based dyes and fluorane-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) and fluorane-based dyes are more preferable.

The colorless compound preferably has a lactone ring, a sultone (sultone) ring, or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the colorless compound can be decolorized by changing the ring to a closed ring state or the colorless compound can be developed by changing the ring to an open ring state by reacting the lactone ring, sulfinolactone ring or sultone ring of the colorless compound with the radical generated by the photo radical polymerization initiator or the acid generated by the photo cation polymerization initiator. As the colorless compound, a compound having a lactone ring, sulfinyl lactone ring, or sultone ring, which develops color by radical or acid ring opening, is preferable, and a compound having a lactone ring, which develops color by radical or acid ring opening, is more preferable.

Examples of the dye N include the following dyes and leuco compounds.

Specific examples of the dye in pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic magenta, methyl violet 2B, quinaldine red, rose bengal, m-amine yellow, thymolsulfonephthalein, xylenol blue, methyl orange, p-methyl red, congo red, benzo red violet 4B, α -naphthalene red, nile blue 2B, nile blue a, methyl violet, malachite green, parafuchsin, victoria pure blue-alkyl naphthalene sulfonate, victoria pure blue BOH (manufactured by HODOGAYA CHEMICAL co., LTD.), oil blue #603 (manufactured by organic CHEMICAL co., LTD.), oil powder #312 (manufactured by organic CHEMICAL co., LTD., oil red 5B (manufactured by organic CHEMICAL co., LTD., bright red #308 (manufactured by organic CHEMICAL co., o., LTD., t., LTD., t #308, d., LTD., t # 1, d., t # is, e, d, e, d., t # 1, d, e, d., t # 1, e, d., t # 1, d, e, d, e, d, e, d, e, d, e, d, e, d, e, LTD, product of philion Red BEH Special (HODOGAYA CHEMICAL co., product of LTD.), m-cresol purple, cresol Red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylimino naphthoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the leuco compound in pigment N include p, p' -hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene Blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluoran, 2-anilino-3-methyl-6- (N-ethyl-p-tolylamino) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylanilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-chlorofluoran, 3- (N, N-diethylamino) -6-methoxy-7-aminofluoran, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluoran, 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, n-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-xylphenylaminofluoran, 3-hydropyridyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminobenzphthalide, phthalide, phenylamide, phenoxide, and the like, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide and 3 ', 6 ' -bis (diphenylamino) spirocyclic isobenzofuran-1 (3H),9 ' - [9H ] xanthen-3-one.

The dye N is preferably a dye whose maximum absorption wavelength changes by a radical, and more preferably a dye that develops color by a radical, from the viewpoints of visibility of an exposed portion and a non-exposed portion, visibility of a pattern after development, and resolution.

As pigment N, leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-alkyl naphthalene sulfonate is preferred.

One kind of the pigment N may be used alone, or two or more kinds thereof may be used.

The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, based on the total mass of the photosensitive resin layer, from the viewpoints of visibility of exposed portions and unexposed portions, pattern visibility after development, and resolution.

The content of the dye N indicates the content of the dye when all the dyes N contained in the photosensitive resin layer are in a colored state. Hereinafter, a method for quantifying the content of pigment N will be described by taking a pigment that develops color by a radical as an example.

Solutions were prepared by dissolving 0.001g and 0.01g of the dye in 100mL of methyl ethyl ketone. To each of the obtained solutions, Irgacure OXE01 (trade name, BASF Jap an Ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated to generate radicals, thereby bringing all the dyes into a colored state.

Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) under an atmospheric atmosphere, and a calibration curve was prepared.

Next, the absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive resin layer was calculated from the absorbance of the obtained photosensitive resin layer-containing solution based on the calibration curve.

Surfactants-

From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferred.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone nonionic surfactants, and fluorine nonionic surfactants.

From the viewpoint of further improving the resolution, the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant. This is considered to be because the photosensitive resin layer contains a fluorine-based nonionic surfactant, and therefore, the penetration of the etching solution into the photosensitive resin layer is suppressed, and the side etching is reduced.

As commercially available fluorine-based nonionic surfactants, MEGAFACE F-551, F-552 and F-554 (both produced by DIC CORPORATION) are exemplified.

Further, examples of commercially available fluorine-based surfactants include MEGAFACE 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-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, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, MFS-5780, MFS-586, MFS-18, MFS-80, R-L-130, R-LM, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC CORPORATION), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTION INC), Ftergent 710FL, 710FM 610, FM 601, AD 601, 2, 602A, 215M, 245F, tdd 251, 212M, 250, F209, 222F, 208G, LA, FS 710, LM, AC, 681, 683 (manufactured by CO OS 650, CO.).

Further, as the fluorine-based surfactant, it is also preferable to use an acrylic compound having a molecular structure with a functional group containing a fluorine atom, and the fluorine atom is cleaved at a portion of the functional group containing the fluorine atom when heated to volatilize. Examples of such a fluorine-based surfactant include MEGAFACEDS series manufactured by DIC CORPORATION (The Chemical Daily (2016, 22/2), and Nikkei Business Daily (2016, 23/2)), and MEGAFACE DS to 21.

Further, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluoroalkyl group or a fluoroalkylene ether group and a hydrophilic vinyl ether compound is also preferably used.

Further, as the fluorine-based surfactant, a block polymer may also be used.

Further, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a constituent unit derived from a (meth) acrylate compound having a fluorine atom and a constituent unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) can also be preferably used.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102 and RS-718K, RS-72-K (manufactured by DIC CORPORATION).

As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, a surfactant derived from a material alternative to a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS), is preferable.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, 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 L10, L31, L61, L62, 10R5, 17R2, 25R2 (of BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (of BASF), Solersspe 20000 (of Lubrol Japan Limited), NCW-101, NCW-1001, NCW-1002 (of JIFILIM, Wako Pure), PIOND-6112, D-6112-W6112, and D-6112-W12-W1002, D-6315 (Takemoto Oil & Fat Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.), and the like.

Examples of the silicone surfactant include a linear polymer having siloxane bonds and a modified siloxane polymer having an organic group introduced into a side chain or a terminal thereof.

Specific examples of the SILICONE surfactant include DOWNSIL 8032ADDITIVE, TORAYSILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30 567, TORAY SILICONE SH8400 (made by Dow Corning Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351 354 68, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, Si-6004, KP-35341, KF-TSTSTSS 441-44945, KF-44444440, KF-44444452, KF-444440, KF-4440-4452 (made by Ether Co., KF-4440, KF-4452, KF-4440, KF-4452, or more than, BYK307, BYK323, BYK330 (manufactured by BYK Japan KK), and the like.

As the surfactant, surfactants described in paragraphs 0120 to 0125 of International publication No. 2018/179640, surfactants described in paragraphs 0017 of Japanese patent No. 4502784, and surfactants described in paragraphs 0060 to 0071 of Japanese patent laid-open No. 2009-237362 can be used.

The photosensitive resin layer may contain one kind of surfactant alone, or may contain two or more kinds of surfactants.

The content of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total mass of the photosensitive resin layer.

Additives-

The photosensitive resin layer may contain known additives in addition to the above components as needed.

Examples of the additive include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, resins other than the polymer a, and solvents. The photosensitive resin layer may contain one kind of each additive alone, or may contain two or more kinds of each additive.

The photosensitive resin layer may contain a radical polymerization inhibitor.

Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. The nitrosophenylhydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive resin layer.

Examples of the benzotriazole include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and the like. As the carboxybenzotriazole, a commercially available product such as CBT-1 (JOOOKU CHEMICAL CO., LTD, trade name) can be used.

The total content of the radical polymerization inhibitor, the benzotriazole compound and the carboxybenzotriazole compound is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, based on 100 mass% of the total mass of the photosensitive resin layer. From the viewpoint of imparting storage stability to the photosensitive resin layer, the content is preferably 0.01 mass% or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing dye discoloration, the content is preferably 3% by mass or less.

The photosensitive resin layer may contain a sensitizer.

The sensitizer is not particularly limited, and a known sensitizer, dye, and pigment can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

The photosensitive resin layer may contain one kind of sensitizer alone, or may contain two or more kinds of sensitizers.

In the case where the photosensitive resin layer contains a sensitizer, the content of the sensitizer may be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by a balance between the polymerization rate and the chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least one selected from a plasticizer and a heterocyclic compound.

Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International publication No. 2018/179640.

The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

The photosensitive resin layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents.

Additives contained in the photosensitive resin layer are described in sections 0165 to 0184 of jp 2014-85643 a, the contents of which are incorporated in the present specification.

< physical Properties, etc.)

The thickness of the photosensitive resin layer is preferably 0.1 to 300. mu.m, more preferably 0.2 to 100. mu.m, still more preferably 0.5 to 50 μm, yet more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm. This improves the developability of the photosensitive resin layer, thereby improving the resolution.

In one embodiment, the thickness is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and still more preferably 0.5 to 3 μm.

Further, from the viewpoint of linearity, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less, and particularly preferably 1 μm or more and 4 μm or less.

The layer thickness of each layer of the photosensitive transfer member is measured as follows: a cross section in a direction perpendicular to the main surface of the photosensitive transfer member was observed with a Scanning Electron Microscope (SEM), and the thickness of each layer was measured at 10 points or more from the obtained observation image, and the average value thereof was calculated.

From the viewpoint of further improving the adhesion, the transmittance of light having a wavelength of 365nm in the photosensitive resin layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

< method of formation >

The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above-described components.

Examples of the method for forming the photosensitive resin layer include a method in which: a photosensitive resin composition containing a binder polymer, a polymerizable compound, a solvent and the like is prepared, the photosensitive resin composition is coated on the surface of a temporary support or the like, and the coating film of the photosensitive resin composition is dried.

Examples of the photosensitive resin composition for forming the photosensitive resin layer include compositions containing a binder polymer, a polymerizable compound, the above-mentioned optional components, and a solvent.

In order to adjust the viscosity of the photosensitive resin composition to facilitate formation of the photosensitive resin layer, the photosensitive resin composition preferably contains a solvent.

(solvent)

The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the binder polymer, the polymerizable compound, and any of the above components, and a known solvent can be used.

Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, and the like), ketone solvents (acetone, methyl ethyl ketone, and the like), aromatic hydrocarbon solvents (toluene, and the like), aprotic polar solvents (N, N-dimethylformamide, and the like), cyclic ether solvents (tetrahydrofuran, and the like), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these solvents.

In the case of producing a photosensitive transfer member provided with a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these solvents, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable, and a mixed solvent containing at least three selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents, and cyclic ether solvents is even more preferable.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

As the solvent, a solvent described in paragraphs 0092 to 0094 of International publication No. 2018/179640 and a solvent described in paragraph 0014 of Japanese patent application laid-open No. 2018-177889 can be used, and the contents thereof are incorporated in the present specification.

The photosensitive resin composition may contain one kind of solvent alone, or may contain two or more kinds of solvents.

The content of the solvent in coating the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.

The method for producing the photosensitive resin composition is not particularly limited, and examples thereof include the following methods: solutions obtained by dissolving the respective components in the above solvents are prepared in advance, and the solutions are mixed at a predetermined ratio.

The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 to 30 μm before forming the photosensitive resin layer.

The method for applying the photosensitive resin composition is not particularly limited, and the coating can be performed by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and spray coating.

The photosensitive resin layer may be formed by applying a photosensitive resin composition to a coating film described later and then drying the coating film.

[ thermoplastic resin layer ]

The photosensitive transfer member may include a thermoplastic resin layer.

The photosensitive transfer member preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. This is because the provision of the thermoplastic resin layer between the temporary support and the photosensitive resin layer by the photosensitive transfer member improves the following property to the substrate in the step of bonding to the substrate, suppresses air bubbles from entering between the substrate and the photosensitive transfer member, and improves the adhesion to an adjacent layer (for example, the temporary support).

< ingredient >

(alkali-soluble resin)

The thermoplastic resin layer contains an alkali-soluble resin as a thermoplastic resin.

In the present specification, "alkali-soluble" means that the solubility in 100g of a 1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more.

Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.

Here, the acrylic resin means a resin having at least one constituent unit selected from a constituent unit derived from (meth) acrylic acid, a constituent unit derived from a (meth) acrylate ester, and a constituent unit derived from a (meth) acrylamide.

The acrylic resin preferably contains a total content of the constituent unit derived from (meth) acrylic acid, the constituent unit derived from (meth) acrylic acid ester, and the constituent unit derived from (meth) acrylamide of 50 mass% or more with respect to the total mass of the acrylic resin.

The total content of the (meth) acrylic acid-derived constituent unit and the (meth) acrylate-derived constituent unit is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

Also, the alkali-soluble resin is preferably a polymer having an acid group.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonate group, and a carboxyl group is preferable.

From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, and still more preferably a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more.

The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is not particularly limited, and can be suitably selected from known resins and used.

Examples thereof include an alkali-soluble resin as a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of Japanese patent application laid-open No. 2011-95716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in the middle stages 0033 to 0052 of Japanese patent application laid-open No. 2010-237589, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the binder polymer described in paragraphs 0053 to 0068 of Japanese patent application laid-open No. 2016-224162.

The copolymerization ratio of the constituent unit having a carboxyl group in the above carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

As the alkali-soluble resin, an acrylic resin having a constituent unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.

The alkali soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples thereof include an ethylenically unsaturated group; a condensation polymerizable group such as a hydroxyl group or a carboxyl group; addition polymerization reactive groups such as epoxy groups, (blocked) isocyanate groups, and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 1 ten thousand to 10 ten thousand, and further preferably 2 ten thousand to 5 ten thousand.

The thermoplastic resin layer may contain one alkali-soluble resin alone or two or more alkali-soluble resins.

From the viewpoint of developability and adhesion to adjacent layers, the content of the alkali-soluble resin is preferably 10 to 99 mass%, more preferably 20 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 50 to 70 mass% with respect to the total mass of the thermoplastic resin layer.

(pigments)

The thermoplastic resin layer preferably contains a dye (also referred to simply as "dye B") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical.

Preferred embodiments of the dye B are the same as those of the dye N except for the points described below.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.

From the viewpoint of visibility and resolution of the exposed portion and the unexposed portion, the thermoplastic layer preferably contains both a dye whose maximum absorption wavelength of the dye B is changed by an acid and a compound that generates an acid by light, which will be described later.

One kind of the pigment B may be used alone, or two or more kinds thereof may be used.

The content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, even more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed portion and the unexposed portion.

Here, the content of the coloring matter B indicates the content of the coloring matter when all the coloring matter B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of pigment B will be described by taking a pigment that develops color by a radical as an example.

Solutions were prepared by dissolving 0.001g and 0.01g of the dye in 100mL of methyl ethyl ketone. To each of the obtained solutions, Irgacure OXE01 (trade name, BASF Japan Ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated to generate radicals, thereby bringing all the dyes into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) under an atmospheric atmosphere, and a calibration curve was prepared.

Next, the absorbance of the solution after all the coloring matters were developed was measured by the same method as described above except that 0.1g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the coloring matters. The amount of the pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer according to the calibration curve.

(Compounds generating acids, bases, or radicals by light)

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical using light (also simply referred to as "compound C").

The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving an activating light such as ultraviolet light or visible light.

As the compound C, a known photoacid generator, photobase generator, and photoradical polymerization initiator (photoradical generator) can be used. Among them, a photoacid generator is preferable.

Photoacid generators-

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator.

Examples of the photoacid generator include a photo cation polymerization initiator that can be contained in the photosensitive resin layer, and preferred embodiments are the same except for the points described below.

The photoacid generator preferably contains at least one compound selected from an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.

Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.

[ chemical formula 2]

Photo radical polymerization initiator

The thermoplastic resin layer may have a photo radical polymerization initiator (photo radical polymerization initiator).

Examples of the photo radical polymerization initiator include photo radical polymerization initiators that can be contained in the photosensitive resin layer, and the same is preferred.

Photobase generators-

The thermoplastic resin layer may contain a photobase generator.

The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, o-carbamoylhydroxyamide, o-carbamoyloxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, bis [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane-1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexammoniacobolt (III) tris (triphenylmethyl borate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, hexakis (methyl) butanone, and the like, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine and 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine.

The thermoplastic resin layer may contain one kind of compound C alone, or may contain two or more kinds of compound C.

The content of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of the exposed portion and the unexposed portion.

(plasticizer)

The thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability.

The plasticizer preferably has a molecular weight smaller than that of the alkali-soluble resin (weight average molecular weight (Mw) in the case of an oligomer or polymer). The plasticizer preferably has a molecular weight (weight average molecular weight (Mw)) of 200 to 2,000.

The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably is a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

The plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.

Examples of the (meth) acrylate compound used as the plasticizer include (meth) acrylate compounds described as polymerizable compounds contained in the photosensitive resin layer.

In the case where the thermoplastic resin layer and the photosensitive resin layer are directly in contact with each other and laminated in the photosensitive transfer member, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound. This is because when the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound, the diffusion of components between the layers is suppressed, and the storage stability is improved.

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize even in an exposed portion after exposure from the viewpoint of adhesion to an adjacent layer.

As the (meth) acrylate compound used as a plasticizer, a polyfunctional (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule is preferable from the viewpoint of resolution, adhesion to adjacent layers, and developability.

Further, as the (meth) acrylate compound used as the plasticizer, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.

The thermoplastic resin layer may contain one kind of plasticizer alone, or may contain two or more kinds of plasticizers.

The content of the plasticizer is preferably 1 to 70 mass%, more preferably 10 to 60 mass%, and particularly preferably 20 to 50 mass% with respect to the total mass of the thermoplastic resin layer, from the viewpoint of resolution, adhesion to adjacent layers, and developability.

(surfactant)

The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.

The surfactant may be a surfactant that can be contained in the photosensitive resin layer, and the same is preferred.

The thermoplastic resin layer may contain one kind of surfactant alone, or may contain two or more kinds of surfactants.

The content of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total mass of the thermoplastic resin layer.

(sensitizer)

The thermoplastic resin layer may contain a sensitizer.

The sensitizer is not particularly limited, and examples thereof include sensitizers that can be contained in the photosensitive resin layer.

The thermoplastic resin layer may contain one sensitizer alone or two or more sensitizers.

The content of the sensitizer may be appropriately selected according to the purpose, but is preferably in the range of 0.01 to 5 mass%, more preferably in the range of 0.05 to 1 mass%, relative to the total mass of the thermoplastic resin layer, from the viewpoints of improvement of sensitivity to a light source and visibility of exposed portions and non-exposed portions.

(additives, etc.)

In addition to the above components, the thermoplastic resin layer may contain known additives as needed.

Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of japanese patent application laid-open No. 2014-85643, and the contents described in this publication are incorporated in the present specification.

< physical Properties etc. >

The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to an adjacent layer. The upper limit is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less.

< method of formation >

The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.

Examples of the method for forming the thermoplastic resin layer include a method in which: a thermoplastic resin composition containing the above components and a solvent is prepared, the thermoplastic resin composition is coated on the surface of a temporary support or the like, and the coating film of the thermoplastic resin composition is dried.

In order to adjust the viscosity of the thermoplastic resin composition to easily form the thermoplastic resin layer, the thermoplastic resin composition preferably contains a solvent.

(solvent)

The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above-mentioned components contained in the thermoplastic resin layer.

Examples of the solvent contained in the thermoplastic resin composition include solvents that can be contained in the photosensitive resin composition, and the preferred embodiments are also the same.

The solvent contained in the thermoplastic resin composition may be one kind alone, or two or more kinds thereof.

The content of the solvent in coating the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be performed according to the method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer.

For example, a thermoplastic resin layer is formed by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in the solvent in advance, and mixing the obtained solutions at a predetermined ratio to prepare a thermoplastic resin composition, then coating the obtained thermoplastic resin composition on the surface of the temporary support, and drying the coating film of the thermoplastic resin composition.

Further, after the photosensitive resin layer and the intermediate layer are formed on the cover film described later, the thermoplastic resin layer may be formed on the surface of the intermediate layer.

[ intermediate layer ]

The photosensitive transfer member preferably includes an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. By providing the intermediate layer, mixing of components can be suppressed during application of a plurality of layers and during storage after application.

The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppression of mixing of components when a plurality of layers are applied and when stored after application.

In the present specification, "water-soluble" means that the solubility in 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more.

The intermediate layer may be an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in Japanese patent laid-open No. 5-72724. The intermediate layer is preferably an oxygen barrier layer because sensitivity at the time of exposure is improved, time load of the exposure apparatus is reduced, and productivity is improved.

The oxygen barrier layer used as the intermediate layer can be appropriately selected from known layers described in the above-mentioned publication and the like. Among them, an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1 mass% aqueous solution of sodium carbonate at 22 ℃) is preferable.

The intermediate layer preferably contains a resin.

Examples of the resin contained in the intermediate layer include resins such as polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

As the resin contained in the intermediate layer, a water-soluble resin is preferable.

From the viewpoint of suppressing the mixing of components between the multiple layers, the resin contained in the intermediate layer is preferably a resin different from both the polymer a contained in the photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

The intermediate layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and during storage after coating.

The intermediate layer may contain one kind of the above-mentioned resin alone, or may contain two or more kinds of the above-mentioned resins.

The content of the resin in the intermediate layer is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to the total mass of the intermediate layer, from the viewpoints of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and during storage after coating.

The intermediate layer may contain an additive such as a surfactant, if necessary.

The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm.

This is because, if the thickness of the intermediate layer is within the above range, mixing of components during coating of a plurality of layers and during storage after coating can be suppressed without lowering the oxygen barrier property, and an increase in the time for removing the intermediate layer during development can be suppressed.

The method for forming the intermediate layer is not particularly limited, and examples thereof include a method for forming an intermediate layer by: an intermediate layer composition containing the above resin and any additive is prepared, applied to the surface of the thermoplastic resin layer or the photosensitive resin layer, and the coating film of the intermediate layer composition is dried.

In order to adjust the viscosity of the intermediate layer composition to easily form the intermediate layer, the intermediate layer composition preferably contains a solvent.

The solvent contained in the intermediate layer composition is not particularly limited as long as it can dissolve or disperse the resin, and is preferably at least one selected from water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and water-miscible organic solvents.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

[ covering film ]

The photosensitive transfer member preferably includes a cover film that is in contact with a surface of the photosensitive resin layer that does not face the temporary support.

Hereinafter, in this specification, the surface of the photosensitive resin layer facing the temporary support is also referred to as "1 st surface", and the surface opposite to the 1 st surface is also referred to as "2 nd surface".

The cover film is made of a resin film and paper, and the resin film is preferable from the viewpoint of strength and flexibility.

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. Among them, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.

The thickness (layer thickness) of the cover film is not particularly limited, but is preferably 5 to 100 μm, and more preferably 10 to 50 μm.

From the viewpoint of further improving the resolution, the arithmetic average roughness Ra value of the surface of the cover film in contact with the photosensitive resin layer (hereinafter, also simply referred to as "the surface of the cover film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less. This is considered to be because the Ra value of the surface of the cover film within the above range improves the uniformity of the layer thickness of the photosensitive resin layer and the resin pattern to be formed.

The lower limit of the Ra value of the surface of the coating film is not particularly limited, but is preferably 0.001 μm or more.

The Ra value of the surface of the cover film was measured by the following method.

The surface profile of the optical film was obtained by measuring the surface of the cover film using a three-dimensional optical profiler (New View7300, manufactured by Zygo) under the following conditions.

As the measurement/analysis software, Microcope application from MetropoPro ver8.3.2 was used. Next, a Surface Map picture is displayed by the above analysis software, and histogram data is obtained in the Surface Map picture. The arithmetic average roughness was calculated from the obtained histogram data, and the Ra value of the surface of the coating film was obtained.

When the cover film is attached to the photosensitive transfer member, the cover film may be peeled from the photosensitive transfer member, and the Ra value of the peeled surface may be measured.

The photosensitive transfer member may include a layer other than the above-described layer (hereinafter, also referred to as "other layer"). As another layer, for example, a contrast enhancement layer can be given.

The contrast enhancement layer is described in paragraph 0134 of international publication No. 2018/179640. The other layers are described in sections 0194 to 0196 of Japanese patent laid-open publication No. 2014-85643. The contents of these publications are incorporated into this specification.

From the viewpoint of further exhibiting the effects of the present invention, the total thickness of the layers other than the temporary support and the cover film in the photosensitive transfer member is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

From the viewpoint of further exhibiting the effects of the present invention, the total thickness of the photosensitive resin layer, the intermediate layer, and the thermoplastic resin layer in the photosensitive transfer member is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[ method for producing photosensitive transfer Member ]

The method for producing the photosensitive transfer member used in the present invention is not particularly limited, and a known production method, for example, a known method for forming each layer, can be used.

Hereinafter, a method for manufacturing a photosensitive transfer member used in the present invention will be described with reference to fig. 2. However, the photosensitive transfer member used in the present invention is not limited to the photosensitive transfer member having the structure shown in fig. 2.

Fig. 2 is a schematic view showing an example of the structure of the photosensitive transfer member used in the present invention. The photosensitive transfer member 100 shown in fig. 2 has a structure in which a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18 are sequentially stacked.

Examples of the method for producing the photosensitive transfer member 100 include a method including the steps of: a step of forming a thermoplastic resin layer 12 by applying a thermoplastic resin composition to the surface of the temporary support 10 and then drying the coating film of the thermoplastic resin composition; a step of forming an intermediate layer 14 by applying the intermediate layer composition to the surface of the thermoplastic resin layer 12 and then drying the coating film of the intermediate layer composition; and a step of forming the photosensitive resin layer 16 by coating a photosensitive resin composition containing a binder polymer and a polymerizable compound on the surface of the intermediate layer 14 and then drying the coating film of the photosensitive resin composition.

In the above production method, it is preferable to use a thermoplastic resin composition containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, an intermediate layer composition containing at least one selected from the group consisting of water and a water-miscible organic solvent, and a photosensitive resin composition containing a binder polymer, a polymerizable compound, and at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Thereby, during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and/or during the storage of the laminate having the coating film of the intermediate layer composition, the mixing of the component contained in the thermoplastic resin layer 12 with the component contained in the intermediate layer 14 can be suppressed, and during the application of the photosensitive resin composition to the surface of the intermediate layer 14 and/or during the storage of the laminate having the coating film of the photosensitive resin composition, the mixing of the component contained in the intermediate layer 14 with the component contained in the photosensitive resin layer 16 can be suppressed.

The photosensitive transfer member 100 is manufactured by pressure-bonding the cover film 18 to the photosensitive resin layer 16 of the laminate manufactured by the above-described manufacturing method.

As a method for producing the photosensitive transfer member used in the present invention, it is preferable to produce the photosensitive transfer member 100 including the temporary support 10, the thermoplastic resin layer 12, the intermediate layer 14, the photosensitive resin layer 16, and the cover film 18 by including a step of providing the cover film 18 so as to be in contact with the 2 nd surface of the photosensitive resin layer 16.

After the photosensitive transfer member 100 is manufactured by the above-described manufacturing method, the photosensitive transfer member in a rolled state can be manufactured and stored by rolling up the photosensitive transfer member 100. The photosensitive transfer member in a roll form can be supplied as it is to a step of bonding to a substrate by a roll-to-roll method described later.

[ method for manufacturing Circuit Wiring ]

The method for manufacturing the circuit wiring according to the present invention is not particularly limited as long as it includes the method for manufacturing the resin pattern according to the present invention.

As the method for manufacturing the circuit wiring, a method including a step of etching a conductive layer located in a region where no resin pattern is arranged (hereinafter, also referred to as an "etching step") in a laminate having a conductive layer on a surface of the substrate on the side where the resin pattern is formed and a resin pattern manufactured by the method for manufacturing a resin pattern according to the present invention laminated in this order is preferable, and a method including a step of using a resin pattern manufactured by a manufacturing method including the bonding step, the exposure step, and the developing step is more preferable.

The steps included in the method for manufacturing the circuit wiring will be described below, but unless otherwise specified, the contents described for the steps included in the method for manufacturing the resin pattern are also applicable to the steps included in the method for manufacturing the circuit wiring.

[ etching Process ]

The method for manufacturing a circuit wiring preferably includes a step (etching step) of etching the conductive layer located in a region where the resin pattern is not arranged in a laminate in which the substrate, the conductive layer, and the resin pattern (more preferably, the resin pattern manufactured by the manufacturing method including the bonding step, the exposure step, and the developing step) are laminated in this order. Specifically, "etching treatment of the conductive layer located in a region where the resin pattern is not arranged" means that the conductive layer is etched to remove a part of the conductive layer on which the resin pattern is not arranged.

In the etching step, the conductive layer is etched using a resin pattern formed of a photosensitive resin layer as a resist.

As the method of the etching treatment, known methods can be applied, and examples thereof include a method described in paragraphs 0209 to 0210 of jp 2017-120435 a, a method described in paragraphs 0048 to 0054 of jp 2010-152155 a, a wet etching method by immersion in an etching solution, and a dry etching method by plasma etching or the like.

The etching solution used for wet etching may be an acidic or alkaline etching solution appropriately selected according to the object of etching.

Examples of the acidic etching solution include an aqueous solution of a single acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of a plurality of acidic components.

Examples of the alkaline etching solution include an aqueous solution of a single alkali component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (e.g., tetramethylammonium hydroxide) and a mixed aqueous solution of an alkali component and a salt (e.g., potassium permanganate). The alkali component may be a combination of a plurality of alkali components.

[ removal Process ]

In the method of manufacturing the circuit wiring, it is preferable to perform a step of removing the remaining resin pattern (removal step).

The removal step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.

The method of removing the residual resin pattern is not particularly limited, and a method of removing by chemical treatment is exemplified, and a method of removing by using a removing solution is preferable.

As a method for removing the photosensitive resin layer, a method in which the substrate having the remaining resin pattern is immersed in a removing liquid under stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes can be mentioned.

Examples of the removing solution include a solution obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.

The removal liquid may be removed by a known method such as a spray method, a shower method, or a spin-coating immersion method.

[ other procedures ]

The method of manufacturing the circuit wiring may include any step (other step) other than the above-described steps. Examples of the process include, but are not limited to, the following processes.

Further, examples of the exposure step, the development step, and other steps applicable to the method for manufacturing circuit wiring include the steps described in paragraphs 0035 to 0051 of jp 2006-a-23696.

< Process for reducing reflectance of visible ray >

The method of manufacturing the circuit wiring may include a step of performing a treatment for reducing visible light reflectance of part or all of the plurality of conductive layers included in the substrate.

As a treatment for reducing the visible light reflectance, an oxidation treatment may be mentioned. In the case where the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing copper to form copper oxide and blackening the conductive layer.

The treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of jp 2014-150118 a and paragraphs 0041, 0042, 0048 and 0058 of jp 2013-206315 a, and the contents of these publications are incorporated in the present specification.

< step of Forming insulating film, step of Forming New conductive layer on surface of insulating film >

The method of manufacturing a circuit wiring preferably further comprises a step of forming an insulating film on a surface of the circuit wiring and a step of forming a new conductive layer on a surface of the insulating film.

Through the above steps, the 2 nd electrode pattern insulated from the 1 st electrode pattern can be formed.

The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film may be mentioned. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.

The step of forming a new conductive layer on the insulating film is not particularly limited, and a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

The method of manufacturing the circuit wiring preferably further includes forming a circuit using a substrate having a plurality of conductive layers on both surfaces of the substrate, respectively, and a conductive layer formed on both surfaces of the substrate sequentially or simultaneously. With this configuration, it is possible to form the circuit wiring for the touch panel in which the 1 st conductive pattern is formed on the surface of one side of the substrate and the 2 nd conductive pattern is formed on the surface of the other side. Further, it is preferable that the circuit wiring for a touch panel having such a structure is formed on both surfaces of the substrate by roll-to-roll.

[ use of circuit wiring ]

The circuit wiring manufactured by the method of manufacturing a circuit wiring can be applied to various devices. Examples of a device including the circuit wiring manufactured by the above-described manufacturing method include an input device, preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[ method for manufacturing touch Panel ]

The method for manufacturing a touch panel according to the present invention is not particularly limited as long as it is a method for manufacturing a circuit wiring including the method for manufacturing a resin pattern according to the present invention.

As the method for manufacturing a touch panel, a method including a step of forming a wiring for a touch panel by etching a conductive layer located in a region where a resin pattern is not arranged in a laminate in which the substrate has the conductive layer on a surface on a side where the resin pattern is formed and the resin pattern manufactured using the photosensitive transfer member is laminated in this order is preferable, and a method including a step of manufacturing a resin pattern including the bonding step, the exposure step, and the development step is more preferable.

The embodiments of the method for manufacturing a touch panel, such as the specific embodiments of the steps and the order of performing the steps, are the same as the preferred embodiments described in the section "method for manufacturing a resin pattern" and "method for manufacturing a circuit wiring".

In the method of manufacturing a touch panel, a known method of manufacturing a touch panel may be used in addition to the method of forming the touch panel wiring.

The method of manufacturing the touch panel may include any process (other process) other than the above.

Fig. 3 and 4 show an example of a pattern of a mask used for manufacturing a touch panel.

In pattern a shown in fig. 3 and pattern B shown in fig. 4, SL and G are non-image portions (light-shielding portions), and DL is a portion where an alignment frame is virtually shown. In the method of manufacturing a touch panel, for example, a touch panel in which circuit wirings having patterns a corresponding to SL and G are formed can be manufactured by exposing a photosensitive resin layer through a mask having the pattern a shown in fig. 3. Specifically, the compound can be produced by the method described in fig. 1 of international publication No. 2016/190405. In an example of a touch panel manufactured, G is a portion where a transparent electrode (electrode for a touch panel) is formed, and SL is a portion where a wiring of a peripheral lead-out portion is formed.

By the above method for manufacturing a touch panel, a touch panel having at least a touch panel wiring can be manufactured. The touch panel preferably has a transparent substrate, an electrode, and an insulating layer or a protective layer.

Examples of a detection method of the touch panel include known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.

Examples of the Touch panel include a so-called embedded type (for example, the types described in fig. 5, 6, 7, and 8 of japanese laid-open patent publication No. 2012-517051), a so-called external embedded type (for example, the type described in fig. 19 of japanese laid-open patent publication No. 2013-168125 and the types described in fig. 1 and 5 of japanese laid-open patent publication No. 2012-89102), an OGS (One Glass Solution) type, a TOL (Touch-on-lines) type (for example, the type described in fig. 2 of japanese laid-open patent publication No. 2013-54727), various external hanging types (for example, GG, G1-G2, GFF, GF2, 1, and G1F), and other structures (for example, the GF type described in fig. 6 of japanese laid-open patent publication No. 2013-871).

Examples of the touch panel include the touch panel described in paragraph 0229 of japanese patent application laid-open nos. 2017-120345.

[ photosensitive transfer Member ]

The photosensitive transfer member according to the present invention is a photosensitive transfer member having a temporary support and a photosensitive resin layer, wherein when a resin pattern a having a pattern width of 6 μm at a position 90% of the maximum height of a substrate is formed on the substrate by the photosensitive transfer member, the pattern width of the resin pattern a in a portion contacting the substrate in a cross section in the width direction of the resin pattern a is 6.2 μm or more.

A preferred embodiment of the photosensitive transfer member according to the present invention is the same as that of the photosensitive transfer member used in the method for producing a resin pattern according to the present invention, except for the following.

In the case where a resin pattern a having a pattern width of 6 μm is formed on a substrate at a position 90% away from the maximum height of the substrate, the pattern width of the resin pattern a in a portion contacting the substrate in a cross section in the width direction of the resin pattern a is preferably 6.2 μm or more and 9.0 μm or less, more preferably 6.2 μm or more and 8.4 μm or less, further preferably 6.3 μm or more and 8.0 μm or less, and particularly preferably 6.4 μm or more and 8.0 μm or less, from the viewpoint of resolution and linearity.

Examples

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the order of the processes, and the like shown in the following examples can be appropriately changed without departing from the gist of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples described below. Unless otherwise specified, "part" and "%" are based on mass.

(examples 1 to 9 and comparative examples 1 to 3)

< production of photosensitive transfer Member >

Formation of a thermoplastic resin layer

As a temporary support, a PET film having a thickness of 25 μm was prepared. The following thermoplastic resin composition was applied onto the surface of the temporary support using a slit nozzle so that the application width was 1.0m and the dried layer thickness was 4.0 μm.

The formed coating film of the thermoplastic resin composition was dried at 80 ℃ for 40 seconds to form a thermoplastic resin layer.

Thermoplastic resin composition

The following components were mixed to prepare a thermoplastic resin composition.

Copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (solid content concentration 30.0%, mw30,000, acid value 153 mgKOH/g): 42.85 parts of

NK ESTETR A-DCP (Dicidol diacrylate, Shin-Nakamura Chemical Co., Ltd.): 4.63 parts

8UX-015A (multifunctional urethane acrylate Compound, TAISEI FINE CHEMICAL CO, manufactured by LTD.): 2.31 parts of

Aronium TO-2349 (multifunctional acrylate compound having carboxyl group, TOAGOSEI co., ltd.): 0.77 part

A compound having a structure shown below (photoacid generator, a compound synthesized by the method described in paragraph 0227 of jp 2013-47765 a): 0.32 part

[ chemical formula 3]

A compound having a structure shown below (a dye that develops color by an acid): 0.08 portion of

[ chemical formula 4]

E-1(MEGAFACE F552 (manufactured by DIC CORPORATION)): 0.03 part

MEK (methyl ethyl ketone, SANKYO CHEMICAL co., ltd.): 39.50 portions

PGMEA (propylene glycol monomethyl ether acetate, SHOWA DENKO k.k.): 9.51 parts of

Formation of an intermediate layer

The intermediate layer composition was applied onto the surface of the formed thermoplastic resin layer using a slit nozzle so that the application width became 1.0m and the layer thickness after drying became 1.2 μm. The coating film of the interlayer composition was dried at 80 ℃ for 40 seconds to form an interlayer.

Intermediate layer composition

The following ingredients were mixed to prepare an intermediate layer composition.

Deionized water: 38.12 parts of

Methanol (mitsubashi GAS CHEMICAL COMPANY, inc.): 57.17 parts

KURARAY POVAL PVA-205 (polyvinyl alcohol, KURARAY co., ltd.): 3.22 parts of

Polyvinylpyrrolidone K-30(Nippon Shokubai co., ltd.): 1.49 parts

MEGAFACE F-444 (fluorine-containing nonionic surfactant, manufactured by DIC CORPORATION): 0.0015 part

Formation of photosensitive resin layer

Any of the photosensitive resin compositions a-1 to a-7 or AH-1 to AH-3 described in table 1 was applied to the surface of the formed intermediate layer using a slit nozzle so that the application width became 1.0m and the thickness after drying became the thickness described in table 1. The coating film of the photosensitive resin composition A-1 to A-7 or AH-1 to AH-3 was dried at 80 ℃ for 40 seconds to form a photosensitive resin layer.

[ Table 1]

The compositions of the photosensitive resin compositions A-1 to A-7 and AH-1 to AH-3 used are shown in Table 2 below.

[ Table 2]

In table 2, "Mm/Mb" represents a value of a ratio Mm/Mb of a content Mm of the polymerizable compound to a content Mb of the binder polymer in the photosensitive resin layer, and "content of the acrylic compound" represents a content of the acrylic compound with respect to a total mass of the (meth) acrylic compound contained in the photosensitive resin layer, and the unit is mass%.

In addition, the details of the abbreviations of table 2 are shown below.

BPE-500: ethoxylated (10 molar equivalents) bisphenol A dimethacrylate (Shin-Nakamura Chemical Co., Ltd.)

BPE-200: ethoxylated (4 molar equivalents) bisphenol A dimethacrylate (Shin-Nakamura Chemical Co., Ltd.)

M-270: polypropylene glycol diacrylate (n is about 12) (TOAGOSEI co., ltd. system)

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

SR-454: ethoxylated trimethylolpropane triacrylate (manufactured by Arkema S.A.)

SR-502: ethoxylated (9 molar equivalent) trimethylolpropane triacrylate (manufactured by Arkema s.a.)

A-9300-CL 1: epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

B-CIM: 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole (polymerization initiator, KUROGANE KASEI Co., manufactured by Ltd.)

SB-PI 701: 4, 4' -bis (diethylamino) benzophenone (sensitizer, SANYO tradingco, ltd. system)

CBT-1: carboxybenzotriazole (Rust preventive, JOHOKU CHEMICAL CO., LTD product)

TDP-G: phenothiazine (polymerization inhibitor, Kawaguchi Chemical Industry Co., LTD. manufactured)

Irganox 245: ethylene bis (oxyethylene) bis (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate) (polymerization inhibitor, manufactured by BASF corporation)

F-552: fluorine-based surfactant (produced by DIC CORPORATION)

Sticking of cover films

A PET film (prepared by inc., lumiror 16QS62, arithmetic average roughness (Ra value) 0.02 μm) was pressure-bonded as a cover film to the surface of the formed photosensitive resin layer, thereby producing photosensitive transfer members of the respective examples.

The obtained photosensitive transfer member was wound up to produce a rolled photosensitive transfer member.

< production of laminate >

The films of the photosensitive transfer members F-1 to F-9, FH-1, and FH-2 produced in the above-described manner were peeled off, the peeled surfaces of the photosensitive transfer members were brought into contact with a copper substrate, and the substrate was laminated on a copper substrate having a copper layer formed by sputtering copper onto a PET film and having a thickness of 200 μm under the following lamination conditions, to obtain a laminate.

Lamination conditions-

Temperature of copper substrate: 40 deg.C

Temperature of rubber roller: 110 deg.C

Line pressure: 3N/cm

Conveying speed: 2 m/min

< Exposure >

Next, an exposure mask having an exposure pattern with a line/space of 6 μm/6 μm was brought into close contact with the temporary support on the side of the laminate on which the photosensitive transfer member was laminated, and exposure was performed with an exposure amount such that the height of the position at 90% of the maximum height of the resist pattern was 6 μm through the exposure mask using a proximity type exposure machine (manufactured by High-Tech Electronics Engineering co., ltd.) having an ultra-High pressure mercury lamp.

< development >

Then, the temporary support was peeled from the exposed laminate, and subjected to a development treatment under development conditions using a 1.0% sodium carbonate aqueous solution at 26 ℃ for 30 seconds.

Subsequently, a washing treatment was performed at 26 ℃ for 30 seconds using pure water.

Subsequently, air is blown to the surface to remove moisture, thereby producing a substrate having a resin pattern.

A shower type developing machine was used for the development and cleaning, and the injection pressure was 0.08 MPa.

< etching and peeling >

The copper layer of the substrate having the resin pattern was subjected to spray etching for 60 seconds using a copper etching solution (KANTO CHEMICAL co., inc., product, Cu-02) at 25 ℃.

Then, the resin pattern was removed by spray stripping using a stripping liquid (KANTO CHEMICAL co., inc. manufactured KP-301) at 60 ℃ for 2 minutes, thereby producing a circuit wiring a.

< measurement of resist line Width in exposed portion >

The manufactured substrate having the resin pattern was cut at a plane perpendicular to the line direction of the line pattern.

The cross section of the line pattern was observed from the cross-sectional side using a Scanning Electron Microscope (SEM), and the width of the resist was measured.

In the same sample as described above, the thickness of the layer in the unexposed portion was measured.

< evaluation >

-resolution evaluation-

A wiring sample from which the resist was peeled was produced by using a circuit wiring pattern mask having line & space widths of a plurality of widths in the same manner as described above. The wiring portion of the obtained wiring sample was observed with an optical microscope, and the resolution was evaluated based on the width of the finest thin wire recognized in the following evaluation criteria.

A: the width of the finest line is less than 6 μm

B: the width of the finest line is greater than 6 μm and less than 10 μm

C: the width of the finest line to be resolved is larger than 10 μm

Evaluation of straightness-

The width of the wiring at 20 randomly selected positions was measured for the wiring sample. A standard deviation σ is calculated from the obtained Line Width data, and a value obtained by multiplying the standard deviation σ by 3 is defined as LWR (Line Width Roughness) as an index of pattern linearity.

By definition, the smaller the LWR, the smaller the linewidth variation, and thus preferred.

A: LWR value of 200nm or less

B: LWR value of more than 200nm and less than 300nm

C: LWR values greater than 300nm

(example 10)

A substrate having a resin pattern and a circuit wiring a were produced in the same manner as in example 5, except that the exposure pattern with a line & space of 6 μm/6 μm was changed to the exposure pattern with a line & space of 8 μm/8 μm at the time of the above exposure.

Also, evaluation was performed in the same manner as in example 5.

(example 11)

A substrate having a resin pattern and a circuit wiring a were produced in the same manner as in example 5, except that the exposure pattern with a line & space of 6 μm/6 μm was changed to the exposure pattern with a line & space of 4 μm/4 μm at the time of the above exposure.

Also, evaluation was performed in the same manner as in example 5.

(example 12)

In the development, a substrate having a resin pattern and a circuit wiring a were produced in the same manner as in example 5 except that the development condition at 26 ℃ for 30 seconds was changed to the development condition at 30 ℃ for 30 seconds using a 1.0% aqueous solution of sodium carbonate to the development condition at 30 ℃ for 30 seconds.

Also, evaluation was performed in the same manner as in example 5.

[ Table 3]

As shown in Table 3, the etching patterns obtained by the method for producing a resin pattern and the wiring of a photosensitive transfer member in examples 1 to 12 were superior in resolution to the method for producing a resin pattern and the photosensitive transfer member in comparative examples 1 to 3.

As shown in table 3, the resin pattern production methods and the etched patterns obtained from the photosensitive transfer members of examples 1 to 12 were also excellent in linearity.

In addition, the invention of Japanese patent application No. 2020-017720, filed on 5/2/2020, is incorporated in its entirety by reference into this specification. All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for manufacturing a resin pattern, which uses a photosensitive transfer member having a temporary support and a photosensitive resin layer to form a resin pattern on a substrate,

in a cross section of the resin pattern in a width direction thereof, a pattern width of a portion of the resin pattern that contacts the substrate is greater than a pattern width of the resin pattern at a position 90% away from a maximum height of the substrate by 0.2 μm or more.

2. The method of manufacturing a resin pattern according to claim 1,

the thickness of the photosensitive resin layer is 8 [ mu ] m or less.

3. The method of manufacturing a resin pattern according to claim 1 or 2, wherein,

the thickness of the temporary support is 25 [ mu ] m or less.

4. The manufacturing method of a resin pattern according to any one of claims 1 to 3,

a value obtained by subtracting a pattern width at a position of 90% of the maximum height of the resin pattern from a pattern width of a portion of the resin pattern in contact with the substrate is 0.2 μm or more and 2.4 μm or less.

5. The method of manufacturing a resin pattern according to any one of claims 1 to 4,

the photosensitive resin layer contains a polymerizable compound and a binder polymer.

6. The method of manufacturing a resin pattern according to claim 5,

the ratio Mm/Mb of the content Mm of the polymerizable compound to the content Mb of the binder polymer in the photosensitive resin layer is 0.9 or less.

7. The method of manufacturing a resin pattern according to claim 5 or 6,

the polymerizable compound in the photosensitive resin layer contains a (meth) acrylic compound,

the content of the acrylic compound is 60 mass% or less with respect to the total mass of the (meth) acrylic compound contained in the photosensitive resin layer.

8. The manufacturing method of a resin pattern according to any one of claims 1 to 7,

the resin pattern to be produced includes a resin pattern having a pattern width of 6 μm or less.

9. A method for manufacturing a circuit wiring, comprising the steps of:

in the laminate having the resin pattern on the substrate manufactured by the method for manufacturing a resin pattern according to any one of claims 1 to 8, the substrate has a conductive layer on a surface on a side where the resin pattern is formed, and the conductive layer located in a region where the resin pattern is not arranged is subjected to etching treatment to form a circuit wiring.

10. A method for manufacturing a touch panel includes the steps of:

in the laminate having the resin pattern on the substrate manufactured by the method for manufacturing a resin pattern according to any one of claims 1 to 8, the substrate has a conductive layer on a surface on a side where the resin pattern is formed, and the conductive layer located in a region where the resin pattern is not arranged is subjected to etching treatment to form wiring for a touch panel.

11. A photosensitive transfer member having a temporary support and a photosensitive resin layer,

when a resin pattern A having a pattern width of 6 [ mu ] m is formed on a substrate at a position 90% of the maximum height of the substrate by the photosensitive transfer member, the pattern width of the resin pattern A at a portion in contact with the substrate in a cross section of the resin pattern A in the width direction is 6.2 [ mu ] m or more.