Photosensitive transfer material, method for manufacturing resin pattern, method for manufacturing circuit wiring, method for manufacturing electronic device, and method for manufacturing laminate

Abstract

The present application provides a photosensitive transfer material, and a method for manufacturing a laminate, a method for manufacturing a resin pattern using the photosensitive transfer material, an etching method, and a method for manufacturing an electronic device, the photosensitive transfer material having a temporary support and a photosensitive layer containing an ethylenically unsaturated compound, wherein the photosensitive layer is exposed to light with an energy density of 100 mJ / cm 2 In the case where the photosensitive layer is exposed, the ratio of the disappearance rate of the ethylenically unsaturated bond in the photosensitive layer before and after the photosensitive layer is peeled from the temporary support is 70% to 100%.

Description

Technical Field

[0001] This invention relates to a photosensitive transfer material, a method for manufacturing resin patterns, a method for manufacturing circuit wiring, a method for manufacturing electronic devices, and a method for manufacturing laminates. Background Technology

[0002] In display devices (such as organic electroluminescent (EL) display devices and liquid crystal display devices) with touch panels equipped with electrostatic capacitive input devices, conductive layer patterns such as electrode patterns of sensors that correspond to visual recognition parts, peripheral wiring parts, and wiring of lead-out wiring parts are provided inside the touch panel.

[0003] Typically, in the formation of patterned layers, since the number of steps required to obtain the desired pattern shape is small, the following method is widely used: a layer of photosensitive resin composition disposed on an arbitrary substrate using a photosensitive transfer material is exposed to a mask having the desired pattern and then developed.

[0004] Furthermore, as a conventional photosensitive resin laminate, the photosensitive resin laminate described in Japanese Patent Application Publication No. 2019-133143 is known.

[0005] Japanese Patent Application Publication No. 2019-133143 discloses a photosensitive resin laminate for exposure after a support film is peeled off. The laminate comprises: a support film; and a photosensitive resin composition layer disposed on the support film, containing the photosensitive resin composition. The photosensitive resin composition in the photosensitive resin laminate for exposure after the support film is peeled off contains: (A) an alkali-soluble polymer, (B) a compound reactive with a photoinitiator, and (C) a photoinitiator. A 0.4 mm thick copper-clad laminate with 35 μm rolled copper foil is jet-polished using #400 abrasive material, preheated to 60°C, and then laminated onto the copper-clad laminate using a hot roller laminator at a roller temperature of 105°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min. Exposure is then performed according to either condition (1) or condition (2).

[0006] (1) Expose the support film by using an exposure device with the focal point aligned with the surface of the support film, and peel the support film off from the exposed photosensitive resin composition layer.

[0007] (2) Peel off the support film, and then expose the area on the surface of the support film using an exposure device with the focal point aligned with the area on the surface of the exposure film.

[0008] In a resist pattern obtained by spraying a 1% Na₂CO₃ aqueous solution at 30°C for twice the minimum development time using a fine alkaline developer to remove unexposed areas, washing with pure water for the same duration as the development time, dehydrating with an air knife, and then drying with warm air, the difference between the minimum patternable independent fine line width of the first resist pattern obtained by exposure under the above conditions (1) and the second resist pattern obtained by exposure under the above conditions (2) is less than 5 μm.

[0009] The aforementioned exposure device is any one of the following:

[0010] (a) An exposure device with a peak wavelength of 350–370 nm for the exposure light;

[0011] (b) An exposure device with a peak wavelength of 400–410 nm for the exposure light;

[0012] (c) An exposure apparatus having peak wavelengths of 360–380 nm and 390–410 nm and a wavelength intensity ratio of 360–380 nm : 390–410 nm = 30 : 70; and

[0013] (d) Short arc mercury lamp. Summary of the Invention

[0014] The technical problem to be solved by the invention

[0015] One embodiment of the present invention aims to provide a photosensitive transfer material with excellent resolution even when the photosensitive layer is directly exposed without a temporary support.

[0016] Another embodiment of the present invention aims to provide a method for manufacturing a laminate with excellent resolution.

[0017] Furthermore, another embodiment of the present invention aims to solve the problem of providing a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing electronic devices.

[0018] means for solving technical problems

[0019] The solution to the above problem includes the following approach.

[0020] <1> A photosensitive transfer material comprising a temporary support and a transfer layer including a photosensitive layer containing an olefinic unsaturated compound, wherein a substrate having a metal layer on its surface is bonded to the transfer layer of the photosensitive transfer material, and the transfer is applied in air at 23°C and 1 atm using an ultra-high pressure mercury lamp at a wavelength of 365nm and an energy density of 100mJ / cm². 2When the above-mentioned photosensitive layer is exposed, the ratio of the olefin unsaturated bond disappearance rate D1 exposed without peeling off the above-mentioned temporary support to the olefin unsaturated bond disappearance rate D2 exposed after peeling off the above-mentioned temporary support, D2 / D1, is 70% to 100%.

[0021] <2> according to <1> The aforementioned photosensitive transfer material, wherein,

[0022] The oxygen permeability of the above transfer layer is 1 mL / (m 2 ·day·atm)~100mL / (m 2 ·day·atm).

[0023] <3> according to <1> or <2> The aforementioned photosensitive transfer material, wherein,

[0024] The aforementioned photosensitive layer contains a photoradical polymerization initiator.

[0025] <4> according to <3> The aforementioned photosensitive transfer material, wherein,

[0026] The aforementioned photoradical polymerization initiator is a photopolymerization initiator that generates one or more of methyl radicals or sulfur-containing radicals as polymerization initiation species.

[0027] <5> according to <1> to <4> In any one of the photosensitive transfer materials, wherein,

[0028] An intermediate layer is also provided between the temporary support and the photosensitive layer.

[0029] <6> according to <5> The aforementioned photosensitive transfer material, wherein,

[0030] The aforementioned intermediate layer contains water-soluble compounds.

[0031] <7> according to <6> The aforementioned photosensitive transfer material, wherein,

[0032] The aforementioned water-soluble compounds are selected from one or more compounds chosen from water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenolic derivatives, and amide compounds.

[0033] <8> according to <6> or <7> The aforementioned photosensitive transfer material, wherein,

[0034] The water-soluble compound mentioned above is polyvinyl alcohol.

[0035] <9> according to <8> The aforementioned photosensitive transfer material, wherein,

[0036] The degree of hydrolysis of the above-mentioned polyvinyl alcohol is 73 mol% to 99 mol%.

[0037] <10> according to <8> or <9> The aforementioned photosensitive transfer material, wherein,

[0038] The polyvinyl alcohol mentioned above contains ethylene as a monomer unit.

[0039] <11> according to <5> to <10> In any one of the photosensitive transfer materials, wherein,

[0040] The aforementioned intermediate layer contains an inorganic layered compound.

[0041] <12> according to <1> to <11> In any one of the photosensitive transfer materials, wherein,

[0042] The above-mentioned olefinic unsaturated compounds include polyfunctional olefinic unsaturated compounds.

[0043] <13> according to <1> to <12> In any one of the photosensitive transfer materials, wherein,

[0044] The above-mentioned olefinic unsaturated compounds include olefinic unsaturated compounds with more than 3 functions.

[0045] <14> according to <1> to <13> In any one of the photosensitive transfer materials, wherein,

[0046] The aforementioned olefinic unsaturated compounds include olefinic unsaturated compounds having a polyoxyethylene structure.

[0047] <15> A method for manufacturing a resin pattern, comprising the following steps:

[0048] make <1> to <14> The process of bonding the transfer layer in the photosensitive transfer material described in any one of the above steps to a substrate; and the process of performing exposure treatment and development treatment on the exposed photosensitive layer to form a pattern.

[0049] <16> A method for manufacturing circuit wiring, comprising the following steps:

[0050] make <1> to <14> The process of bonding the transfer layer of the photosensitive transfer material described in any one of the above steps to a substrate having a conductive layer; the process of performing exposure and development treatment on the exposed photosensitive layer to form a pattern; and the process of etching the substrate in the area where the resin pattern is not disposed.

[0051] <17> A method for manufacturing an electronic device, comprising the following steps:

[0052] make <1> to <14> The process of bonding the transfer layer of the photosensitive transfer material described in any one of the above steps to a substrate having a conductive layer; the process of performing exposure and development treatment on the exposed photosensitive layer to form a pattern; and the process of etching the substrate in the area where the resin pattern is not disposed.

[0053] <18> A method for manufacturing a laminate, comprising the following steps:

[0054] The lamination process involves bonding the transfer layer, which includes a temporary support and a transfer layer comprising a photosensitive layer containing an olefinically unsaturated compound, to a substrate to create a laminate. The peeling process involves peeling the temporary support from the laminate. The patterning process involves exposing and developing the exposed photosensitive layer to form a pattern, using an ultra-high pressure mercury lamp at 23°C and 1 atm of air with a wavelength of 365 nm and an energy density of 100 mJ / cm². 2 When exposure is performed, the ratio D4 / D3 of the olefin unsaturated bond disappearance rate D3 when the photosensitive layer of the laminate produced in the bonding process is exposed via the temporary support to the olefin unsaturated bond disappearance rate D4 when the photosensitive layer is exposed after the temporary support is peeled off in the peeling process is 80% to 100%.

[0055] Invention Effects

[0056] According to one embodiment of the present invention, a photosensitive transfer material with excellent resolution can be provided even when the photosensitive layer is directly exposed without a temporary support.

[0057] According to another embodiment of the present invention, a method for manufacturing a laminate with excellent resolution can be provided.

[0058] Furthermore, according to another embodiment of the present invention, a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing an electronic device can be provided. Attached Figure Description

[0059] Figure 1 This is a schematic diagram illustrating an example of the structure of a photosensitive transfer material.

[0060] Figure 2 This is a schematic top view representing pattern A.

[0061] Figure 3 This is a schematic top view representing pattern B. Detailed Implementation

[0062] The present invention will now be described. The description will be made with reference to the accompanying drawings, although symbols may sometimes be omitted.

[0063] In addition, in this specification, the numerical range indicated by “~” refers to the range included by taking the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0064] Furthermore, in this specification, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acryloyl" means either or both of acryloyl and methacryloyl.

[0065] Furthermore, in this specification, the amount of each component in the composition refers to the total amount of the corresponding multiple substances present in the composition, unless otherwise specified, when multiple substances equivalent to each component are present in the composition.

[0066] In this specification, the term "process" refers not only to an independent process, but also to any process that achieves its intended purpose, even if it cannot be clearly distinguished from other processes.

[0067] In the designation of groups (atomic groups) in this specification, the designations without indicating whether they are substituted or unsubstituted include both unsubstituted and substituted groups. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0068] Unless otherwise specified, in this specification, "exposure" includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used in exposure include bright-line spectra of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and active light rays (active energy rays) such as electron beams.

[0069] Furthermore, the chemical structural formulas in this specification are sometimes described as simplified structural formulas with the hydrogen atom omitted.

[0070] In this invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0071] Furthermore, in this invention, a combination of two or more preferred methods is a more preferred method.

[0072] Furthermore, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this invention are obtained as follows: using a gel permeation chromatography (GPC) analysis apparatus with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by TOSOHCORPORATION), detection is performed using the solvent THF (tetrahydrofuran) and a differential refractometer, and polystyrene is used as a standard substance for conversion.

[0073] In this specification, "total solids content" refers to the total mass of the components after removing the solvent from the overall composition of the composition. Furthermore, as mentioned above, "solids content" refers to the components after removing the solvent, which may be solid or liquid at 25°C.

[0074] (Photosensitive transfer material)

[0075] The photosensitive transfer material of this invention comprises a temporary support and a transfer layer including a photosensitive layer containing an olefinically unsaturated compound. In this photosensitive transfer material, a substrate with a metal layer on its surface is bonded to the transfer layer. The transfer is then applied in air at 23°C and 1 atm using an ultra-high pressure mercury lamp with an energy density of 100 mJ / cm² at a wavelength of 365 nm. 2 When the above-mentioned photosensitive layer is exposed, the ratio of the olefin unsaturated bond disappearance rate D1 exposed without peeling off the above-mentioned temporary support to the olefin unsaturated bond disappearance rate D2 exposed after peeling off the above-mentioned temporary support, D2 / D1, is 70% to 100%.

[0076] Furthermore, examples of layers included in the aforementioned transfer layer include a photosensitive layer, an intermediate layer (described later), and a thermoplastic resin layer (described later). The temporary support and the transfer film (described later) are not included in the aforementioned transfer layer.

[0077] The inventors have discovered that in the wiring process using conventional photosensitive transfer materials, when the temporary support is peeled off and the photosensitive layer attached to the substrate is exposed, oxygen present in the atmosphere permeates into the photosensitive layer, causing polymerization obstacles and reducing resolution.

[0078] Through careful research, the inventors discovered that by adopting the above-described manner, excellent resolution is achieved even when the photosensitive layer is directly exposed without a temporary support.

[0079] In the photosensitive transfer material of the present invention, a substrate having a metal layer on its surface is bonded to the transfer layer of the photosensitive transfer material in a photosensitive layer containing an olefinic unsaturated compound. The transfer layer is then subjected to an ultra-high pressure mercury lamp at a wavelength of 365 nm and an energy density of 100 mJ / cm² in air at 23°C and 1 atm. 2 When the above-mentioned photosensitive layer is exposed, the ratio of the disappearance rate of olefin unsaturated bonds D1 when exposed without peeling off the temporary support to the disappearance rate of olefin unsaturated bonds D2 when exposed after peeling off the temporary support, D2 / D1, is 70% to 100%. Thus, although the detailed mechanism is not yet clear, it is possible to produce a photosensitive layer that is not easily hindered by oxygen, and the resolution is excellent even when the photosensitive layer is directly exposed without passing through the temporary support.

[0080] <Ratio of the disappearance rate of olefinic unsaturated bonds D2 / D1>

[0081] In the photosensitive transfer material of this invention, a substrate with a metal layer on its surface is bonded to the transfer layer of the photosensitive transfer material. The transfer is performed in air at 23°C and 1 atmosphere using an ultra-high pressure mercury lamp with an energy density of 100 mJ / cm² at a wavelength of 365 nm. 2 When the photosensitive layer is exposed, the ratio D2 / D1 of the disappearance rate of olefin unsaturated bonds exposed without stripping the temporary support to the disappearance rate D2 of olefin unsaturated bonds exposed after stripping the temporary support is 70% to 100%. From the viewpoint of resolution (hereinafter referred to as "resolution") and pattern forming properties when the photosensitive layer is exposed directly without passing through the temporary support, it is preferably 80% to 100%, more preferably 85% to 100%, further preferably 90% to 100%, and especially preferably 95% to 100%.

[0082] The following methods are preferred as methods for determining and calculating the values ​​of D1, D2, and D2 / D1 in this invention.

[0083] A copper-coated PET substrate was fabricated on a 100μm thick polyethylene terephthalate (PET) film using a sputtering method to create a copper layer with a thickness of 200nm.

[0084] The prepared photosensitive transfer material was laminated onto the copper-coated PET substrate under lamination conditions of 100°C roller temperature, 1.0 MPa linear pressure, and 4.0 m / min linear speed.

[0085] In the D1 measurement, the temporary support was not peeled off from the laminated substrate, but instead placed on the substrate stage of a projection exposure machine (Ushio Inc. UX-2023SM). A glass chromium photomask with a line and space pattern (duty cycle 1:1, linewidth varying in 1μm increments from 1μm to 10μm) was placed on the mask holder of the exposure machine, and the photomask was exposed at an exposure dose of 100mJ / cm² through a projection lens. 2 To expose it.

[0086] In the D2 measurement, a temporary support was peeled off from the laminated substrate and placed on the substrate stage of a projection exposure machine (Ushio Inc. UX-2023SM). A glass chromium photomask with a line and space pattern (duty cycle 1:1, linewidth varying in 1μm increments from 1μm to 10μm) was placed on the mask holder of the exposure machine. The photomask was then exposed to a projection lens at an exposure dose of 100mJ / cm². 2 Exposure was performed 10 minutes after the temporary support was removed.

[0087] The determination of the disappearance rate of olefinic unsaturated bonds was carried out after exposure and storage in air at 1 atmosphere, 23°C, and 55% RH for 3 hours.

[0088] The disappearance rate of olefinic unsaturated bonds (C=C disappearance rate) was determined by the following method.

[0089] In the determination of the disappearance rate of olefinic unsaturated bonds in samples with an intermediate layer, the photosensitive layer exposed after wiping away the intermediate layer with water was used.

[0090] A Bruker Optics LUMOS (fully automated Fourier transform infrared (FT-IR) microscope) was used with an MCT (mercury cadmium telluride) detector and a wavenumber and resolution of 4 cm⁻¹. -1 A total of 32 total internal reflection (ATR) measurements were performed (Ge crystallization). The C=C stretching ratio (1,635 cm⁻¹) was calculated from the exposed and unexposed samples. -1 The peak height (after background processing) is scaled using CH (2,900cm). -1 The value obtained by standardizing the peak height of the samples is used to set the ratio of exposed samples to unexposed samples as the olefin unsaturated bond disappearance rate (C=C residual rate). The C=C disappearance rate is calculated by 1-(C=C residual rate).

[0091] Furthermore, when the photosensitive transfer material has a protective film described later, the protective film is peeled off before bonding with the aforementioned substrate in the determination of the disappearance rate of olefinic unsaturated bonds.

[0092] There are no particular limitations on the methods for increasing the D2 / D1 value. Examples include methods that use an intermediate layer or other layers that function as an oxygen barrier, or methods that use free radicals that are not easily deactivated as the free radicals that are photoradical polymerization initiators (e.g., methyl radicals, sulfur-containing radicals, etc.).

[0093] <Oxygen permeability of the photosensitive layer>

[0094] From the viewpoint of resolution and pattern formation, the oxygen permeability of the transfer layer in the photosensitive transfer material of the present invention is preferably 20,000 mL / (m²). 2 ·day·atm) or less, more preferably 5,000mL / (m 2 ·day·atm) or less, more preferably 1,000mL / (m 2 ·day·atm) or less, especially preferably 1mL / (m 2 ·day·atm)~100mL / (m 2 ·day·atm).

[0095] Oxygen permeability was measured as follows.

[0096] A photosensitive transfer material was laminated onto a cellulose triacetate (TAC) substrate (40 μm thick) from the photosensitive layer side under lamination conditions of 100°C roller temperature, 1.0 MPa linear pressure, and 4.0 m / min linear speed. A temporary support was then peeled off to prepare the test sample. The test sample was attached to the electrode area via silicone grease, and the measurement environment was adjusted to 23°C and 50% RH. The oxygen permeability coefficient (i.e., oxygen permeability) was determined from the amount of oxygen reaching the electrode under steady-state conditions (Apparatus: oxygen meter, e.g., Hach UltraAnalytics, Inc. Oxygen Meter MODEL3600).

[0097] There are no particular limitations on the method for adjusting the oxygen permeability of the transfer layer to the range described above. Examples include methods such as having an intermediate layer or other layers as an oxygen barrier layer in addition to the photosensitive layer, adding an inorganic layered compound to the intermediate layer, or including a water-soluble compound with low oxygen permeability, preferably a water-soluble resin, in the intermediate layer.

[0098] The photosensitive transfer material involved in this invention has a temporary support and a photosensitive layer in sequence, and preferably has a temporary support, a photosensitive layer and a protective film in sequence.

[0099] Furthermore, the photosensitive transfer material involved in this invention may have other layers between the temporary support and the photosensitive layer, or between the photosensitive layer and the protective film.

[0100] Furthermore, the photosensitive transfer material involved in this invention preferably has an intermediate layer between the temporary support and the photosensitive layer.

[0101] From the viewpoint of further maximizing the effects of the present invention, the photosensitive transfer material involved in the present invention is preferably a roller-shaped photosensitive transfer material.

[0102] The following illustrates one example of the photosensitive transfer material involved in the present invention, but is not limited thereto.

[0103] (1) "Temporary support / photosensitive layer / refractive index adjustment layer / protective film"

[0104] (2) "Temporary support / photosensitive layer / protective film"

[0105] (3) "Temporary support / intermediate layer / photosensitive layer / protective film"

[0106] (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer / protective film"

[0107] Furthermore, in the above structures, the photosensitive layer is preferably a negative photosensitive layer. Also, the photosensitive layer is preferably a colored resin layer. The photosensitive transfer material according to the present invention is preferably used as a photosensitive transfer material for etching resist.

[0108] When the photosensitive transfer material is used as an etch resist, the structure of the photosensitive transfer material is preferably, for example, the structure of (2) to (4) described above.

[0109] In a photosensitive transfer material, where the photosensitive layer has other layers on the side opposite to the temporary support, the total thickness of the other layers disposed on the side opposite to the temporary support of the photosensitive layer is preferably 0.1% to 30% relative to the thickness of the photosensitive layer, more preferably 0.1% to 20%.

[0110] The following is an example of a specific embodiment to illustrate the photosensitive transfer material involved in the present invention.

[0111] The following example illustrates the use of photosensitive transfer materials.

[0112] Figure 1 The photosensitive transfer material 20 shown has a temporary support 11, a transfer layer 12 comprising a thermoplastic resin layer 13, an intermediate layer 15 and a photosensitive layer 17, and a protective film 19.

[0113] and, Figure 1 The photosensitive transfer material 20 shown is configured with a thermoplastic resin layer 13 and an intermediate layer 15, but it is also possible to omit the thermoplastic resin layer 13 and the intermediate layer 15.

[0114] The following describes the components that constitute photosensitive transfer materials.

[0115] [Temporary support]

[0116] The photosensitive transfer material used in this invention has a temporary support.

[0117] The temporary support is a support that supports the photosensitive layer or a laminate containing the photosensitive layer and is peelable.

[0118] From the viewpoint that exposure of the photosensitive layer through the temporary support is possible during pattern exposure of the photosensitive layer, the temporary support preferably has light transmittance. Furthermore, in this specification, "having light transmittance" means that the transmittance of light of the wavelength used in pattern exposure is 50% or more.

[0119] From the viewpoint of improving the exposure sensitivity of the photosensitive layer, the transmittance of light at the wavelength (more preferably 365 nm) used in pattern exposure by the temporary support is preferably 60% or more, and more preferably 70% or more.

[0120] Furthermore, the transmittance of a layer in a photosensitive transfer material is the ratio of the intensity of the emitted light to the intensity of the incident light when light is incident along a direction perpendicular to the main surface of the layer (thickness direction), and is measured using an MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0121] Materials that constitute a temporary support include, for example, glass substrates, resin films and paper, with resin films being preferred from the viewpoints of strength, flexibility and light transmittance.

[0122] Examples of resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, PET films are preferred, and biaxially stretched PET films are more preferred.

[0123] There are no particular restrictions on the thickness (layer thickness) of the temporary support. From the viewpoints of the strength of the support, the flexibility required in bonding with the substrate for forming circuit wiring, and the light transmittance required in the initial exposure process, the material can be selected accordingly.

[0124] The thickness of the temporary support is preferably in the range of 5μm to 100μm, and more preferably in the range of 10μm to 50μm for ease of operation and versatility, even more preferably in the range of 10μm to 20μm, and especially preferably in the range of 10μm to 16μm.

[0125] Furthermore, from the viewpoint of defect suppression, resolution, and linearity of the resin pattern, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, and especially preferably 20 μm or less.

[0126] Furthermore, it is preferable that the membrane used as a temporary support is free from deformations such as wrinkles, scratches, and defects.

[0127] From the viewpoint of pattern formation properties during pattern exposure via a temporary support and the transparency of the temporary support, it is preferable that the temporary support contains a small number of particles, foreign matter, defects, precipitates, etc. Regarding the number of particles, foreign matter, and defects with a diameter of 1 μm or larger, it is preferably 50 per 10 mm. 2 The following is more preferably 10 per 10mm 2 The following is a further preferred option: 3 per 10mm 2 The following is particularly preferred: 0 per 10mm 2 .

[0128] From the viewpoints of defect suppression, resolution, and transparency of the temporary support, it is preferable that the temporary support has low haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, even more preferably less than 1.0%, and particularly preferably 0.5% or less.

[0129] The haze value in this invention is measured using a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.) according to the method of JIS K 7105:1981.

[0130] From an operational perspective, a layer containing microparticles (lubricant layer) can be provided on the surface of the temporary support. The lubricant layer can be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be set, for example, from 0.05 μm to 0.8 μm. Furthermore, the thickness of the lubricant layer can be set, for example, from 0.05 μm to 1.0 μm.

[0131] From the viewpoints of transportability, resin pattern defect suppression, and resolution, the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is preferably at least Ra.

[0132] From the viewpoints of transportability, resin pattern defect suppression, and resolution, the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 20 nm or less, and especially preferably 10 nm or less.

[0133] From the viewpoints of peelability of the temporary support, defect suppression of the resin pattern, and resolution, the arithmetic mean roughness Ra of the surface of the photosensitive layer side in the temporary support is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 20 nm or less, and especially preferably 10 nm or less.

[0134] Furthermore, from the viewpoints of transportability, resin pattern defect suppression, and resolution, the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is preferably 0 nm to 10 nm, more preferably 0 nm to 5 nm.

[0135] The arithmetic mean roughness Ra of the surface of the temporary support or protective film in this invention is determined by the following method.

[0136] Using a three-dimensional optical profilometer (New View 7300, manufactured by Zygo Corporation), the surface profile of a temporary support or protective film is measured under the following conditions to obtain the surface profile of the film.

[0137] The measurement and analysis software used was the Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen was displayed using the aforementioned analysis software, and histogram data was obtained from the Surface Map screen. The arithmetic mean roughness was calculated based on the obtained histogram data to obtain the Ra value of the surface of the temporary support or protective film.

[0138] When a temporary support or protective film is attached to a photosensitive layer, the temporary support or protective film can be peeled off from the photosensitive layer, and the Ra value of the surface on the peeled side can be measured.

[0139] From the viewpoint of inhibiting the peeling of the temporary support caused by the adhesion between the upper and lower laminates when the laminate is re-wound by a roll-to-roll method, the peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive layer or thermoplastic resin layer, is preferably 0.5 mN / mm or more, more preferably 0.5 mN / mm to 2.0 mN / mm.

[0140] The peeling force of the temporary support in this invention was measured as follows.

[0141] A copper layer with a thickness of 200 nm was fabricated on a 100 μm thick polyethylene terephthalate (PET) film by sputtering, and a PET substrate with the copper layer was then fabricated.

[0142] The protective film is peeled off from the prepared photosensitive transfer material and laminated onto the aforementioned copper-coated PET substrate under lamination conditions of 100°C lamination roller temperature, 0.6 MPa linear pressure, and 1.0 m / min linear speed (lamination speed). Next, after applying adhesive tape (NITTO DENKO CORPORATION. PRINTACK) to the surface of the temporary support, the laminate containing at least the temporary support and photosensitive layer on the copper-coated PET substrate is cut into 70 mm × 10 mm pieces to create a sample. The PET substrate side of the sample is then fixed onto a sample stage.

[0143] Using a tensile compression tester (IMADA-SS Corporation, SV-55), the tape is stretched at 5.5 mm / s along a 180-degree direction to peel it from the photosensitive layer or thermoplastic resin layer to the temporary support, and the force required for peeling (peel force) and adhesion force are measured.

[0144] Preferred methods for temporary supports are described, for example, in paragraphs 0017-0018 of Japanese Patent Application Publication No. 2014-85643, paragraphs 0019-0026 of Japanese Patent Application Publication No. 2016-27363, paragraphs 0041-0057 of International Publication No. 2012 / 081680, paragraphs 0029-0040 of International Publication No. 2018 / 179370, and paragraphs 0012-0032 of Japanese Patent Application Publication No. 2019-101405, the contents of which are incorporated herein by reference.

[0145] [Photosensitive layer]

[0146] The photosensitive transfer material involved in this invention has a photosensitive layer containing an olefinic unsaturated compound.

[0147] The photosensitive layer is preferably a negative photosensitive layer.

[0148] The photosensitive layer preferably comprises an alkali-soluble resin, an olefin unsaturated compound, and a photopolymerization initiator. More preferably, based on the total mass of the photosensitive layer, it comprises: alkali-soluble resin: 10% to 90% by mass; olefin unsaturated compound: 5% to 70% by mass; and photopolymerization initiator: 0.01% to 20% by mass.

[0149] The following is a description of each component.

[0150] <Alkene unsaturated compounds>

[0151] The photosensitive layer contains olefinic unsaturated compounds.

[0152] An olefin unsaturated compound is a compound having one or more olefin unsaturated groups.

[0153] There are no particular limitations on the olefinic unsaturated groups present in olefinic unsaturated compounds. Examples include vinyl, acryloyl, methacryloyl, acrylamide, methacrylamido, styrene, allyl, and maleimide.

[0154] As an olefinic unsaturated group, it is preferably acryloyl, methacryloyl, acrylamide, methacrylamide, or styryl, more preferably acryloyl or methacryloyl.

[0155] Furthermore, as an olefinic unsaturated compound, it preferably contains a (meth)acrylate compound.

[0156] From the viewpoint of resolution and pattern formation, the photosensitive layer preferably contains olefinic unsaturated compounds with two or more functions (polyfunctional olefinic unsaturated compounds), and more preferably contains olefinic unsaturated compounds with three or more functions.

[0157] Here, "a 2 or more functional olefin unsaturated compounds" refers to compounds having two or more olefin unsaturated groups in one molecule.

[0158] Furthermore, from the viewpoint of excellent resolution and exfoliation properties, the number of olefinic unsaturated groups in a molecule of an olefinic unsaturated compound is preferably 6 or less.

[0159] From the perspective of achieving a better balance between photosensitivity, resolution, and peelability of the photosensitive layer, the photosensitive layer preferably contains a difunctional or trifunctional olefin unsaturated compound, and more preferably contains a difunctional olefin unsaturated compound.

[0160] From the perspective of excellent peelability, the content of difunctional or trifunctional olefinic unsaturated compounds in the photosensitive 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 total content of olefinic unsaturated compounds. There is no particular limit to the upper limit, and it can be 100% by mass. That is, all the olefinic unsaturated compounds contained in the photosensitive layer can be difunctional olefinic unsaturated compounds.

[0161] From the viewpoint of resolution and pattern formation, the photosensitive layer preferably contains an olefin unsaturated compound having a polyoxyalkylene structure, and more preferably contains an olefin unsaturated compound having a polyoxyethylene structure.

[0162] Examples of olefinic unsaturated compounds having a polyepoxide structure include polyalkylene glycol di(meth)acrylate and epoxide-modified compounds, which are described later.

[0163] -Alkene unsaturated compound B1-

[0164] The photosensitive layer preferably contains an olefinic unsaturated compound B1 having an aromatic ring and two olefinic unsaturated groups. The olefinic unsaturated compound B1 is a difunctional olefinic unsaturated compound having one or more aromatic rings in one molecule, as described above.

[0165] From the perspective of superior resolution, the mass ratio of the content of the olefinically unsaturated compound B1 in the photosensitive layer to the content of the olefinically unsaturated compound is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more. There is no particular limitation on the upper limit, but from the perspective of peelability, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0166] The aromatic rings present in the olefinically unsaturated compound B1 can include, for example, aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings, as well as their fused rings, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. Furthermore, the aforementioned aromatic rings may also have substituents.

[0167] The olefinic unsaturated compound B1 can have only one aromatic ring or more than two aromatic rings.

[0168] From the perspective of improving resolution by suppressing the swelling of the photosensitive layer caused by the developer, the olefinic unsaturated compound B1 preferably has a bisphenol structure.

[0169] Examples of bisphenol structures include, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0170] As an olefinic unsaturated compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0171] The two ends of the bisphenol structure and the two polymerizable groups can be directly bonded, or they can be bonded via one or more alkylene oxides. Ethylene oxides or propylene oxides are preferred as the alkylene oxides added to the two ends of the bisphenol structure, with ethylene oxide being more preferred. There is no particular limitation on the number of alkylene oxides added to the bisphenol structure, but 4 to 16 are preferred per molecule, with 6 to 14 being more preferred.

[0172] The olefinic unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated into this specification.

[0173] As the olefinic unsaturated compound B1, it is preferably a difunctional olefinic unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane.

[0174] Examples of 2,2-bis(4-((methacryloyloxypolyalkoxy)phenyl)propane include, for instance, 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentathoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.). 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0175] As an olefinic unsaturated compound B1, compounds represented by the following formula (Bis) can be used.

[0176] [Chemical Formula 1]

[0177]

[0178] In formula (Bis), R1 and R2 independently represent hydrogen atoms or methyl groups, A is C2H4, B is C3H6, n1 and n3 are independent integers from 1 to 39 and n1+n3 is an integer from 2 to 40, n2 and n4 are independent integers from 0 to 29 and n2+n4 is an integer from 0 to 30, and the repeating units of -(AO)- and -(BO)- can be arranged randomly or in blocks. Moreover, in the case of blocks, either -(AO)- or -(BO)- can be on the bisphenol structure side.

[0179] In one embodiment, n1+n2+n3+n4 is preferably an integer from 2 to 20, more preferably an integer from 2 to 16, and even more preferably an integer from 4 to 12. Furthermore, n2+n4 is preferably an integer from 0 to 10, more preferably an integer from 0 to 4, even more preferably an integer from 0 to 2, and particularly preferably 0.

[0180] The olefinic unsaturated compound B1 can be used alone or in combination with two or more compounds.

[0181] From the perspective of superior resolution, the content of the olefinic unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the photosensitive layer. There is no particular limit to the upper limit, but from the perspective of transferability and edge melting (the phenomenon of components in the photosensitive layer seeping out from the ends of the photosensitive transfer material), it is preferably 70% by mass or less, more preferably 60% by mass or less.

[0182] The photosensitive layer may also contain olefin unsaturated compounds other than the aforementioned olefin unsaturated compound B1.

[0183] There are no particular restrictions on olefin unsaturated compounds other than olefin unsaturated compound B1, and appropriate choices can be made from known compounds. For example, compounds having one olefin unsaturated group in one molecule (monofunctional olefin unsaturated compounds), difunctional olefin unsaturated compounds without an aromatic ring, and olefin unsaturated compounds with three or more functions can be cited.

[0184] Examples of monofunctional alkenyl unsaturated compounds include, for example, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0185] Examples of difunctional olefinic unsaturated compounds that do not have an aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.

[0186] Examples of alkylene glycol di(meth)acrylates include, for example, tricyclodecanediethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0187] Examples of polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0188] Examples of urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available examples include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0189] Examples of olefinic unsaturated compounds with more than three functions include, for example, pentaerythritol (tris / tetra / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, and their epoxide-modified forms.

[0190] Here, "(tri / tetra / penta / hexa)meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the photosensitive layer preferably includes the above-mentioned olefin unsaturated compound B1 and olefin unsaturated compounds with 3 or more functions, more preferably it includes the above-mentioned olefin unsaturated compound B1 and two or more olefin unsaturated compounds with 3 or more functions. In this case, the mass ratio of olefin unsaturated compound B1 to olefin unsaturated compounds with 3 or more functions is preferably (total mass of olefin unsaturated compound B1) : (total mass of olefin unsaturated compounds with 3 or more functions) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0191] Furthermore, in one embodiment, the photosensitive layer preferably comprises the aforementioned olefinic unsaturated compound B1 and two or more trifunctional olefinic unsaturated compounds.

[0192] Examples of epoxide-modified compounds that are trifunctional or higher-functionalized olefinic unsaturated compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), ethoxylated glycerol triacrylates (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), and ARONIX. M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0193] Furthermore, as an olefinic unsaturated compound other than olefinic unsaturated compound B1, an olefinic unsaturated compound having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 may be used.

[0194] From the viewpoint of resolution and linearity, the ratio of the content of the olefinic unsaturated compound Mm in the photosensitive layer to the content of the alkali-soluble resin Mb, Mm / Mb, is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.

[0195] Furthermore, from the viewpoint of curability and resolution, the olefinic unsaturated compound in the photosensitive layer preferably includes (meth)propylene oxide.

[0196] Furthermore, from the viewpoints of curability, resolution, and linearity, the olefinic unsaturated compound in the photosensitive layer more preferably includes (meth)propene oxide, and the content of the propene oxide is 60% by mass or less relative to the total mass of the aforementioned (meth)propene oxide contained in the photosensitive layer.

[0197] The molecular weight (in the case of a distribution, the weight-average molecular weight (Mw)) of the olefinic unsaturated compound containing olefinic unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0198] Alkenes can be used alone or in combination with two or more.

[0199] The content of olefinic unsaturated compounds in the photosensitive layer relative to the total mass of the photosensitive layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass.

[0200] Photopolymerization initiators

[0201] The photosensitive layer preferably contains a photopolymerization initiator.

[0202] Photopolymerization initiators are compounds that initiate the polymerization of olefinic unsaturated compounds upon exposure to active light sources such as ultraviolet light, visible light, and X-rays. There are no particular limitations on photopolymerization initiators; any known photopolymerization initiator can be used.

[0203] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators.

[0204] From the viewpoint of resolution and pattern formation, the photosensitive layer is preferably a photoradical polymerization initiator.

[0205] Furthermore, from the viewpoint of resolution and pattern formation, the photoradical polymerization initiator is preferably a photopolymerization initiator that generates either methyl radicals (·CH3) or sulfur-containing radicals (·SR) as polymerization initiators. From the viewpoint of reactivity, it is more preferably a photopolymerization initiator that generates methyl radicals as polymerization initiators. From the viewpoint of ease of preparation, it is more preferably a photopolymerization initiator that generates sulfur-containing radicals as polymerization initiators. Additionally, there are no particular limitations on the aforementioned R that forms sulfur-containing radicals, but from the viewpoint of reactivity, alkyl groups are preferred.

[0206] Oxime acetate compounds are preferred examples of polymerization initiators, specifically photopolymerization initiators that generate methyl radicals.

[0207] Furthermore, as a polymerization initiator, a combination of a photopolymerization initiator and a thiol compound can be cited as an example of a photopolymerization initiator that generates sulfur-containing free radicals.

[0208] There are no particular limitations on the thiol compound used, and well-known thiol compounds can be preferred as chain transfer agents.

[0209] Examples of photoradical polymerization initiators include, for example, photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having an acylphosphine oxide structure, photopolymerization initiators having an N-phenylglycine structure, and bimidazole compounds.

[0210] As a photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-14783 can be used.

[0211] Examples of photoradical polymerization initiators include, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl)anisyl ester, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0212] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(o-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), and 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (trade name: Omnirad). 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: emnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (trade name: Iunar 6, manufactured by DKSH Holding Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (trade name: B-CIM, manufactured by Hampford) and 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0213] Photocationic polymerization initiators (photoacid generators) are compounds that generate acids upon receiving active light. Preferably, these initiators are compounds that generate acids upon receiving active light with a wavelength of 300 nm or higher, particularly 300–450 nm, but their chemical structure is not limited. Furthermore, for photocationic polymerization initiators that do not directly receive active light with a wavelength of 300 nm or higher, as long as they are compounds that generate acids upon receiving active light with a wavelength of 300 nm or higher through use in conjunction with a sensitizer, they can be used in combination with the sensitizer and are preferred.

[0214] As a photocationic polymerization initiator, a photocationic polymerization initiator that produces acids with a pKa of 4 or less is preferred, a photocationic polymerization initiator that produces acids with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that produces acids with a pKa of 2 or less is particularly preferred. There is no particular specification regarding the lower limit value of pKa; for example, -10.0 or higher is preferred.

[0215] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0216] Examples of ionic photocationic polymerization initiators include, for example, onium salts such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts.

[0217] As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 may be used.

[0218] Examples of nonionic photocationic polymerization initiators include trichloromethyltriazine derivatives, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among the trichloromethyltriazine derivatives, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 can be used. Furthermore, among the oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640 can be used.

[0219] The photosensitive layer may contain one type of photopolymerization initiator or two or more types.

[0220] There is no particular limitation on the content of the photopolymerization initiator in the photosensitive layer, but it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total mass of the photosensitive layer. There is no particular limitation on the upper limit, but it is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive layer.

[0221] Alkali-soluble resins

[0222] The photosensitive layer preferably contains an alkali-soluble resin.

[0223] In addition, in this specification, "alkali solubility" means that the solubility of sodium carbonate in 100g of a 1% by mass aqueous solution is greater than 0.1g at a liquid temperature of 22°C.

[0224] There are no particular limitations on the type of alkali-soluble resin used; for example, well-known alkali-soluble resins used in etching resists are preferred.

[0225] Furthermore, the alkali-soluble resin is preferably an adhesive polymer.

[0226] As an alkali-soluble resin, an alkali-soluble resin having acid groups is preferred.

[0227] Among them, polymer A, which will be described later, is preferred as an alkali-soluble resin.

[0228] -Polymer A-

[0229] As an alkali-soluble resin, it preferably contains polymer A.

[0230] From the perspective of achieving better resolution by suppressing the swelling of the photosensitive layer caused by the developer, the acid value of polymer A is preferably less than 220 mg KOH / g, more preferably less than 200 mg KOH / g, and even more preferably less than 190 mg KOH / g.

[0231] There is no particular limitation on the lower limit of the acid value of polymer A, but from the perspective of better developability, it is preferred to be 60 mg KOH / g or more, more preferably 120 mg KOH / g or more, further preferably 150 mg KOH / g or more, and especially preferably 170 mg KOH / g or more.

[0232] Additionally, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1g of the sample.

[0233] In this specification, the unit is stated as mgKOH / g. Acid value can be calculated, for example, based on the average content of acid groups in the compound.

[0234] The acid value of polymer A can be adjusted according to the types of structural units that make up polymer A and the content of structural units containing acid groups.

[0235] The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, it is preferable to set the weight-average molecular weight to 500,000 or less. More preferably, it is preferable to set the weight-average molecular weight to 100,000 or less, even more preferably, it is preferable to set it to 60,000 or less, and especially preferably, it is preferable to set it to 50,000 or more. On the other hand, from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film, such as edge melting and chipping, when forming a photosensitive resin laminate, it is preferable to set the weight-average molecular weight to 5,000 or more. More preferably, it is preferable to set the weight-average molecular weight to 10,000 or more, even more preferably, it is preferable to set it to 20,000 or more, and especially preferably, it is preferable to set it to 30,000 or more. Edge melting refers to the ease with which the photosensitive layer overflows from the end face of the roller when the photosensitive transfer material is rolled into a roll. Chipping refers to the ease with which chips splatter when the unexposed film is cut with a knife. If the chips adhere to the upper surface of the photosensitive resin laminate, they will be transferred to the mask in subsequent exposure processes, resulting in defective products. The dispersibility of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. In this invention, the molecular weight is a value obtained by gel permeation chromatography. Furthermore, the dispersibility is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0236] From the viewpoint of suppressing linewidth thickening or resolution degradation due to focus position shift during exposure, the photosensitive layer preferably contains a monomeric component having aromatic hydrocarbons as polymer A. Examples of such aromatic hydrocarbons include substituted or unsubstituted phenyl groups or substituted or unsubstituted aralkyl groups. Regarding the proportion of the monomeric component having aromatic hydrocarbons in polymer A, based on the total mass of the total monomeric components, it is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. There is no particular upper limit, but it is preferably 95% by mass or less, more preferably 85% by mass or less. Furthermore, the proportion of the monomeric component having aromatic hydrocarbons when multiple polymers A are contained is calculated as a weight average.

[0237] Examples of aromatic hydrocarbon monomers include, for example, aralkyl monomers, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, styrene trimers, etc.). Among these, aralkyl monomers or styrene are preferred. In one embodiment, when the aromatic hydrocarbon monomer component in polymer A is styrene, the styrene monomer content is preferably 20% to 50% by mass, more preferably 25% to 45% by mass, further preferably 30% to 40% by mass, and particularly preferably 30% to 35% by mass, based on the total mass of the total monomer components.

[0238] Examples of aryl alkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl) or substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0239] Examples of monomers containing phenyl alkyl groups include phenylethyl (meth)acrylate.

[0240] Examples of monomers containing a benzyl group include (meth)acrylates, such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; and vinyl monomers containing a benzyl group, such as vinyl benzyl chloride and vinyl benzyl alcohol. Benzyl (meth)acrylate is preferred. In one embodiment, when the aromatic hydrocarbon monomer component in polymer A is benzyl (meth)acrylate, the content of the benzyl (meth)acrylate monomer component is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, further preferably 70% to 90% by mass, and particularly preferably 75% to 90% by mass, based on the total mass of the total monomer components.

[0241] Polymer A containing a monomer component having aromatic hydrocarbons is preferably obtained by polymerizing a monomer having aromatic hydrocarbons with at least one of the first monomers described later and / or at least one of the second monomers described later.

[0242] Polymer A, which does not contain monomeric components with aromatic hydrocarbons, is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0243] The first monomer is a monomer having a carboxyl group in its molecule. Examples of first monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half-ester. Among these, (meth)acrylic acid is preferred.

[0244] Based on the total mass of the total monomer components, the content of the first monomer in polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass.

[0245] Based on the total mass of the total monomer components, the copolymerization ratio of the first monomer is preferably 10% to 50% by mass. From the viewpoints of exhibiting good developability and controlling edge melting, it is preferable to set the above copolymerization ratio to 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. From the viewpoints of high resolution and curled edge shape of the resist pattern, and further from the viewpoints of chemical resistance of the resist pattern, it is preferable to set the above copolymerization ratio to 50% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 27% by mass or less.

[0246] The second monomer is a non-acidic monomer that has at least one polymerizable unsaturated group in its molecule. Examples of second monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, etc. (meth)acrylates; vinyl acetate and other vinyl alcohol esters; and (meth)acrylonitrile, etc. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, and n-butyl methacrylate are preferred, and methyl methacrylate is particularly preferred.

[0247] Based on the total mass of the total monomer components, the content of the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass.

[0248] From the viewpoint of suppressing linewidth thickening or resolution degradation due to focus position shift during exposure, monomers containing aralkyl groups and / or styrene are preferred as monomers. For example, copolymers containing methacrylic acid, benzyl methacrylate, and styrene, or copolymers containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferred.

[0249] In one embodiment, polymer A is preferably a polymer comprising 25% to 40% by mass of an aromatic hydrocarbon monomer component, 20% to 35% by mass of a first monomer component, and 30% to 45% by mass of a second monomer component. Furthermore, in another embodiment, it is preferably a polymer comprising 70% to 90% by mass of an aromatic hydrocarbon monomer component and 10% to 25% by mass of a first monomer component.

[0250] Polymer A may have a branched structure or an alicyclic structure in its side chain. By using monomers containing groups with branched structures in their side chains or monomers containing groups with alicyclic structures in their side chains, branched or alicyclic structures can be introduced into the side chains of polymer A.

[0251] Specific examples of monomers containing groups having branched structures in their side chains include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tert-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl (meth)acrylate are preferred, and isopropyl (meth)acrylate or tert-butyl (meth)acrylate are more preferred.

[0252] Examples of monomers containing alicyclic groups in their side chains include monomers with monocyclic aliphatic hydrocarbon groups, monomers with polycyclic aliphatic hydrocarbon groups, and (meth)acrylates having alicyclic hydrocarbon groups with 5 to 20 carbon atoms. As more specific examples, one could cite (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate-2-methyl-2-adamantyl ester, (meth)acrylate-2-ethyl-2-adamantyl ester Alkyl esters, 3-hydroxy-1-adamantyl ester of (meth)acrylate, octahydro-4,7-methyl-indene-5-yl ester of (meth)acrylate, octahydro-4,7-methyl-indene-1-yl methyl ester of (meth)acrylate, 1-menthol ester of (meth)acrylate, tricyclodecane of (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester of (meth)acrylate, 3,7,7-trimethyl-4-hydroxybicyclo[4.1.0]heptyl ester of (meth)acrylate, (nor)bornyl ester of (meth)acrylate, isobornyl ester of (meth)acrylate, fenyl acrylate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate, cyclohexyl ester of (meth)acrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentanyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, with particular preference for cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

[0253] Polymer A can be used alone or in combination with two or more polymers. When using two or more polymers in combination, it is preferable to use two polymers A containing monomers with aromatic hydrocarbons, or to use a polymer A containing monomers with aromatic hydrocarbons and a polymer A without monomers with aromatic hydrocarbons. In the latter case, the proportion of polymer A containing monomers with aromatic hydrocarbons relative to the total amount of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0254] The synthesis of polymer A is preferably carried out as follows: A solution prepared by diluting one or more monomers described above with solvents such as acetone, methyl ethyl ketone, or isopropanol is added, along with an appropriate amount of free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile, and the mixture is heated and stirred. Sometimes, a portion of the mixture is added dropwise to the reaction solution while the synthesis is proceeding. After the reaction is complete, solvent is sometimes added further to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used as synthesis methods.

[0255] The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. By using polymer A with a Tg of 135°C or lower in the photosensitive layer, it is possible to suppress linewidth thickening or resolution degradation due to focus position shift during exposure. From this viewpoint, the Tg of polymer A is more preferably 130°C or lower, further preferably 120°C or lower, and especially preferably 110°C or lower. Furthermore, from the viewpoint of improving edge melt resistance, it is preferable to use polymer A with a Tg of 30°C or higher. From this viewpoint, the Tg of polymer A is more preferably 40°C or higher, further preferably 50°C or higher, especially preferably 60°C or higher, and most preferably 70°C or higher.

[0256] The photosensitive layer may contain resins other than alkali-soluble resins.

[0257] Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic acid copolymers (wherein the styrene content is less than 40% by mass), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0258] Alkali-soluble resins can be used alone or in combination with two or more.

[0259] The ratio of alkali-soluble resin to the total mass of the photosensitive layer is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the ratio of alkali-soluble resin to the photosensitive layer to 90% by mass or less. On the other hand, from the viewpoint of improving resistance to edge melting, it is preferable to set the ratio of alkali-soluble resin to the photosensitive layer to 10% by mass or more.

[0260] Pigment

[0261] From the viewpoint of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, the photosensitive layer preferably contains pigment, and more preferably contains a pigment (also simply referred to as "pigment N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or higher and whose maximum absorption wavelength changes due to acids, bases, or free radicals. While the detailed mechanism is not yet fully understood, the inclusion of pigment N improves adhesion to adjacent layers (e.g., the temporary support and the first resin layer) and results in superior resolution.

[0262] In this specification, the phrase "the maximum absorption wavelength of a pigment changes due to acid, alkali, or free radicals" can refer to any of the following: a pigment in a colored state is decolored by acid, alkali, or free radicals; a pigment in a decolored state is colored by acid, alkali, or free radicals; or a pigment in a colored state changes to a different hue.

[0263] Specifically, pigment N can be a compound that changes color from a decolorized state through exposure, or a compound that changes color from a color-developed state through exposure. In this case, it can be a pigment that changes color or decolorizes by generating acids, bases, or free radicals within the photosensitive layer through exposure, or a pigment that changes color or decolorizes by a change in the state (e.g., pH) within the photosensitive layer through acids, bases, or free radicals. Furthermore, it can also be a pigment that changes color or decolorizes directly upon stimulation by acids, bases, or free radicals without exposure.

[0264] From the viewpoint of visual recognition and resolution of the exposed and unexposed portions, pigment N is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to free radicals.

[0265] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, the photosensitive layer preferably contains both a pigment N, which changes its maximum absorption wavelength through free radicals, and a photoradical polymerization initiator.

[0266] Furthermore, from the viewpoint of visual recognition of the exposed and unexposed parts, pigment N is preferably a pigment that develops color through acid, alkali or free radicals.

[0267] As an example of the color-developing mechanism of pigment N in this invention, the following method can be used: a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator is added to the photosensitive layer, and the free radical reactive pigment, acid reactive pigment, or alkali reactive pigment (e.g., colorless pigment) is developed by free radicals, acids, or bases generated by the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator after exposure.

[0268] From the viewpoint of visual recognition of the exposed and unexposed portions, the maximum absorption wavelength of pigment N in the wavelength range of 400nm to 780nm during color development is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm.

[0269] Furthermore, pigment N may have only one maximum absorption wavelength in the wavelength range of 400nm to 780nm for color development, or it may have two or more. When pigment N has two or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450nm or higher.

[0270] The maximum absorption wavelength of pigment N was obtained as follows: Under atmospheric conditions, the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) was measured in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation), and the wavelength at which the light intensity was minimal (maximum absorption wavelength) was detected.

[0271] As pigments that develop or fade color through exposure, colorless compounds can be cited as an example.

[0272] Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthones, iminonaphthoquinone pigments, azomethyl alkaloid pigments, and anthraquinone pigments.

[0273] From the viewpoint of visual recognition of the exposed and unexposed areas, colorless compounds are preferred as pigment N.

[0274] Examples of colorless compounds include, for example, colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorane skeleton (fluorane pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a colorless auramine skeleton (colorless auramine pigments).

[0275] Preferably, the pigment is a triarylmethane pigment or a fluorane pigment, and more preferably, it is a colorless compound (triphenylmethane pigment) or a fluorane pigment having a triphenylmethane skeleton.

[0276] From the viewpoint of visual recognition of both the exposed and unexposed areas, it is preferable for the colorless compound to have a lactone ring, a sultine ring, or a sulfonyl ring. This allows the lactone ring, sultine ring, or sulfonyl ring of the colorless compound to react with free radicals generated by a photoradical polymerization initiator or acids generated by a photocationic polymerization initiator, thereby causing the colorless compound to either become a closed-ring state and decolorize, or become an open-ring state and develop color. Preferably, the colorless compound is a compound having a lactone ring, sultine ring, or sulfonyl ring that develops color through ring-opening by a free radical or acid; more preferably, it is a compound having a lactone ring that develops color through ring-opening by a free radical or acid.

[0277] As pigment N, examples include the following dyes and colorless compounds.

[0278] Specific examples of dyes in pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurpurine 4B, α-naphthalene red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue naphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), and Oil Pink #312 (manufactured by Orient Chemical Industries). Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spilonred BEH Special (Hodogaya Chemical Co., Ltd.) (manufactured by Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyoctadecylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0279] Specific examples of colorless compounds in pigment N include p,p',p”-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6-methyl 3-(N,N-diethylamino)-6-methyl-7-aniline fluorane, 3-(N,N-diethylamino)-6-methyl-7-dimethylaniline fluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7-dimethylanilinofluorane, 3-hydropyridyl-6-methyl-7-anilinofluorane, 3-pyrrolidinyl-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis( 1-n-Butyl-2-methylindole-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthon-3-one.

[0280] From the viewpoints of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, pigment N is preferably a pigment whose maximum absorption wavelength changes through free radicals, and more preferably a pigment that develops color through free radicals.

[0281] As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0282] One pigment can be used alone, or two or more pigments can be used.

[0283] From the viewpoint of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, the pigment content relative to the total mass of the photosensitive layer 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.

[0284] Furthermore, from the viewpoint of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, the content of pigment N relative to the total mass of the photosensitive layer 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.

[0285] The content of pigment N refers to the amount of pigment that enables all pigments N contained in the photosensitive layer to be in a colored state. The following explanation uses pigments that develop color via free radicals as an example to illustrate the quantitative method for determining the content of pigment N.

[0286] Two solutions were prepared by dissolving 0.001 g or 0.01 g of pigment in 100 mL of methyl ethyl ketone. Irgacure OXE01 (trade name, BASF Japan Ltd.) as a photoradioactive polymerization initiator was added to each solution, and the solutions were irradiated with 365 nm light to generate free radicals, causing all pigments to become colored. Then, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25 °C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and calibration curves were constructed.

[0287] Next, except that 3g of the photosensitive layer was dissolved in methyl ethyl ketone instead of the pigment, the absorbance of the solution that caused the pigment to fully develop was measured using the same method as described above. Based on the absorbance of the solution containing the photosensitive layer, the content of pigment contained in the photosensitive layer was calculated based on the calibration curve.

[0288] <Thermocrosslinking compounds>

[0289] From the viewpoint of the strength of the cured film and the adhesion of the uncured film, the photosensitive layer preferably contains a thermally crosslinking compound. Furthermore, in this specification, the thermally crosslinking compound having olefinically unsaturated groups described later is treated as a thermally crosslinking compound, not as a polymerizable compound.

[0290] Examples of thermally crosslinking compounds include hydroxymethyl compounds and end-capped isocyanate compounds. Among these, end-capped isocyanate compounds are preferred from the viewpoint of the strength of the cured film and the adhesion of the uncured film.

[0291] Since the capped isocyanate compound reacts with hydroxyl and carboxyl groups, the hydrophilicity of the formed film is reduced, for example, in the case of resins and / or polymeric compounds having at least one of hydroxyl and carboxyl groups. There is a tendency for the film formed by curing the photosensitive layer to enhance its function as a protective film.

[0292] In addition, capped isocyanate compounds are defined as "compounds having a structure in which the isocyanate group of the isocyanate is protected (so-called masking) by a capping agent".

[0293] There are no particular limitations on the dissociation temperature of the capped isocyanate compound, but it is preferably 100°C to 160°C, and more preferably 130°C to 150°C.

[0294] The dissociation temperature of capped isocyanates refers to "the temperature of the endothermic peak accompanying the deprotection reaction of capped isocyanates when measured using a differential scanning calorimeter and analyzed by DSC (Differential Scanning Calorimetry)".

[0295] As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. is preferred. However, the differential scanning calorimeter is not limited to this.

[0296] Examples of end-capping agents with dissociation temperatures of 100℃ to 160℃ include active methylene compounds (malonate esters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, etc., which have the structure represented by -C (=N-OH)- in the molecule).

[0297] Among these, oxime compounds are preferred as capping agents with a dissociation temperature of 100°C to 160°C, for example, from the viewpoint of preservation stability.

[0298] For example, from the viewpoint of improving the brittleness of the film and enhancing the adhesion to the substrate, the end-capped isocyanate compound preferably has an isocyanurate structure.

[0299] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuric acid esterification of hexamethylene diisocyanate.

[0300] Among the isocyanurate-capped isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a capping agent are more preferable from the viewpoint that it is easier to set the dissociation temperature within a preferred range and easier to reduce development residue compared to compounds without an oxime structure.

[0301] End-capped isocyanate compounds can have polymerizable groups.

[0302] There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, with free radical polymerizable groups being preferred.

[0303] Examples of polymerizable groups include olefinic unsaturated groups such as (meth)acryloyloxy, (meth)acrylamido, and styryl, as well as groups with epoxy groups such as glycidyl.

[0304] Among them, the polymerizable group is preferably an olefinic unsaturated group, more preferably (meth)acryloyloxy, and even more preferably acryloyloxy.

[0305] As a capped isocyanate compound, it can be used in commercially available products.

[0306] Examples of commercially available end-capped isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and end-capped Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0307] Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0308] [Chemical Formula 2]

[0309]

[0310] One type of thermally crosslinking compound can be used alone, or two or more types can be used.

[0311] When the photosensitive layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive layer is preferably 1% to 50% by mass, more preferably 5% to 30% by mass.

[0312] <Other Ingredients>

[0313] The photosensitive layer may contain components other than the alkali-soluble resin, olefinic unsaturated compound, photopolymerization initiator, pigment and thermal crosslinking compound mentioned above.

[0314] -surfactant-

[0315] From the viewpoint of thickness uniformity, the photosensitive layer preferably contains a surfactant.

[0316] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.

[0317] As surfactants, examples include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Application No. 2009-237362.

[0318] Fluorinated surfactants or silicone surfactants are preferred as surfactants.

[0319] Commercially available fluorinated surfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F- 568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628 , EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above is DIC (Manufactured by Corporation), Fluorad (trade name) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) Solutions Inc.), Ftergent (trade name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (the above are manufactured by Neos Company Limited), U-120E (Uni-chem Co., Ltd.), etc.

[0320] Furthermore, acrylic compounds are also preferred as fluorinated surfactants. These acrylic compounds have a molecular structure containing functional groups with fluorine atoms, and when heated, the functional groups containing fluorine atoms are cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the Megafac (trade name) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)), such as Megafac (trade name) DS-21.

[0321] Furthermore, fluorinated surfactants are preferably polymers of vinyl ether compounds containing fluorine atoms and hydrophilic vinyl ether compounds, which have fluorinated alkyl or fluorinated alkylene ether groups.

[0322] Fluorinated surfactants can utilize block polymers. Fluorinated surfactants can also preferably utilize fluorinated polymers comprising structural units derived from (meth)acrylate compounds having fluorine atoms and structural units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxide or propylene oxide).

[0323] Fluorinated surfactants can also be used on fluoropolymers with olefinically unsaturated side chains. Examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0324] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol octadecanoate, and dehydrated sorbitol fatty acid esters.

[0325] Specific examples include Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (all manufactured by BASF), Solsperse (trade name) 20000 (all manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, and Surfynol. 104, 400, 440 (the above are manufactured by Nissin Chemical Co., Ltd.), etc.

[0326] Furthermore, in recent years, the environmental adaptability of compounds with straight-chain perfluoroalkyl groups having 7 or more carbon atoms has become a concern. Therefore, it is preferable to use surfactants that use alternatives to perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS).

[0327] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends.

[0328] Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray). Co., Ltd.) and X-22-4952, , 121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Chemical, Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive...) BYK 300, BYK 306, BYK 307, BYK 310, BYK 320, BYK 323, BYK 325, BYK 330, BYK 313, BYK 315N, BYK 331, BYK 333, BYK 345, BYK 347, BYK 348, BYK 349, BYK 370, BYK 377, BYK 378 (all manufactured by BYK Chemie), etc.

[0329] The photosensitive layer may contain one surfactant or two or more surfactants.

[0330] The surfactant content relative to the total mass of the photosensitive layer is preferably 0.001% to 10% by mass, more preferably 0.01% to 3% by mass.

[0331] -additive-

[0332] In addition to the above-mentioned components, the photosensitive layer may also contain known additives as needed.

[0333] Examples of additives include, for example, polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and solvents. The photosensitive layer may contain one or more of these additives.

[0334] The photosensitive layer may also contain a polymerization inhibitor. A free radical polymerization inhibitor is preferred as the polymerization inhibitor.

[0335] Examples of polymerization inhibitors include the heat-inhibiting agents described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, cuprous chloride, aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive resin composition, aluminum nitrosophenylhydroxylamine is preferably used as the polymerization inhibitor.

[0336] Examples of benzotriazoles include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0337] Examples of carboxylated benzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxylated benzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxylated benzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylcarboxylated benzotriazole. Commercially available products such as CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD., trade name) can also be used as carboxylated benzotriazoles.

[0338] The total content of the polymerization inhibitor, benzotriazole, and carboxybenzotriazole is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, relative to the total mass of the photosensitive layer. From the viewpoint of imparting storage stability to the photosensitive resin composition, it is preferable to set the above content to 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing dye decolorization, it is preferable to set the above content to 3% by mass or less.

[0339] The photosensitive layer may contain sensitizers.

[0340] There are no particular restrictions on sensitizers; well-known sensitizers, dyes, and pigments can be used. Examples of sensitizers include, for instance, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridinone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedicarboximide compounds, triarylamine compounds, and aminoacridine compounds.

[0341] The photosensitive layer may contain one type of sensitizer or two or more types.

[0342] When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. However, from the viewpoint of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer, the content of the sensitizer relative to the total mass of the photosensitive layer is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass.

[0343] The photosensitive layer may contain at least one selected from plasticizers and heterocyclic compounds.

[0344] As plasticizers and heterocyclic compounds, examples include the compounds described in paragraphs 0097–0103 and 0111–0118 of International Publication No. 2018 / 179640.

[0345] The photosensitive layer may contain solvent. In cases where the photosensitive layer is formed from a photosensitive resin composition containing solvent, the solvent may sometimes remain in the photosensitive layer.

[0346] Furthermore, the photosensitive layer may also contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferation agents, development promoters, conductive fibers, thermal free radical polymerization initiators, thermal acid-producing agents, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-precipitating agents.

[0347] The additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated into this specification.

[0348] <Impurities, etc.>

[0349] The photosensitive layer may contain a specified amount of impurities.

[0350] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions. Among these, halide ions, sodium ions, and potassium ions are easily introduced as impurities, and therefore the following concentrations are preferred.

[0351] The impurity content in the photosensitive layer, measured by mass, is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content, measured by mass, can be set to 1 ppb or more, or 0.1 ppm or more.

[0352] As a method for keeping impurities within the aforementioned range, examples include selecting raw materials with low impurity content as raw materials for the composition, preventing impurity contamination during the fabrication of the photosensitive layer, and cleaning and removing impurities. By employing these methods, the amount of impurities can be kept within the aforementioned range.

[0353] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) luminescence spectrometry, atomic absorption spectrometry, and ion chromatography.

[0354] The photosensitive layer preferably contains low levels of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, on a mass basis.

[0355] The lower limit, based on mass relative to the total mass of the photosensitive layer, can be set to 10 ppb or more, or 100 ppb or more. The content of these compounds can be suppressed using the same methods as for impurities in the aforementioned metals. Furthermore, quantification can be performed using known methods.

[0356] From the viewpoint of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01% to 1.0% by mass, more preferably 0.05% to 0.5% by mass.

[0357] <Residual Monomer>

[0358] The photosensitive layer sometimes contains residual monomers corresponding to the structural units of the aforementioned alkali-soluble resin.

[0359] From the perspective of pattern formation and reliability, the content of residual monomer relative to the total mass of alkali-soluble resin is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less. There is no particular limitation on the lower limit, but it is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more.

[0360] From the perspective of pattern formation and reliability, the residual monomer of each structural unit of the alkali-soluble resin relative to the total mass of the photosensitive layer is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less. There is no particular limitation on the lower limit, but it is preferably 0.1 ppm by mass or more, more preferably 1 ppm by mass or more.

[0361] The residual monomer content during the synthesis of alkali-soluble resins via polymer reactions is preferably set within the above-mentioned range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with carboxylic acid side chains, it is preferable to set the glycidyl acrylate content within the above-mentioned range.

[0362] The amount of residual monomers can be determined by known methods such as liquid chromatography and gas chromatography.

[0363] <Physical properties, etc.>

[0364] The thickness of the photosensitive layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, even more preferably 0.5 μm to 50 μm, even more preferably 0.5 μm to 15 μm, particularly preferably 0.5 μm to 10 μm, and most preferably 0.5 μm to 8 μm. This improves the developability of the photosensitive layer and increases resolution.

[0365] Furthermore, in one embodiment, the preferred size is 0.5 μm to 5 μm, more preferably 0.5 μm to 4 μm, and even more preferably 0.5 μm to 3 μm.

[0366] Furthermore, from the viewpoint of resolution, the thickness of the photosensitive layer is preferably 10 μm or less, and more preferably 8 μm or less.

[0367] The thickness of each layer of the photosensitive transfer material is determined as follows: a cross-section perpendicular to the main surface of the photosensitive transfer material is observed using a scanning electron microscope (SEM). Based on the obtained observation images, the thickness of each layer is measured at more than 10 points, and the average value is calculated.

[0368] Furthermore, in terms of superior adhesion, the transmittance of light with a wavelength of 365 nm in the photosensitive layer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular limit to the upper limit, but it is preferably 99.9% or less.

[0369] <Formation Method>

[0370] There are no particular restrictions on the method for forming the photosensitive layer, as long as it is a method that can form a layer containing the above-mentioned components.

[0371] As a method for forming a photosensitive layer, for example, the following method can be used: preparing a photosensitive resin composition containing an alkali-soluble resin, an olefinic unsaturated compound, a photopolymerization initiator, and a solvent, coating the photosensitive resin composition onto a surface such as a temporary support, and drying the coating of the photosensitive resin composition to form the layer.

[0372] Examples of photosensitive resin compositions used in the formation of the photosensitive layer include compositions containing an alkali-soluble resin, an olefinic unsaturated compound, a photopolymerization initiator, any of the above-mentioned components, and a solvent.

[0373] In order to adjust the viscosity of the photosensitive resin composition to facilitate the formation of a photosensitive layer, the photosensitive resin composition preferably contains a solvent.

[0374] -solvent-

[0375] As a solvent contained in the photosensitive resin composition, there are no particular restrictions as long as it can dissolve or disperse alkali-soluble resins, olefinic unsaturated compounds, photopolymerization initiators, and any of the above-mentioned components; any known solvent can be used.

[0376] Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (such as toluene), aprotic polar solvents (such as N,N-dimethylformamide), cyclic ether solvents (such as tetrahydrofuran), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0377] When manufacturing a photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive layer, and a protective film, the photosensitive resin composition preferably contains at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. More preferably, it contains a mixed solvent comprising at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from ketone solvents and cyclic ether solvents. Even more preferably, it contains a mixed solvent comprising at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0378] Examples of alkylene glycol ether solvents include, for example, 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.

[0379] Examples of solvents for alkylene glycol ether acetates include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0380] As solvents, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and solvents described in paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated into this specification.

[0381] The photosensitive resin composition may contain one solvent alone or two or more solvents.

[0382] The solvent content when coating the photosensitive resin composition is preferably 50 to 1,900 parts by weight, more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the total solids in the photosensitive resin composition.

[0383] There are no particular limitations on the preparation method of the photosensitive resin composition. For example, the following method can be used: prepare a solution by dissolving each component in the above-mentioned solvent in advance, and mix the resulting solution in a specified ratio to prepare the photosensitive resin composition.

[0384] Before forming the photosensitive layer, it is preferable to filter the photosensitive resin composition using a filter with a pore size of 0.2 μm to 30 μm.

[0385] There are no particular limitations on the coating method for the photosensitive resin composition; any known method can be used. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0386] Furthermore, the photosensitive layer can also be formed by coating the photosensitive resin composition onto the protective film described later and allowing it to dry.

[0387] Furthermore, from the viewpoint of resolution and the peelability of the temporary support, the photosensitive transfer material of the present invention preferably has other layers between the temporary support and the photosensitive layer.

[0388] Other preferred layers include intermediate layers, thermoplastic resin layers, and protective films.

[0389] Among these other layers, an intermediate layer is preferred, and a thermoplastic resin layer and an intermediate layer are more preferred.

[0390] [Intermediate layer]

[0391] When a photosensitive transfer material has a thermoplastic resin layer (described later) between a temporary support and a photosensitive layer, it is preferable to have an intermediate layer between the thermoplastic resin layer and the photosensitive layer. This intermediate layer helps to suppress the mixing of components during the formation of multiple layers and during storage.

[0392] From the viewpoint of developability and the inhibition of mixing of components during multi-layer coating and post-coating storage, the intermediate layer is preferably a water-soluble layer. In this invention, "water-soluble" means having a solubility of 0.1g or more in 100g of water at pH 7.0 and a liquid temperature of 22°C.

[0393] As an intermediate layer, for example, an oxygen barrier layer with oxygen barrier function described as a "separation layer" in Japanese Patent Application Publication No. 5-72724 can be cited. By using an oxygen barrier layer as the intermediate layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and consequently, productivity is increased. The oxygen barrier layer used as the intermediate layer can be appropriately selected from known layers. Preferably, the oxygen barrier layer used as the intermediate layer is one that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).

[0394] Furthermore, from the viewpoints of oxygen barrier properties, resolution, and pattern formation, the intermediate layer preferably comprises an inorganic layered compound.

[0395] As inorganic layered compounds, examples include particles with thin, flat plate shapes, such as natural mica, synthetic mica and other mica compounds, talc represented by the formula: 3MgO·4SiO·H2O, taeniolite, montmorillonite, soapstone, hectorite, zirconium phosphate, etc.

[0396] As a mica compound, for example, the formula A(B, C) can be given. 2-5 D4O 10(OH, F, O)₂ [where A is any one of K, Na, or Ca; B and C are any one of Fe(II), Fe(III), Mn, Al, Mg, or V; and D is Si or Al.] represents natural mica, synthetic mica, and other mica groups.

[0397] Within the mica group, natural mica includes muscovite, paragonite, phlogopite, biotite, and kepidolite. Synthetic mica includes fluorophlogopite (KMg3(AlSi3O4)). 10 F2, potassium tetrasilica KMg 2.5 (Si40 10 Non-swellable mica such as F2, and Na tetrasilicic mica (NaMg) 2.5 (Si4O 10 F2, Na or Li with mica (Na, Li)Mg2Li(Si4O) 10 F2, Na or Li hectorite of the montmorillonite series (Na, Li) 1 / 8 Mg 2 / 5 Li 1 / 8 (Si4O 10 Swellable mica such as F2. In addition, it is also used in the synthesis of montmorillonite.

[0398] From a diffusion control perspective, the thinner the thickness of the inorganic layered compound, the better, and the larger the planar dimensions, the better, without hindering the smoothness of the coating surface or the transmissibility of active light. Therefore, an aspect ratio of 20 or more is preferred, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the major axis to the particle thickness, and can be determined, for example, from a projection image of a particle-based microscopic photograph. A larger aspect ratio results in a greater effect.

[0399] The average major diameter of the inorganic layered compound particles is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swollen synthetic mica as a representative compound, the thickness is preferably about 1 nm to 50 nm, and the surface size (major diameter) is about 1 μm to 20 μm.

[0400] From the viewpoints of oxygen barrier properties, resolution, and pattern formation, the content of inorganic layered compounds relative to the total mass of the intermediate layer is preferably 0.1% to 50% by mass, more preferably 1% to 20% by mass.

[0401] The intermediate layer preferably comprises a resin. Examples of resins included in the intermediate layer include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. The resin included in the intermediate layer is preferably a water-soluble resin.

[0402] From the viewpoint of suppressing the mixing of components between multiple layers, the resin contained in the intermediate layer is preferably a resin that is different from both the polymer A contained in the negative photosensitive layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

[0403] Furthermore, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties, the intermediate layer preferably contains a water-soluble compound, and more preferably a water-soluble resin.

[0404] There are no particular limitations on the water-soluble compound, but from the viewpoint of oxygen barrier properties, developability, resolution and pattern forming properties, it is preferable to select one or more compounds selected from water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenolic derivatives and amide compounds, and more preferably at least one water-soluble resin selected from polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl methylcellulose.

[0405] Examples of water-soluble resins include, for example, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resin, (meth)acrylate resin, polyethylene oxide resin, gelatin, vinyl ether resin, polyamide resin, and copolymers thereof.

[0406] From the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties, the water-soluble compound preferably includes polyvinyl alcohol, and more preferably polyvinyl alcohol.

[0407] There are no particular limitations on the degree of hydrolysis of polyvinyl alcohol, but from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties, 73 mol% to 99 mol% is preferred.

[0408] Furthermore, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern forming properties, polyvinyl alcohol preferably contains ethylene as a monomer unit.

[0409] There are no particular restrictions on the method for determining the degree of hydrolysis; for example, it can be determined by the method described in JIS K 6726:1994.

[0410] From the viewpoint of oxygen barrier properties and the inhibition of mixing of components during multi-layer coating and storage after coating, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinylpyrrolidone.

[0411] The intermediate layer may contain one or more resins.

[0412] From the viewpoint of oxygen barrier properties and the inhibition of mixing of components during multilayer coating and storage after coating, the proportion of water-soluble compounds in the intermediate layer is preferably 50% to 100% by mass relative to the total mass of the intermediate layer, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and especially preferably 90% to 100% by mass.

[0413] Furthermore, the intermediate layer may also contain additives as needed. Examples of additives include, for instance, surfactants.

[0414] There is no limitation on the thickness of the intermediate layer. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. By keeping the thickness of the intermediate layer within the above range, it is possible to suppress the mixing of components during the formation of multiple layers and during storage without reducing oxygen barrier properties, and it is also possible to suppress the increase in the removal time of the intermediate layer during development.

[0415] Regarding the method for forming the intermediate layer, there are no limitations as long as the method is capable of forming a layer containing the above-mentioned components. For example, a method for forming the intermediate layer can be described as applying the intermediate layer composition to the surface of a thermoplastic resin layer or a photosensitive layer and then drying the coating film of the intermediate layer composition.

[0416] Examples of intermediate layer compositions include, for instance, compositions comprising a resin and any additives. To facilitate intermediate layer formation by adjusting the viscosity of the intermediate layer composition, the intermediate layer composition preferably contains a solvent. There are no limitations on the solvent, as long as it is capable of dissolving or dispersing the resin. The solvent is preferably at least one selected from water-miscible organic solvents, more preferably water or a mixture of water-miscible organic solvents.

[0417] Examples of water-miscible organic solvents include alcohols, acetone, ethylene glycol, and glycerol having 1 to 3 carbon atoms. Preferably, alcohols having 1 to 3 carbon atoms are water-miscible organic solvents, and more preferably methanol or ethanol.

[0418] [Thermoplastic resin layer]

[0419] The photosensitive transfer material of this invention may have a thermoplastic resin layer. Preferably, the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the photosensitive layer. This is because having a thermoplastic resin layer between the temporary support and the photosensitive layer in the photosensitive transfer material improves the followability of the adhered material, suppresses air bubble incorporation between the adhered material and the photosensitive transfer material, and consequently improves the interlayer adhesion.

[0420] The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

[0421] Examples of alkali-soluble resins include, for example, acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0422] From the viewpoint of developability and adhesion to layers adjacent to the thermoplastic resin layer, the alkali-soluble resin is preferably an acrylic resin. Here, "acrylic resin" refers to a resin having at least one structural unit selected from (meth)acrylic acid, (meth)acrylate, and (meth)acrylamide.

[0423] In the acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin. The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate is preferably 30% to 100% by mass, more preferably 50% to 100% by mass, relative to the total mass of the acrylic resin.

[0424] Furthermore, the alkali-soluble resin is preferably a polymer having an acid group. Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being the most preferred.

[0425] From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin with an acid value of 60 mg KOH / g or higher, and more preferably an acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher. There is no upper limit on the acid value. The acid value of the alkali-soluble resin is preferably 200 mg KOH / g or lower, and more preferably 150 mg KOH / g or lower.

[0426] There are no restrictions on the type of acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher, and it can be appropriately selected from known resins. Examples of acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher include the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher in the polymer described in paragraph 0025 of Japanese Patent Application Publication No. 2011-95716, the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher in the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher in the adhesive polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0427] The proportion of carboxyl-containing structural units in the carboxyl-containing acrylic resin relative to the total mass of the carboxyl-containing acrylic resin is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and particularly preferably 12% to 30% by mass.

[0428] From the viewpoint of developability and adhesion to the adjacent thermoplastic resin layer, alkali-soluble resin is particularly preferred to be an acrylic resin having structural units derived from (meth)acrylic acid.

[0429] Alkali-soluble resins can have reactive groups. Reactive groups can be, for example, any group capable of addition polymerization. Examples of reactive groups include olefinic unsaturated groups, condensation groups (e.g., hydroxyl and carboxyl groups), and addition polymerization reactive groups (e.g., epoxy and (terminated) isocyanate groups).

[0430] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and especially preferably 20,000 to 50,000.

[0431] The thermoplastic resin layer may contain one or more alkali-soluble resins.

[0432] From the viewpoint of developability and adhesion to the adjacent thermoplastic resin layer, the content of alkali-soluble resin relative to the total mass of the thermoplastic resin layer is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, further preferably 40% to 80% by mass, and especially preferably 50% to 70% by mass.

[0433] The thermoplastic resin layer preferably contains a pigment (hereinafter, sometimes referred to as "pigment B"), which has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and the maximum absorption wavelength changes due to acids, bases or free radicals. The preferred embodiments of pigment B are the same as those of pigment N described above, except for the points mentioned later.

[0434] From the viewpoints of visual recognition of the exposed portion, visual recognition of the unexposed portion, and resolution, pigment B is preferably a pigment whose maximum absorption wavelength changes due to acid or free radicals, and more preferably a pigment whose maximum absorption wavelength changes due to acid.

[0435] From the viewpoints of visual recognition of the exposed portion, visual recognition of the unexposed portion, and resolution, the thermoplastic resin layer preferably includes a pigment B that changes its maximum absorption wavelength when exposed to acid and a compound that generates acid when exposed to light (described later).

[0436] The thermoplastic resin layer may also contain one or more pigments B.

[0437] From the viewpoint of visual recognition of both the exposed and unexposed areas, the proportion of pigment B relative to the total mass of the thermoplastic resin layer is preferably 0.2% by mass or more, more preferably 0.2% to 6% by mass, even more preferably 0.2% to 5% by mass, and particularly preferably 0.25% to 3.0% by mass.

[0438] Here, the content ratio of pigment B refers to the proportion of pigment that makes all pigment B contained in the thermoplastic resin layer appear colored. The following describes the quantitative method for the content ratio of pigment B, using a pigment that appears colored via free radicals as an example. Two solutions were prepared, in which pigment (0.001 g) and pigment (0.01 g) were dissolved in methyl ethyl ketone (100 mL), respectively. Free radicals were generated by adding IRGACURE OXE-01 (BASF) as a photoradioactive polymerization initiator to each solution and then irradiating it with 365 nm light, causing all pigments to appear colored. Next, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve was created. Then, instead of pigment, the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone, and the absorbance of the solution that made all pigments appear colored was measured using the same method as above. Based on the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of pigment contained in the thermoplastic resin layer is calculated according to the calibration curve.

[0439] The thermoplastic resin layer may also contain a compound (hereinafter, sometimes referred to as "compound C") that generates acids, bases, or free radicals upon exposure to light. Compound C is preferably a compound that generates acids, bases, or free radicals upon receiving active light (e.g., ultraviolet and visible light). Known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical generators) can be cited as examples of compound C. Compound C is preferably a photoacid generator.

[0440] From a resolution point of view, the thermoplastic resin layer preferably contains a photoacid generator. Examples of photoacid generators that can be included in the photosensitive layer, as described above, are photocationic polymerization initiators, and the preferred methods are the same, except as will be discussed later.

[0441] From the viewpoint of sensitivity and resolution, the photoacid generator preferably includes at least one selected from onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is more preferably to include oxime sulfonate compounds.

[0442] Furthermore, the photoacid generator is preferably a photoacid generator having the following structure.

[0443] [Chemical Formula 3]

[0444]

[0445] The thermoplastic resin layer may also contain a photoalkali-generating agent. Examples of photoalkali-generating agents include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, o-carbamoylhydroxyamide, o-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinylethane, and (4-morpholinylbenzoyl)-1-benzyl-1-di... Methylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaaminocobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 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.

[0446] The thermoplastic resin layer may also contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators that can be included in the photosensitive layer described above are, for instance, the preferred method being the same.

[0447] The thermoplastic resin layer may also contain one or more compounds C.

[0448] From the viewpoints of visual recognition of the exposed area, visual recognition of the unexposed area, and resolution, the content of compound C relative to the total mass of the thermoplastic resin layer is preferably 0.1% to 10% by mass, more preferably 0.5% to 5% by mass.

[0449] From the viewpoints of resolution, adhesion to adjacent thermoplastic resin layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0450] The molecular weight of the plasticizer (for oligomers or polymers, the molecular weight refers to the weight-average molecular weight (Mw). The same applies hereinafter in this paragraph.) is preferably smaller than that of the alkali-soluble resin. The molecular weight of the plasticizer is preferably between 200 and 2,000.

[0451] There are no limitations on plasticizers as long as they are compounds that exhibit plasticizing properties when miscible with alkali-soluble resins. From the viewpoint of imparting plasticizing properties, plasticizers are preferably compounds having alkylene groups in their molecules, and more preferably polyalkylene glycol compounds. The alkylene groups contained in the plasticizer preferably have a polyvinyloxy structure or a polyacryloxy structure.

[0452] From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to the adjacent thermoplastic resin layer, the alkali-soluble resin is more preferably an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0453] Examples of (meth)acrylate compounds used as plasticizers include those described in the aforementioned olefinic unsaturated compounds. In photosensitive transfer materials, where a thermoplastic resin layer and a photosensitive layer are in direct contact, both the thermoplastic resin layer and the photosensitive layer preferably contain the same (meth)acrylate compound. This is because by containing the same (meth)acrylate compound in both the thermoplastic resin layer and the photosensitive layer, interlayer diffusion is suppressed, and storage stability is improved.

[0454] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesion to the adjacent thermoplastic resin layer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure.

[0455] In one embodiment, from the viewpoints of resolution, adhesion to the adjacent thermoplastic resin layer, and developability, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule.

[0456] In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

[0457] The thermoplastic resin layer may also contain one or more plasticizers.

[0458] From the viewpoints of resolution, adhesion to adjacent thermoplastic resin layers, and developability, the plasticizer content relative to the total mass of the thermoplastic resin layer is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and especially preferably 20% to 50% by mass.

[0459] From the viewpoint of uniform thickness, the thermoplastic resin layer preferably contains a surfactant. Examples of surfactants that can be included in the aforementioned photosensitive layer are, for instance, those preferred in the same manner.

[0460] The thermoplastic resin layer may also contain one or more surfactants.

[0461] The surfactant content relative to the total mass of the thermoplastic resin layer is preferably 0.001% to 10% by mass, more preferably 0.01% to 3% by mass.

[0462] The thermoplastic resin layer may also contain a sensitizer. Examples of sensitizers include those that can be contained in the negative photosensitive layer described above.

[0463] The thermoplastic resin layer may also contain one or more sensitizers.

[0464] From the viewpoint of improving the sensitivity to light sources, the visual recognition of the exposed part, and the visual recognition of the unexposed part, the content of the sensitizer relative to the total mass of the thermoplastic resin layer is preferably 0.01% to 5% by mass, more preferably 0.05% to 1% by mass.

[0465] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives as needed.

[0466] Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-85643. The contents of the aforementioned publication are incorporated herein by reference.

[0467] There is no limitation on the thickness of the thermoplastic resin layer. From the viewpoint of adhesion to adjacent layers, the average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. There is no upper limit on the average thickness of the thermoplastic resin layer. From the viewpoint of developability and resolution, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0468] There are no limitations on the method for forming the thermoplastic resin layer, as long as it is capable of forming a layer containing the above-mentioned components. For example, a method for forming the thermoplastic resin layer can be described by coating a thermoplastic resin composition onto the surface of a temporary support and drying the coating film of the thermoplastic resin composition.

[0469] Examples of thermoplastic resin compositions include those containing the aforementioned components. To adjust the viscosity of the thermoplastic resin composition for easy formation of a thermoplastic resin layer, the thermoplastic resin composition preferably contains a solvent.

[0470] There are no limitations on the solvent used in the thermoplastic resin composition, as long as it is capable of dissolving or dispersing the components contained in the thermoplastic resin layer. Examples of solvents that can be included in the aforementioned photosensitive resin composition are also possible, and the preferred methods are the same.

[0471] Thermoplastic resin compositions may contain one or more solvents.

[0472] The solvent content in the thermoplastic resin composition is preferably 50 to 1,900 parts by weight, more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the total solids in the thermoplastic resin composition.

[0473] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be carried out by following the methods described above for preparing the photosensitive resin composition and forming the negative photosensitive layer. For example, a solution in which each component of the thermoplastic resin layer is dissolved in a solvent can be prepared in advance. The resulting solutions are then mixed in a predetermined ratio to prepare the thermoplastic resin composition. After this process, the thermoplastic resin composition is coated onto the surface of a temporary support, and the coating of the thermoplastic resin composition is dried to form the thermoplastic resin layer. Alternatively, a thermoplastic resin layer can be formed on the surface of the negative photosensitive layer after a negative photosensitive layer has been formed on the protective film.

[0474] [Protective film]

[0475] Photosensitive transfer materials have a protective film.

[0476] The photosensitive layer and the protective film are preferably in direct contact.

[0477] As materials for forming the protective film, resin film and paper can be cited as examples. From the point of view of strength and flexibility, resin film is preferred.

[0478] Examples of resin membranes include polyethylene membranes, polypropylene membranes, polyethylene terephthalate membranes, cellulose triacetate membranes, polystyrene membranes, and polycarbonate membranes. Among these, polyethylene membranes, polypropylene membranes, or polyethylene terephthalate membranes are preferred.

[0479] There are no particular limitations on the thickness (layer thickness) of the protective film, but it is preferably 5μm to 100μm, and more preferably 10μm to 50μm.

[0480] From the viewpoints of transportability, resin pattern defect suppression, and resolution, the arithmetic mean roughness Ra of the side of the protective film opposite to the photosensitive layer side is preferably less than or equal to the arithmetic mean roughness Ra of the side of the protective film opposite to the photosensitive layer side, and more preferably smaller than the arithmetic mean roughness Ra of the side of the protective film opposite to the photosensitive layer side.

[0481] From the viewpoint of transportability and rollability, the arithmetic mean roughness Ra of the side of the protective film opposite to the photosensitive layer side is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and especially preferably 50 nm or less.

[0482] Furthermore, in terms of superior resolution, the arithmetic mean roughness Ra of the surface of the photosensitive layer side in the protective film is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and particularly preferably 50 nm or less. This is believed to be because, with the Ra value of the protective film surface within the above range, the uniformity of the thickness of the photosensitive layer and the formed resin pattern is improved.

[0483] There is no particular limitation on the lower limit of the Ra value of the surface of the protective film, but it is preferred that both sides have a value of 1 nm or more, more preferably 10 nm or more, and especially preferably 20 nm or more.

[0484] Furthermore, the peeling force of the protective film is preferably smaller than that of the temporary support.

[0485] Photosensitive transfer materials may have layers other than those described above (hereinafter also referred to as "other layers"). For example, a contrast-enhancing layer can be cited as an example of an other layer.

[0486] Regarding the contrast enhancement layer, it is described in paragraph 0134 of International Publication No. 2018 / 179640. Furthermore, regarding other layers, they are described in paragraphs 0194 to 0196 of Japanese Patent Application Publication No. 2014-85643. The contents of these publications are incorporated herein by reference.

[0487] The total thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and particularly preferably 20 μm to 40 μm. The total thickness of the photosensitive transfer material is measured by means of the method described above for measuring the thickness of each layer.

[0488] From the viewpoint of further maximizing the effects of the present invention, the total thickness of all layers in the photosensitive transfer material, excluding the temporary support and the protective film, 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.

[0489] Furthermore, from the viewpoint of further maximizing the effects of the present invention, the total thickness of the photosensitive layer, intermediate layer and thermoplastic resin layer in the photosensitive transfer material 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.

[0490] [Manufacturing method of photosensitive transfer material]

[0491] There are no particular limitations on the manufacturing method of the photosensitive transfer material involved in this invention, and known manufacturing methods, such as known methods for forming the layers, can be used.

[0492] The following is for reference. Figure 1 The method for manufacturing the photosensitive transfer material according to the present invention will be described. However, the photosensitive transfer material according to the present invention is not limited to having... Figure 1 The structure shown is a photosensitive transfer material.

[0493] Figure 1 This is a schematic cross-sectional view illustrating an example of the layer structure in one embodiment of the photosensitive transfer material according to the present invention. Figure 1 The photosensitive transfer material 20 shown has a structure consisting of a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive layer 17, and a protective film 19 stacked sequentially.

[0494] As a method for manufacturing the aforementioned photosensitive transfer material 20, for example, a method including the following steps can be described: after coating a thermoplastic resin composition on the surface of a temporary support 11, drying the coating of the thermoplastic resin composition to form a thermoplastic resin layer 12; after coating an intermediate layer composition on the surface of a thermoplastic resin layer 13, drying the coating of the intermediate layer composition to form an intermediate layer 15; and after coating a photosensitive resin composition containing an olefin unsaturated compound on the surface of the intermediate layer 15, drying the coating of the photosensitive resin composition to form a photosensitive layer 16.

[0495] In the above manufacturing method, the following composition is preferably used: a thermoplastic resin composition containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents; an intermediate layer composition containing at least one selected from water and water-miscible organic solvents; and a photosensitive resin composition containing an adhesive polymer, an olefinic unsaturated compound, and at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. This suppresses the mixing of components contained in the thermoplastic resin layer 13 with components contained in the intermediate layer 15 during the application of the intermediate layer composition to the surface of the thermoplastic resin layer 13 and / or during the storage of the laminate having the intermediate layer composition, and also suppresses the mixing of components contained in the intermediate layer 15 with components contained in the photosensitive layer 16 during the application of the photosensitive resin composition to the surface of the intermediate layer 15 and / or during the storage of the laminate having the photosensitive resin composition.

[0496] Photosensitive transfer material 20 is manufactured by pressing a protective film 19 onto the photosensitive layer 17 of a laminate manufactured using the above-described manufacturing method.

[0497] As a method for manufacturing the photosensitive transfer material used in this invention, it is preferable to manufacture a photosensitive transfer material 20 having a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive layer 17 and a protective film 19 by including a step of setting a protective film 19 in contact with the second surface of the photosensitive layer 17.

[0498] After manufacturing the photosensitive transfer material 20 using the above-described manufacturing method, the photosensitive transfer material 20 can be wound up, thereby producing and storing a roll-shaped photosensitive transfer material. The roll-shaped photosensitive transfer material can be directly supplied in this form to the bonding process with the substrate in the roll-to-roll method described later.

[0499] The photosensitive transfer material of this invention is preferably used in various applications requiring precision microfabrication based on photolithography. After patterning the photosensitive layer, it can be etched as a substrate or electroformed primarily by electroplating. Furthermore, the cured film obtained through patterning can be used as a permanent film, for example, as an interlayer insulating film, a wiring protection film, or a wiring protection film with a refractive index matching layer. Moreover, the photosensitive transfer material of this invention is preferably used in various wiring formation applications in semiconductor packaging, printed circuit boards, and sensor substrates, as well as in touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, and the formation of structures in the fields of micromechanics or microelectronics.

[0500] Furthermore, the photosensitive transfer material involved in this invention can preferably be a coloring resin layer containing pigments as the photosensitive layer.

[0501] In addition to the above, the coloring resin layer is suitable for, for example, forming colored pixels or black matrices for color filters in liquid crystal display devices (LCDs) and solid-state imaging elements (e.g., CCDs and CMOSs).

[0502] The same applies to the methods described above, excluding pigments, in the coloring resin layer.

[0503] Pigments

[0504] The photosensitive layer can be a coloring resin layer containing pigments.

[0505] In recent years, electronic devices have liquid crystal display windows, which are sometimes fitted with a cover glass to protect the liquid crystal display window. A black frame-shaped light-shielding layer is formed on the periphery of the back side of a transparent glass substrate or similar material. A colored resin layer can be used to form this light-shielding layer.

[0506] As for the pigment, it can be selected appropriately according to the desired hue, and can be chosen from black pigment, white pigment, and colored pigments other than black and white. Among them, when forming a black pattern, black pigment is preferred.

[0507] As the black pigment, any known black pigment (organic or inorganic pigment, etc.) can be appropriately selected, provided it does not impair the effects of this invention. From the viewpoint of optical density, examples of preferred black pigments include carbon black, titanium dioxide, titanium carbide, iron oxide, and graphite, with carbon black being particularly preferred. From the viewpoint of surface resistivity, carbon black with at least a portion of its surface coated with resin is preferred.

[0508] From the viewpoint of dispersion stability, the particle size of the black pigment, in terms of number average particle size, is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm.

[0509] Here, particle size refers to the diameter of a circle whose area is calculated from a photograph of pigment particles taken by an electron microscope, taking into account the area of ​​a circle with the same area as the pigment particle. Number-average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes.

[0510] As a pigment other than black pigment, the white pigment described in paragraphs 0015 and 0114 of Japanese Patent Application Publication No. 2005-007765 can be used. Specifically, among the white pigments, the preferred inorganic pigments are titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon black, aluminum oxide, aluminum hydroxide, or barium sulfate, more preferably titanium dioxide or zinc oxide, and even more preferably titanium dioxide. As an inorganic pigment, rutile or anatase titanium dioxide is even more preferred, and rutile titanium dioxide is particularly preferred.

[0511] Furthermore, the surface of titanium oxide can be treated with silica, alumina, zirconium oxide, or organic materials, or two or more of these treatments can be applied. This inhibits the catalytic activity of titanium oxide and improves its heat resistance and fading properties.

[0512] From the viewpoint of reducing the thickness of the heated photosensitive layer, at least one of aluminum oxide treatment and zirconium oxide treatment is preferred as a surface treatment for the surface of titanium oxide, and both aluminum oxide treatment and zirconium oxide treatment are particularly preferred.

[0513] Furthermore, when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is preferable that the photosensitive layer also contains colored pigments other than black and white pigments. When colored pigments are included, the particle size of the colored pigments is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the perspective of better dispersibility.

[0514] As colored pigments, examples include Victoria Blue BO (Color Index 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hostaperm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Supura (CI Pigment Red 81), and Monastralfast. The pigments include: Monolight Black B (CI Pigment Black 1), carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23. Among these, CI Pigment Red 177 is preferred.

[0515] When the photosensitive layer contains pigment, the pigment content relative to the total mass of the photosensitive layer is preferably more than 3% by mass and less than 40% by mass, more preferably more than 3% by mass and less than 35% by mass, even more preferably more than 5% by mass and less than 35% by mass, and especially preferably more than 10% by mass and less than 35% by mass.

[0516] When the photosensitive layer contains pigments other than black pigment (white pigment and colored pigment), the content of pigments other than black pigment is preferably 30% by mass or less relative to black pigment, more preferably 1% to 20% by mass, and even more preferably 3% to 15% by mass.

[0517] In addition, when the photosensitive layer contains a black pigment and the photosensitive layer is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion.

[0518] A dispersion can be prepared by adding a pre-mixed mixture of black pigment and pigment dispersant to an organic solvent (or carrier) and dispersing it using a disperser. The pigment dispersant can be selected based on the pigment and solvent; for example, commercially available dispersants can be used. The carrier refers to the medium through which the pigment is dispersed during the preparation of the pigment dispersion. It is liquid and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0519] There are no particular limitations on the type of dispersing machine; for example, well-known dispersing machines such as kneaders, roller mills, attritors, super mills, dissolvers, homogenizers, and sand mills can be cited. Alternatively, mechanical grinding can be used to achieve micronization through friction. For information on dispersing machines and micronization, please refer to the "Dictionary of Pigments" (Kunozou Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0520] (Methods for manufacturing resin patterns, methods for manufacturing laminates, and methods for manufacturing circuit wiring)

[0521] The method for manufacturing resin patterns according to the present invention is a method for forming resin patterns on a substrate using the photosensitive transfer material according to the present invention.

[0522] As a method for manufacturing resin patterns, a preferred method includes the following steps in sequence: a step of bringing the transfer layer in the photosensitive transfer material according to the present invention into contact with and bonding it to a substrate, preferably a substrate having a conductive layer (hereinafter also referred to as the "bonding step"); and a step of performing exposure treatment and development treatment on the exposed photosensitive layer to form a pattern (hereinafter also referred to as the "pattern forming step").

[0523] Furthermore, as a method for manufacturing resin patterns, it is preferable to include a step of peeling off the temporary support (hereinafter also referred to as the "temporary support peeling step") between the above-mentioned bonding step and the above-mentioned pattern forming step.

[0524] Furthermore, as a method for manufacturing resin patterns, it is preferable to include a process of peeling off the protective film (hereinafter also referred to as the "protective film peeling process") before the above-mentioned bonding process.

[0525] The method for manufacturing the laminate involved in this invention is a method for manufacturing a laminate having a resin pattern on a substrate using the photosensitive transfer material involved in this invention.

[0526] The preferred method for manufacturing a laminated body is a method that sequentially includes the above-described bonding process and the above-described exposure and development process.

[0527] Furthermore, as a method for manufacturing the laminate, it is preferable to include a temporary support peeling process between the above-mentioned bonding process and the above-mentioned exposure and development process.

[0528] Furthermore, as a method for manufacturing the laminate, it is preferable to include a protective film peeling process before the aforementioned bonding process.

[0529] Furthermore, the manufacturing method of the laminate according to the present invention preferably includes the following steps in sequence: a bonding step, wherein the transfer layer of a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer containing an olefinic unsaturated compound is bonded to a substrate to form a laminate; a peeling step, wherein the temporary support is peeled off from the laminate; and a pattern forming step, wherein the exposed photosensitive layer is exposed and developed to form a pattern, wherein a pattern is formed in air at 23°C and 1 atmosphere using an ultra-high pressure mercury lamp with an energy density of 100 mJ / cm at a wavelength of 365 nm. 2 When exposure is performed, the ratio D4 / D3 of the olefin unsaturated bond disappearance rate D3 when the photosensitive layer of the laminate produced in the bonding process is exposed via the temporary support to the olefin unsaturated bond disappearance rate D4 when the photosensitive layer is exposed after the temporary support is peeled off in the peeling process is 80% to 100%.

[0530] In the method for manufacturing the laminated body involved in this invention, from the viewpoint of resolution and pattern forming properties, in air at 23°C and 1 atmosphere, an ultra-high pressure mercury lamp with an energy density of 100 mJ / cm² at a wavelength of 365 nm is used. 2 When exposure is performed, the ratio D4 / D3 of the olefin unsaturated bond disappearance rate D3 when the photosensitive layer of the laminate in the bonding process is exposed via the temporary support to the olefin unsaturated bond disappearance rate D4 when the photosensitive layer is exposed after the temporary support is peeled off in the peeling process is preferably 70% to 100%, more preferably 80% to 100%, further preferably 85% to 100%, particularly preferably 90% to 100%, and most preferably 95% to 100%.

[0531] Regarding the values ​​of D3, D4, and D4 / D3 in this invention, apart from measuring the olefin unsaturated bond disappearance rate when the photosensitive layer of the laminate in the bonding process is exposed via the temporary support, and measuring the olefin unsaturated bond disappearance rate when the photosensitive layer is exposed after the temporary support is peeled off in the peeling process, the values ​​can be measured and calculated using the same method as the methods for measuring and calculating the values ​​of D1, D2, and D2 / D1 described above.

[0532] There are no particular limitations on the method of manufacturing the circuit wiring involved in this invention, as long as it uses the photosensitive transfer material involved in this invention.

[0533] As a method for manufacturing circuit wiring according to the present invention, a preferred method includes the following steps in sequence: a step of bringing the transfer layer in the photosensitive transfer material according to the present invention into contact with and bonding it to a substrate, preferably a substrate having a conductive layer; a pattern forming step of exposing and developing the exposed photosensitive layer to form a pattern; and a step of etching the conductive layer in areas where the resin pattern is not disposed (hereinafter also referred to as the "etching step").

[0534] Furthermore, as a method for manufacturing circuit wiring, it is preferable to include a temporary support peeling process between the above-mentioned bonding process and the above-mentioned pattern forming process.

[0535] Furthermore, as a method for manufacturing circuit wiring, it is preferable to include a protective film peeling process before the aforementioned bonding process.

[0536] The following describes the steps involved in the manufacturing methods of resin patterns, laminates, and circuit wiring. However, unless otherwise specified, the descriptions of the steps involved in the manufacturing methods of resin patterns or laminates also apply to the steps involved in the manufacturing methods of circuit wiring.

[0537] <Protective film peeling process>

[0538] The method for manufacturing the resin pattern or the laminate preferably includes a step of peeling off the protective film from the photosensitive transfer material involved in the present invention. There are no limitations on the method for peeling off the protective film; known methods can be used.

[0539] <Lamination Process>

[0540] The method for manufacturing resin patterns or laminates preferably includes a bonding process.

[0541] In the bonding process, it is preferable to bring the transfer layer of the photosensitive transfer material into contact with the substrate (or, if a conductive layer is provided on the surface of the substrate), thereby pressing the photosensitive transfer material and the substrate together. If this is done, the adhesion between the transfer layer of the photosensitive transfer material and the substrate is improved, and therefore the patterned photosensitive layer formed after exposure and development can preferably be used as an etch resist when etching the conductive layer.

[0542] Furthermore, in the bonding process, if the photosensitive transfer material has a layer other than a protective film (e.g., a high refractive index layer and / or a low refractive index layer) on the side of the photosensitive layer that does not face the temporary support, then the side of the photosensitive layer that does not have the temporary support is bonded to the substrate through this layer.

[0543] There are no particular limitations on the method of bonding the substrate to the photosensitive transfer material; known transfer methods and lamination methods can be used.

[0544] Regarding the bonding of photosensitive transfer material to a substrate, it is preferable to overlap the outermost layer of the photosensitive transfer material, which has a photosensitive layer relative to the temporary support, with the substrate, and then apply pressure and heat using a mechanism such as rollers. Known laminators, vacuum laminators, and automated cutting laminators that can further improve productivity can be used for bonding.

[0545] There are no particular limitations on the lamination temperature; for example, 70°C to 130°C is preferred.

[0546] Regarding the manufacturing method of the resin pattern including the bonding process and the manufacturing method of the laminate, it is preferable to carry out the process by roll-to-roll.

[0547] The following explains the roll-to-roll method.

[0548] The so-called roll-to-roll method refers to the following method: using a substrate capable of being rolled up and rolled out, including a process of rolling out the substrate or a structure containing the substrate before any step included in the resin pattern manufacturing method or etching method (also called a "roll-out process") and a process of rolling up the substrate or a structure containing the substrate after any step (also called a "roll-up process"), and performing at least one step (preferably all steps, or all steps except the heating step) while conveying the substrate or the structure containing the substrate.

[0549] There are no particular restrictions on the winding method in the winding process and the winding method in the winding process. In manufacturing methods that are applicable to roll-to-roll manufacturing, any known method may be used.

[0550] <Substrate>

[0551] As the substrate used in the method for manufacturing the resin pattern according to the present invention, a known substrate can be used, but a substrate having a conductive layer is preferred, and a substrate having a conductive layer on its surface is more preferred.

[0552] The substrate can have any layer other than the conductive layer, as needed.

[0553] Examples of substrates include resin substrates, glass substrates, and semiconductor substrates.

[0554] As a preferred substrate, for example, the method described in paragraph 0140 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0555] Examples of substrates that form a substrate include glass, silicon, and films.

[0556] The substrate constituting the substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400nm to 700nm is 80% or more.

[0557] Furthermore, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

[0558] As a transparent glass substrate, tempered glass, such as Corning Incorporated Gorilla Glass, can be used. Furthermore, as a transparent glass substrate, the materials used in Japanese Patent Application Publication Nos. 2010-86684, 2010-152809, and 2010-257492 can be used.

[0559] When using a film substrate as the substrate, it is preferable to use a film substrate with low optical strain and / or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cyclic olefin polymers.

[0560] When manufacturing using a roll-to-roll method, a film substrate is preferred as the substrate. Furthermore, when manufacturing circuit wiring for a touch panel using a roll-to-roll method, a sheet-like resin composition is preferred as the substrate.

[0561] As a conductive layer in a substrate, examples include the conductive layers used in typical circuit wiring or touch panel wiring.

[0562] From the viewpoint of conductivity and fine line formation, the conductive layer is preferably selected from at least one of 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.

[0563] The substrate may have a single conductive layer or two or more conductive layers. When there are two or more conductive layers, it is preferable that the conductive layers are made of different materials.

[0564] Materials that can be used as conductive layers include metals and conductive metal oxides.

[0565] Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0566] Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO2.

[0567] Furthermore, in this specification, "conductivity" refers to a volume resistivity of less than 1×10⁻⁶. 6 Ωcm. The volume resistivity of conductive metal oxides is preferably less than 1×10⁻⁶. 4 Ωcm.

[0568] When using a substrate having multiple conductive layers to manufacture resin patterns, at least one of the multiple conductive layers preferably contains a conductive metal oxide.

[0569] As a conductive layer, it is preferable to be the electrode pattern of the sensor or the wiring of the peripheral lead-out portion, which corresponds to the visual recognition part used in an electrostatic capacitive touch panel.

[0570] As a preferred method for the conductive layer, for example, the method described in paragraph 0141 of International Publication No. 2018 / 155193, the contents of which are incorporated herein by reference.

[0571] The substrate having a conductive layer is preferably a substrate having at least one of a transparent electrode and a circuitous wiring. The substrate described above can preferably be used as a substrate for a touch panel.

[0572] Transparent electrodes are preferably used as electrodes for touch panels. The transparent electrodes are preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), as well as fine metal wires such as metal mesh and silver nanowires.

[0573] Examples of fine metal wires include those made of silver and copper. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

[0574] Metal is the preferred material for circuitous wiring.

[0575] Metals suitable for use as materials for circuit routing include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys composed of two or more of these metallic elements. Copper, molybdenum, aluminum, or titanium are preferred materials for circuit routing, with copper being particularly preferred.

[0576] For the purpose of protecting electrodes (i.e., at least one of the electrodes for touch panels and the wiring for touch panels), the electrode protective film for touch panels formed using the photosensitive transfer material involved in the present invention is preferably provided in a manner that covers the electrodes directly or through other layers.

[0577] <Temporary Support Removal Process>

[0578] The method for manufacturing resin patterns or laminates preferably includes a temporary support peeling process between the bonding process and the exposure process.

[0579] There are no particular restrictions on the method for peeling off the temporary support; the same mechanism as the covering film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Publication No. 2010-072589 can be used.

[0580] <Pattern Formation Process>

[0581] The method for manufacturing a resin pattern or a laminate preferably includes, after the above-mentioned lamination process, a process of exposing and developing the exposed photosensitive layer to form a pattern (pattern forming process).

[0582] The above exposure processing is a patterned exposure processing (also known as "patterned exposure"), that is, an exposure processing in which there are exposed and unexposed parts.

[0583] There are no particular restrictions on the positional relationship between the exposed and unexposed areas in the pattern exposure; it can be adjusted appropriately.

[0584] There are no particular limitations on the detailed configuration and specific dimensions of the pattern in the pattern exposure. For example, in order to improve the display quality of a display device (e.g., a touch panel) having an input device with circuit wiring manufactured by an etching method, and to reduce the area occupied by the lead wiring, at least a portion of the pattern (preferably the electrode pattern and / or the lead wiring portion of the touch panel) preferably includes fine lines with a width of 20 μm or less, and more preferably fine lines with a width of 10 μm or less.

[0585] Regarding the light source used in the exposure, any light source that illuminates the photosensitive layer at a wavelength capable of exposing the photosensitive layer (e.g., 365nm or 405nm) can be appropriately selected and used. Specifically, examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

[0586] The preferred exposure level is 5 mJ / cm². 2 ~200mJ / cm 2 More preferably 10 mJ / cm 2 ~100mJ / cm 2 .

[0587] Preferred methods for the light source, exposure amount, and exposure method used in the exposure process include, for example, those described in paragraphs 0146-0147 of International Publication No. 2018 / 155193, which are incorporated herein by reference.

[0588] In the exposure process, pattern exposure can be performed after the temporary support is peeled off from the photosensitive layer, or pattern exposure can be performed with the temporary support in between, before peeling off the temporary support, and then the temporary support is peeled off. When the temporary support is peeled off before exposure, the mask can be exposed in contact with the photosensitive layer, or it can be exposed close to it without contact. When exposure is performed without peeling off the temporary support, the mask can be exposed in contact with the temporary support, or it can be exposed close to it without contact. To prevent mask contamination caused by contact between the photosensitive layer and the mask, and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. Furthermore, regarding the exposure method, in the case of contact exposure, a contact exposure method can be appropriately selected and used; in the case of non-contact exposure, a proximity exposure method, a projection exposure method using a lens system or mirror system, or a direct exposure method using an exposure laser can be appropriately selected and used. In the case of projection exposure using a lens system or mirror system, an exposure machine with an appropriate number of lens apertures (NA) can be used depending on the required resolution and depth of focus. In the direct exposure method, the photosensitive layer can be directly depicted, or the photosensitive layer can be exposed by projecting a reduced image through a lens. Furthermore, exposure can be performed not only in the atmosphere, but also under reduced pressure or vacuum conditions, and even with a liquid such as water between the light source and the photosensitive layer.

[0589] In the pattern forming process, after exposure, the exposed photosensitive layer is developed to form a pattern.

[0590] It can use a developer to develop the exposed photosensitive layer in the pattern forming process.

[0591] As for the developer, there are no particular limitations as long as it can remove the non-image portion of the photosensitive layer. For example, known developers such as the developer described in Japanese Patent Application Publication No. 5-72724 can be used.

[0592] The preferred developer is an alkaline aqueous solution containing a compound with pKa = 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain water-soluble organic solvents and / or surfactants.

[0593] Examples of alkaline compounds that can be included in alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0594] As a developer, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 is preferably cited. As a preferred developing method, for example, the developing method described in paragraph 0195 of International Publication No. 2015 / 093271 can be cited.

[0595] There are no particular restrictions on the development method; it can be any of the following: spin-dip development, spray development, spray and spin development, or immersion development. Spray development is a development process that removes non-image areas by spraying the developer solution onto the exposed photosensitive layer.

[0596] Preferably, after the pattern forming process, the developing residue is removed by spraying a cleaning agent while wiping with a brush.

[0597] There are no particular restrictions on the temperature of the developer solution, but it is preferably 20℃~40℃.

[0598] <Etching Process>

[0599] The manufacturing method of the circuit wiring preferably includes a process of etching the substrate in the area where the resin pattern is not configured (etching process).

[0600] In the etching process, the resin pattern formed by the photosensitive layer is used as the etching resist, and the conductive layer is etched.

[0601] As a method for etching, known methods can be applied, such as the methods described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435, the methods described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, wet etching methods immersed in etching solution, and dry etching methods based on plasma etching, etc.

[0602] In wet etching, the etching solution used can be either acidic or alkaline, depending on the object being etched.

[0603] Examples of acidic etching solutions include, for example, aqueous solutions of a single acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as aqueous solutions of the acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component can also be a combination of multiple acidic components.

[0604] Examples of alkaline etching solutions include aqueous solutions of the alkaline component alone, selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), as well as aqueous solutions of the alkaline component mixed with salts (such as potassium permanganate). The alkaline component can also be a combination of multiple alkaline components.

[0605] <Removal Process>

[0606] In the manufacturing method of circuit wiring, it is preferable to perform a process to remove residual resin patterns (removal process).

[0607] There are no particular restrictions on the removal process; it can be performed as needed, but it is preferred to do so after the etching process.

[0608] There are no particular limitations on the method for removing residual resin patterns. Methods such as removal by chemical treatment can be cited, but removal by using a removal solution is preferred.

[0609] As a method for removing the photosensitive layer, one example is to immerse a substrate with residual resin patterns in a removal solution at a temperature preferably 30°C to 80°C, more preferably 50°C to 80°C, under stirring, for 1 minute to 30 minutes.

[0610] Examples of removal solutions include those made by dissolving an inorganic or organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic base components include sodium hydroxide and potassium hydroxide. Examples of organic base components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0611] Furthermore, a removal liquid can be used to remove it by known methods such as spraying, rinsing, and immersion.

[0612] <Other processes>

[0613] The methods for manufacturing resin patterns, laminates, and circuit wiring may include any steps other than those described above (other steps). For example, the following steps may be cited, but are not limited to these steps.

[0614] Furthermore, as exposure, development and other processes applicable to the manufacturing method of circuit wiring, examples can be found in paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-23696.

[0615] In addition, other processes may include, for example, the process of reducing visible light reflectivity described in paragraph 0172 of International Publication No. 2019 / 022089, and the process of forming a new conductive layer on an insulating film described in paragraph 0172 of International Publication No. 2019 / 022089, but are not limited to these processes.

[0616] -Processes to reduce visible light reflectivity-

[0617] The manufacturing method of circuit wiring may include a process of performing a treatment to reduce the visible light reflectivity of some or all of the multiple conductive layers on a substrate.

[0618] Oxidation is an example of a process to reduce visible light reflectivity. When a substrate has a conductive layer containing copper, copper is oxidized to produce copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer.

[0619] Treatments for reducing visible light reflectivity are described in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, the contents of which are incorporated herein by reference.

[0620] -The process of forming an insulating film, and the process of forming a new conductive layer on the surface of the insulating film-

[0621] The preferred method for manufacturing circuit wiring includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.

[0622] Through the above-described process, a second electrode pattern that is insulated from the first electrode pattern can be formed.

[0623] There are no particular limitations on the process of forming the insulating film, and well-known methods for forming permanent films can be cited. Furthermore, an insulating photosensitive material with insulating properties can be used, and an insulating film with the desired pattern can be formed by photolithography.

[0624] There are no particular restrictions on the process of forming a new conductive layer on the insulating film. For example, a photosensitive material with conductivity can be used, and a new conductive layer with the desired pattern can be formed by photolithography.

[0625] Regarding the manufacturing method of the circuit wiring, it is preferable to use a substrate having multiple conductive layers on each of its two surfaces, and to form circuits sequentially or simultaneously on the conductive layers formed on the two surfaces of the substrate. With this structure, it is possible to form touch panel circuit wiring with a first conductive pattern formed on one surface of the substrate and a second conductive pattern formed on the other surface. Furthermore, it is also preferable to form this type of touch panel circuit wiring from both sides of the substrate in a roll-to-roll manner.

[0626] <Application>

[0627] The resin pattern manufactured by the resin pattern manufacturing method according to the present invention, the laminate manufactured by the laminate manufacturing method according to the present invention, and the circuit wiring manufactured by the circuit wiring manufacturing method according to the present invention can be applied to various devices. As a device equipped with the above-mentioned laminate, examples include input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the above-mentioned input devices can be applied to display devices such as organic light-emitting display devices and liquid crystal display devices.

[0628] When the laminate is suitable for a touch panel, the formed resin pattern is preferably used as a protective film for electrodes or wiring of the touch panel. That is, the photosensitive transfer material involved in the present invention is preferably used for forming protective films for electrodes or wiring of the touch panel.

[0629] (Manufacturing methods for electronic devices)

[0630] There are no particular limitations on the manufacturing method of the electronic device involved in this invention, as long as the method uses the photosensitive transfer material involved in this invention.

[0631] As a method for manufacturing an electronic device according to the present invention, it preferably includes the following steps in sequence: a step of peeling off the protective film from the photosensitive transfer material according to the present invention; a step of bringing the outermost layer of the photosensitive transfer material on the side having the photosensitive layer relative to the temporary support into contact with and bonding it to a substrate having a conductive layer; and a step of performing exposure treatment and development treatment on the exposed photosensitive layer to form a pattern, and the manufactured electronic device has the resin pattern.

[0632] The electronic device manufactured by the manufacturing method of the electronic device involved in the present invention preferably has the above-mentioned resin pattern as a permanent film.

[0633] Regarding the specific methods and sequence of each step in the manufacturing method of electronic devices, the preferred methods are the same as those described in the sections on "method for manufacturing resin patterns" and "etching method" above.

[0634] In the manufacturing method of electronic devices, the wiring for electronic devices is formed by the above-described method. Otherwise, any other known manufacturing method of electronic devices may be referred to.

[0635] Furthermore, the manufacturing method of electronic devices may also include any other process (other processes) besides those mentioned above.

[0636] As an electronic device, there are no particular limitations, but preferred examples include semiconductor packaging, printed circuit boards, various wiring applications for sensor substrates, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, and structures in the fields of micromechanics or microelectronics.

[0637] The resin pattern described above is preferably used as a permanent film in the aforementioned electronic device, such as an interlayer insulating film, a wiring protection film, or a wiring protection film with a refractive index matching layer.

[0638] Among these, touch panels are particularly preferred as electronic devices.

[0639] exist Figure 2 and Figure 3 The image shows an example of a mask pattern used in the manufacture of a touch panel.

[0640] exist Figure 2 Pattern A shown Figure 3 In pattern B shown, GR represents the non-image area (light-shielding area), EX represents the image area (exposure area), and DL virtually represents the alignment frame. In a touch panel manufacturing method, for example, by means of having... Figure 2 By exposing the photosensitive layer to a mask showing pattern A, a touch panel with circuit wiring corresponding to pattern A corresponding to FX can be manufactured. Specifically, this can be achieved through International Publication No. 2016 / 190405. Figure 1 The touch panel is manufactured using the method described herein. In one example of the manufactured touch panel, the central part of the exposure section EX (the patterned part formed by connecting the four corners) is the part that forms the transparent electrode (the electrode for the touch panel), and the peripheral part of the exposure section EX (the fine line part) is the part that forms the wiring of the peripheral lead-out part.

[0641] By using the above-described method for manufacturing electronic devices, an electronic device with at least wiring for electronic devices is manufactured, and preferably a touch panel with at least wiring for a touch panel is manufactured.

[0642] The touch panel preferably has a transparent substrate, electrodes, an insulating layer, or a protective layer.

[0643] Commonly known detection methods used in touch panels include resistive film detection, capacitive detection, ultrasonic detection, electromagnetic induction, and optical detection. Among these, capacitive detection is preferred.

[0644] As for touch panel types, examples include so-called embedded types (e.g., those shown in Figures 5, 6, 7, and 8 of Japanese Patent Application Publication No. 2012-517051) and so-called external types (e.g., those shown in Figure 19 of Japanese Patent Application Publication No. 2013-168125 and those shown in Japanese Patent Application Publication No. 2012-89102). Figure 1 (and the contents shown in Figure 5), OGS (One Glass Solution: monolithic glass touch technology) type, TOL (Touch-on-Lens: overlay touch) type (for example, Japanese Patent Application Publication No. 2013-54727). Figure 2 The contents described therein), various plug-in types (such as GG, G1·G2, GFF, GF2, GF1 and G1F, etc.) and other structures (for example, the contents described in Figure 6 of Japanese Patent Application Publication No. 2013-164871).

[0645] As a touch panel, for example, the touch panel described in paragraph 0229 of Japanese Patent Application Publication No. 2017-120435 can be cited.

[0646] Example

[0647] The following examples illustrate the implementation of the present invention in more detail. The materials, amounts, proportions, processing methods, and processing order shown in the following examples can be appropriately modified without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Furthermore, unless otherwise specified, "parts" and "%" refer to quality standards.

[0648] <Polymer>

[0649] In the following synthetic examples, the following abbreviations refer to the following compounds.

[0650] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0651] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0652] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0653] PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[0654] V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (Prepared by FUJIFILM Wako Pure Chemical Corporation)

[0655] <Synthesis of Polymer A-1>

[0656] PGMEA (116.5 parts) was added to a three-necked flask, and the mixture was heated to 90°C under a nitrogen atmosphere. A solution containing St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts) was added dropwise to the solution in the three-necked flask maintained at 90°C ± 2°C over 2 hours. After the addition was complete, the mixture was stirred at 90°C ± 2°C for 2 hours to obtain polymer A-1 (30.0% solids concentration).

[0657] <Alkene unsaturated compounds>

[0658] B-1: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0659] B-2: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.)

[0660] B-3: SR454 (3 moles of ethoxylated trimethylolpropane triacrylate, manufactured by Sartamomer Company, Inc.)

[0661] <Photoradical polymerization initiator>

[0662] C-1: Irgacure OXE02 (Photoradical polymerization initiator, oxime ester-based photopolymerization initiator, generates methyl radicals, manufactured by BASF)

[0663] C-2: BIMD (photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer, B-CIM manufactured by Hampford Company)

[0664] C-3: EAB-F (Photoradical polymerization initiator (sensitizer), 4,4'-bis(diethylamino)benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0665] C-4: Karenz MTBD1 (produced by combining polyfunctional thiols and free radical polymerization initiators to generate sulfur-containing free radicals, manufactured by SHOWA DENKO KK)

[0666] C-5 (N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)): 0.02 parts

[0667] <Additives>

[0668] D-1: CBT-1 (carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD)

[0669] D-2: LCV (colorless crystal violet, manufactured by YAMADA CHEMICAL CO., LTD.)

[0670] D-3: Phenothiazine (manufactured by Seiko Chemical Co., Ltd.)

[0671] D-4: 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0672] D-5: Kunipia F (an inorganic layered compound (bentonite), manufactured by KUNIMINE INDUSTRIES CO., LTD.)

[0673] <surfactants>

[0674] E-1: Megafac F-552 (Fluoropolymer surfactant, manufactured by DIC Corporation)

[0675] E-2: Megafac F-444 (Fluoropolymer surfactant, manufactured by DIC Corporation)

[0676] Water-soluble resins

[0677] F-1: Kuraray EVAL E105B (Polyvinyl alcohol (ethylene-polyvinyl alcohol copolymer), hydrolysis degree 100 mol%, manufactured by KURARAY CO., LTD.)

[0678] F-2: Kuraray Poval PVA-4-88LA (polyvinyl alcohol, saponification degree 88, hydrolysis degree 88 mol%, manufactured by KURARAYC0., LTD.)

[0679] F-3: Kuraray Poval PVA-L-8 (Polyvinyl alcohol, saponification degree 71, hydrolysis degree 71 mol%, manufactured by KURARAY CO., LTD.)

[0680] F-4: Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.)

[0681] F-5: METOLOSE 60SH (Hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0682] The degree of hydrolysis of polyvinyl alcohol (F-1 to F-3) was determined according to the method described in JISK 6726:1994.

[0683] <Preparation of Photosensitive Resin Composition 1>

[0684] The following components were mixed to prepare photosensitive resin composition 1. The amount of each component is expressed in parts by mass.

[0685] Polymer A-1 (solids concentration 30.0%): 25.2 parts

[0686] B-1 (NK ester BPE-500, ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 2.81 parts

[0687] B-2 (ARONIX M-270, polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.): 0.58 parts

[0688] B-3 (SR454, 3 moles of ethoxylated trimethylolpropane triacrylate, manufactured by Sartamomer Company, Inc.): 2.81 parts

[0689] C-1 (Irgacure OXE02, photoradical polymerization initiator, oxime ester photopolymerization initiator, manufactured by BASF): 0.11 parts

[0690] C-5 (N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)): 0.02 parts

[0691] D-1 (CBT-1 (manufactured by J0HOKU CHEMICAL CO., LTD): 0.015 copies

[0692] D-2 (LCV, colorless crystal violet, manufactured by YAMADA CHEMICAL CO., LTD., a pigment that develops color via free radicals): 0.06 parts

[0693] D-3 (Phenothiazine, manufactured by Seiko Chemical Co., Ltd.): 0.04 parts

[0694] D-4 (4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolone, manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.002 parts

[0695] E-1 (Megafac F552, manufactured by DIC Corporation): 0.048 copies

[0696] Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 43.8 parts

[0697] PGMEA (made by SHOWA DENKO KK): 19.7 servings

[0698] Propylene glycol monomethyl ether (MFG, manufactured by Nippon Nyukazai Co, Ltd.): 3.89 parts

[0699] <Preparation of Intermediate Layer Composition 1>

[0700] The intermediate layer composition was prepared by mixing the following components.

[0701] Ion-exchanged water: 38.12 parts

[0702] Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts

[0703] F-2 (Kuraray PovalPVA-4-88LA, polyvinyl alcohol, manufactured by KURARAY CO., LTD.): 3.22 parts

[0704] F-4 (Polyvinylpyrrolidone K-30, manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts

[0705] F-5 (METOLOSE 60SH, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.04 parts

[0706] D-5 (Made by Kunipia G, KUNIMINE INDUSTRIES CO., LTD.): 0.08 parts

[0707] E-2 (Megafac F-444 (fluorinated surfactant, manufactured by DIC Corporation): 0.001 parts)

[0708] After pre-dispersing the above mixture in high-speed stirring (3,000 rpm, circumferential speed = 8.2 m / min), it was then dispersed using a high-pressure dispersion device 1 (trade name: NANOMIZER NMII-2000AR, manufactured by Yoshida Kikai Co., Ltd.) at 1,000 kgf / cm³. 2 The intermediate layer composition 1 was obtained by processing under pressure conditions.

[0709] (Example 1)

[0710] <Preparation of Photosensitive Transfer Materials>

[0711] In the manner shown in Table 1 below, an intermediate layer composition 1 was applied to a 16 μm thick polyethylene terephthalate film (TORAY INDUSTRIES, INC., Lumirror 16QS62) serving as a temporary support using a slit nozzle with a coating width of 1.0 μm and a layer thickness of 1.1 μm. The film was then passed through a drying zone at 80°C for 40 seconds, thereby forming an intermediate layer. Subsequently, a photosensitive resin composition 1 was applied to the intermediate layer using a slit nozzle with a coating width of 1.0 μm and a layer thickness of 5.0 μm. This photosensitive layer was then passed through a drying zone at 80°C for 40 seconds, thereby forming a photosensitive layer.

[0712] -Oxygen permeability measurement of the transfer layer-

[0713] A photosensitive transfer material was laminated onto a cellulose triacetate (TAC) substrate (40 μm thick) from the photosensitive layer side under lamination conditions of 100°C roller temperature, 1.0 MPa linear pressure, and 4.0 m / min linear speed. A temporary support was then peeled off to prepare the test sample. The test sample was attached to the electrode area via silicone grease, and the measurement environment was adjusted to 23°C and 50% RH. The oxygen permeability coefficient (i.e., oxygen permeability) was determined from the amount of oxygen reaching the electrode under steady-state conditions (Apparatus: Hach Ultra Analytics, Inc., MODEL3600 oxygen meter).

[0714] -Ratio of the rate of disappearance of olefinic unsaturated bonds (C=C disappearance rate) after exfoliation / exposure before exfoliation-

[0715] In the resolution evaluation described below, the C=C disappearance rate was measured and compared when exposed without a mask after peeling off the temporary support and when exposed without peeling off the temporary support. Measurements were performed after exposure and storage in air at 1 atm pressure and 23 μm / 5% RH for 3 hours. The C=C disappearance rate was determined using the following method. In the disappearance rate determination of samples with an intermediate layer, the photosensitive layer exposed after wiping away the intermediate layer with water was used.

[0716] Using a LUMOS sensor manufactured by Bruker Optics, ATR measurements (Ge crystallization) were performed with an MCT detector, a wavenumber resolution of 4 cm⁻¹, and a total of 32 measurements. The C=C stretching (1,635 cm⁻¹) was determined from the exposed and unexposed samples. -1 The peak height (after background processing) is scaled using CH (2,900cm). -1 The value is obtained by standardizing the peak height of the samples. Their ratio (exposed / unexposed) is set as C=C residual rate. The disappearance rate of C=C is calculated by 1-(C=C residual rate).

[0717] <Performance Evaluation>

[0718] A PET substrate with a copper layer was used, on which a copper layer with a thickness of 200 nm was fabricated by sputtering on a 100 μm thick polyethylene terephthalate (PET) film.

[0719] -Resolution-

[0720] The prepared photosensitive transfer material was laminated onto the copper-coated PET substrate under lamination conditions of 100°C roller temperature, 1.0 MPa linear pressure, and 4.0 m / min linear speed. A temporary support was peeled off from the laminated substrate, and it was placed on the substrate mounting stage of a projection exposure machine (Ushio Inc. UX-2023SM). A glass chromium photomask with a linear and spatial pattern (duty cycle 1:1, linewidth varying in 1 μm increments between 1 μm and 10 μm) was placed on the mask holder of the exposure machine. The photomask was then exposed to a projection lens at an exposure dose of 100 mJ / cm². 2 After the temporary support was removed, the sample was exposed 10 minutes later, followed by development.

[0721] For development, a 1.0% sodium carbonate aqueous solution at 25°C was used, and development was carried out by spraying for 30 seconds.

[0722] When a 10 μm line and space pattern is formed using the above method, the residue in the space is observed using a scanning electron microscope (SEM). When the exposure is performed with an exposure amount that is exactly 10 μm for the resist linewidth, the minimum linewidth at which the resist pattern can be distinguished without peeling or residue is used as the resolution.

[0723] A: Resolution below 2μm

[0724] B: Resolution of 3μm or higher and 4μm or lower

[0725] C: Resolution of 5μm or higher and 6μm or lower

[0726] D: Resolution of 7μm or higher

[0727] The preferred options are A to C.

[0728] -Pattern Shape-

[0729] The cross-section of the minimum linewidth pattern for which the above resolution evaluation was performed was observed using a scanning electron microscope (SEM), and the pattern shape was evaluated.

[0730] A: The pattern shape is rectangular.

[0731] B: The pattern shape is slightly reduced.

[0732] C: The top of the pattern is rounded and narrows.

[0733] D: Pattern collapses, hem widens

[0734] The preferred options are A to C.

[0735] (Examples 2-11 and Comparative Examples 1 and 2)

[0736] The composition of the intermediate layer and the photosensitive layer was changed as described in Table 1. Otherwise, the photosensitive transfer materials of Examples 2 to 11, and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1.

[0737] Furthermore, the performance was evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 1.

[0738] [Table 1]

[0739]

[0740] The values ​​of D4 / D3 in Examples 1-11, and Comparative Examples 1 and 2 are the same as the values ​​of D2 / D1 recorded in Table 1.

[0741] As shown in Table 1 above, the photosensitive transfer materials of Examples 1 to 11 have superior resolution compared to the photosensitive transfer materials of Comparative Example 1 or Comparative Example 2, even when the photosensitive layer is directly exposed without passing through a temporary support.

[0742] Furthermore, as shown in Table 1 above, the photosensitive transfer materials of Examples 1 to 11 also exhibit excellent pattern-forming properties.

[0743] (Example 101: Contact Exposure)

[0744] Under lamination conditions of 100 μm roller temperature, 1.0 MPa linear pressure, and 4.0 m / min linear speed, the photosensitive transfer material prepared in Example 1 was laminated onto the copper-coated PET substrate. The temporary support was peeled off, and the substrate was exposed using an ultra-high pressure mercury lamp through a line and space pattern mask (duty cycle 1:1, line width varying in 1 μm increments from 1 μm to 10 μm), followed by development.

[0745] For development, a 1.0% sodium carbonate aqueous solution at 25°C was used, and development was carried out by spraying for 30 seconds.

[0746] The patterned substrate obtained by microscopic observation shows a pattern with good resolution and shape.

[0747] (Example 102: Direct Laser Drawing)

[0748] Under lamination conditions of 100°C roller temperature, 1.0 MPa linear pressure, and 4.0 m / min linear speed, the photosensitive transfer material prepared in Example 1 was laminated onto the copper-coated PET substrate. Using a direct drawing exposure machine (ViaMechanics, Ltd., DE-1DH, light source: GaN cyan-violet diode (main wavelength 405 nm ± 5 nm)), a Stouffer 21-step exposure table or a specified DI exposure mask pattern was used at an illuminance of 80 mW / cm². 2 Exposure was performed under the specified conditions. The exposure was conducted using the aforementioned Stouffer 21-step steptablet as a mask, with the highest residual film level during exposure and development being 6. For development, a 1.0% sodium carbonate aqueous solution at 25°C was used, and development was performed by spraying for 30 seconds.

[0749] The patterned substrate obtained by microscopic observation shows a pattern with good resolution and shape.

[0750] (Example 103)

[0751] A circuit board was fabricated by sputtering an ITO film to a thickness of 150 nm on a 100 μm thick PET substrate as the second conductive layer, and then forming a copper film to a thickness of 200 nm on top of it as the first conductive layer by vacuum evaporation.

[0752] On the copper layer, a cover film is peeled off, and the photosensitive transfer material obtained in Example 1 is bonded to the substrate (lamination roller temperature 100°C, linear pressure 0.8 MPa, linear speed 3.0 m / min) to form a laminate. A structure with conductive layer pads connected in one direction by a temporary peel support is used. Figure 2The photomask of pattern A shown was used to perform contact pattern exposure on the resulting stack. During the exposure, a high-pressure mercury lamp with i-rays (365nm) as the dominant exposure wavelength was used.

[0753] Afterwards, development and washing were performed to obtain pattern A. Next, the copper layer was etched using copper etching solution (KANTO CHEMICAL CO., INC. Cu-02), and the ITO layer was etched using ITO etching solution (KANTO CHEMICAL CO., INC. ITO-02), thereby obtaining a substrate in which both copper and ITO are depicted as pattern A.

[0754] Next, the cover film was peeled off, and under the same conditions as in Example 101, the photosensitive transfer material obtained in Example 1 was again adhered to the remaining resist (cured negative photosensitive layer). With the material aligned, the temporary support was peeled off, and... Figure 3 The pattern B is obtained by exposing the photomask with pattern B, followed by development and washing. Next, the copper wiring is etched using Cu-02, and the residual cured negative photosensitive layer is removed using stripping solution (KANTO CHEMICAL CO., INC. KP-301) to obtain the circuit wiring substrate.

[0755] The results of microscopic observation of the circuit wiring substrate showed no peeling or defects, indicating a perfect pattern.

[0756] The entire contents of Japanese Patent Application No. 2020-217789, filed on December 25, 2020, are incorporated herein by reference. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as those specifically and separately described and incorporated herein by reference.

Claims

1. A photosensitive transfer material having a temporary support and a transfer layer comprising a photosensitive layer containing an olefinically unsaturated compound, A substrate with a metal layer on its surface is bonded to the transfer layer in the photosensitive transfer material. The bonding is performed in air at 23°C, 1 atm pressure, and 55% RH using an ultra-high pressure mercury lamp with an energy density of 100 mJ / cm² at a wavelength of 365 nm. 2 When the photosensitive layer is exposed, the ratio of the disappearance rate of olefinic unsaturated bonds D1 (without peeling off the temporary support) to the disappearance rate of olefinic unsaturated bonds D2 (after peeling off the temporary support), measured using a fully automated Fourier transform infrared (FT-IR) microscope, is 70% to 100%. In the D1 measurement, the temporary support is not peeled off from the laminated substrate, but is placed on the substrate mounting stage of a projection exposure machine, namely the Ushio Inc. UX-2023SM. A glass chrome photomask with line and spatial patterns is set on the mask holder of the exposure machine, and the exposure is performed through a projection lens at an exposure dose of 100 mJ / cm². 2 Exposure is performed, with the duty cycle of the lines and spatial pattern at 1:1, and the line width varying in 1μm increments between 1μm and 10μm. In the D2 measurement, a temporary support was peeled off from the laminated substrate and placed on the substrate mounting stage of a projection exposure machine, specifically a Ushio Inc. UX-2023SM. A glass chrome photomask with line and spatial patterns was placed on the mask holder of the exposure machine, and the exposure was performed through a projection lens at an exposure dose of 100 mJ / cm². 2 After the temporary support is removed, exposure is performed 10 minutes later. The duty cycle of the line and the spatial pattern is 1:1, and the line width varies in stages every 1 μm between 1 μm and 10 μm.

2. The photosensitive transfer material according to claim 1, wherein, The oxygen permeability of the transfer layer is 1 mL / (m²). 2 ·day·atm)~100mL / (m 2 ·day·atm).

3. The photosensitive transfer material according to claim 1, wherein, The photosensitive layer contains a photoradical polymerization initiator.

4. The photosensitive transfer material according to claim 3, wherein, The photoradical polymerization initiator is a photopolymerization initiator that generates one or more of methyl radicals or sulfur-containing radicals as polymerization initiation species.

5. The photosensitive transfer material according to claim 1, wherein, An intermediate layer is also provided between the temporary support and the photosensitive layer.

6. The photosensitive transfer material according to claim 5, wherein, The intermediate layer contains a water-soluble compound.

7. The photosensitive transfer material according to claim 6, wherein, The water-soluble compound is selected from one or more compounds chosen from water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenolic derivatives, and amide compounds.

8. The photosensitive transfer material according to claim 6, wherein, The water-soluble compound is polyvinyl alcohol.

9. The photosensitive transfer material according to claim 8, wherein, The degree of hydrolysis of the polyvinyl alcohol is 73 mol% to 99 mol%.

10. The photosensitive transfer material according to claim 8, wherein, The polyvinyl alcohol contains ethylene as a monomer unit.

11. The photosensitive transfer material according to claim 5, wherein, The intermediate layer contains an inorganic layered compound.

12. The photosensitive transfer material according to any one of claims 1 to 11, wherein, The olefinic unsaturated compounds include polyfunctional olefinic unsaturated compounds.

13. The photosensitive transfer material according to any one of claims 1 to 11, wherein, The olefinic unsaturated compounds include olefinic unsaturated compounds with more than three functions.

14. The photosensitive transfer material according to any one of claims 1 to 11, wherein, The olefinic unsaturated compounds include olefinic unsaturated compounds having a polyoxyethylene structure.

15. A method for manufacturing a resin pattern, comprising the following steps: A process of bringing the transfer layer in any one of the photosensitive transfer materials according to claims 1 to 14 into contact with a substrate for bonding; and The process of exposing and developing the exposed photosensitive layer to form a pattern.

16. A method for manufacturing circuit wiring, comprising the following steps: A process of bonding the transfer layer in the photosensitive transfer material according to any one of claims 1 to 14 to a substrate having a conductive layer; The process of exposing and developing the exposed photosensitive layer to form a pattern; and The process of etching the substrate in areas where the resin pattern is not configured.

17. A method for manufacturing an electronic device, comprising, in sequence: A process of bonding the transfer layer in the photosensitive transfer material according to any one of claims 1 to 14 to a substrate having a conductive layer; The process of exposing and developing the exposed photosensitive layer to form a pattern; and The process of etching the substrate in areas where the resin pattern is not configured.

18. A method for manufacturing a laminate, comprising the following steps: The bonding process involves bonding the transfer layer of a photosensitive transfer material, which has a temporary support and includes a transfer layer comprising a photosensitive layer containing an olefinic unsaturated compound, to a substrate to create a laminate. The peeling process involves peeling the temporary support from the laminate; as well as The pattern forming process involves exposing and developing the exposed photosensitive layer to form a pattern. In air at 23°C, 1 atm pressure, and 55% RH, an ultra-high pressure mercury lamp was used to achieve an energy density of 100 mJ / cm² at a wavelength of 365 nm. 2 When exposure is performed, the ratio D4 / D3, which is the percentage disappearance of olefinic unsaturated bonds in the photosensitive layer of the laminate produced in the bonding process via the temporary support, measured using a fully automated Fourier transform infrared (FT-IR) microscope, is 80% to 100% to the percentage disappearance of olefinic unsaturated bonds in the photosensitive layer after the temporary support has been peeled off in the release process. In the D3 measurement, the temporary support is not peeled off from the laminated substrate. Instead, the substrate is placed on the substrate mounting stage of a projection exposure machine, specifically a Ushio Inc. UX-2023SM. A glass chrome photomask with line and spatial patterns is placed on the mask holder of the exposure machine. The photomask is then exposed through a projection lens at an exposure dose of 100 mJ / cm². 2 Exposure is performed, with the duty cycle of the lines and spatial pattern at 1:1, and the line width varying in 1μm increments between 1μm and 10μm. In the D4 measurement, a temporary support was peeled off from the laminated substrate and placed on the substrate mounting stage of a projection exposure machine, specifically a Ushio Inc. UX-2023SM. A glass chrome photomask with line and spatial patterns was placed on the mask holder of the exposure machine, and the exposure was performed through a projection lens at an exposure dose of 100 mJ / cm². 2 After the temporary support is removed, exposure is performed 10 minutes later. The duty cycle of the line and the spatial pattern is 1:1, and the line width varies in stages every 1 μm between 1 μm and 10 μm.

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