Photosensitive transfer material, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel

Abstract

This invention provides a photosensitive transfer material, a method for manufacturing a resin pattern using the aforementioned photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel. The photosensitive transfer material comprises: a temporary support; and a photosensitive resin layer comprising an alkali-soluble resin, an olefinic unsaturated compound, and a photopolymerization initiator. The photosensitive resin layer is then used to... (The sentence is incomplete and requires further context to translate accurately.) 2 The width of the double bond reaction region (W3) after 3 hours and the width of the double bond reaction region (W) after 24 hours are calculated using exposure units (Ep) to expose 10μm / 10μm line and space patterns. 24 Satisfying W 24 / W3≤1.05.

Description

Technical Field

[0001] This invention relates to a photosensitive transfer material, a method for manufacturing resin patterns, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel. 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, the number of steps to obtain the desired pattern shape is small. Therefore, the method of exposing a layer of photosensitive resin composition disposed on any substrate through a mask with the desired pattern using a photosensitive transfer material and then developing it is widely used.

[0004] Furthermore, as a conventional photosensitive resin composition, the composition described in Patent Document 1 is known.

[0005] Patent Document 1 describes a photosensitive resin composition characterized in that, after exposure curing in such a way that the reaction rate of the olefinic unsaturated compound contained as a photosensitive component in the exposed surface is 70%, when stored in the dark, the reaction rate of the unsaturated compound in the entire plate does not change substantially, and the difference in local reaction rate between the exposed and unexposed surfaces remains above 20% after 24 hours.

[0006] Patent Document 1: Japanese Patent Application Publication No. 2001-356493 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] In the wiring process using photosensitive transfer materials, when exposing the photosensitive resin layer bonded to a substrate with a conductive layer, the elapsed time from exposure completion to development varies among the individual photosensitive resin layers, sometimes by several hours. Furthermore, sometimes the exposed photosensitive resin layer is not developed immediately but left to stand for a certain period, further extending the elapsed time from exposure completion. Regarding the post-exposure resting time described above, this tends to increase, especially in roll-to-roll processes where transport from the roll exit to the roll core takes time.

[0009] One embodiment of the present invention aims to solve the problem of providing a photosensitive transfer material in which the linewidth of the resin pattern changes little over time after exposure.

[0010] 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 a touch panel.

[0011] means for solving technical problems

[0012] The solution to the above problem includes the following approach.

[0013] <1> A photosensitive transfer material comprises: a temporary support; and a photosensitive resin layer comprising an alkali-soluble resin, an olefinic unsaturated compound, and a photopolymerization initiator, wherein the photosensitive resin layer is used to transfer the material at a concentration of mJ / cm². 2 After exposing 10μm / 10μm line and space patterns with an exposure dose Ep, the double bond reaction region width W3 after 3 hours and the double bond reaction region width W after 24 hours are compared. 24 Satisfy W 24 / W3≤1.05.

[0014] W3 and W 24 Let's assume the width of the double bond reaction region is obtained by secondary ion mass spectrometry analysis after bromine staining of the exposed photosensitive transfer material.

[0015] The above Ep satisfies Ep = 2 × Eb.

[0016] The above-mentioned Eb setting indicates that after the photosensitive resin layer is attached to the substrate, light passes through a 15-step stepped light wedge with an illuminance of 20mW / cm². 2 The high-pressure mercury lamp has an exposure of 180 mJ / cm 2 Exposure is performed, and the exposure level is set to the residual thickness of the developed photosensitive resin layer by ±1%.

[0017] <2> according to <1> The aforementioned photosensitive transfer material, wherein,

[0018] After exposing the above-mentioned photosensitive resin layer to the above-mentioned exposure amount Ep with a 10μm / 10μm line and space pattern, the width W3 of the double bond reaction region after 3 hours and the width W of the double bond reaction region after 72 hours are compared. 72 Satisfy W 72 / W3≤1.10.

[0019] W 72 Let's say we define the width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining of the exposed photosensitive transfer material.

[0020] <3> according to <1> or <2> The aforementioned photosensitive transfer material, wherein,

[0021] The aforementioned olefinic unsaturated compounds include olefinic unsaturated compounds having a bisphenol structure.

[0022] <4> according to <1> to <3> In any one of the photosensitive transfer materials, wherein,

[0023] The aforementioned photopolymerization initiators include biimidazole compounds and benzophenone compounds.

[0024] <5> according to <1> to <4> In any one of the photosensitive transfer materials, wherein,

[0025] The aforementioned photosensitive resin layer also contains a polymerization inhibitor.

[0026] <6> according to <5> The aforementioned photosensitive transfer material, wherein,

[0027] The aforementioned polymerization inhibitors include at least one compound selected from phenothiazine, phenothiazine, and compounds having a hindered phenolic structure.

[0028] <7> according to <5> or <6> The aforementioned photosensitive transfer material, wherein,

[0029] When the content of the photopolymerization initiator in the above-mentioned photosensitive resin layer is set to Rc and the content of the above-mentioned polymerization inhibitor is set to Rd, the mass ratio Rd / Rc is 0.02 or more and 0.1 or less.

[0030] <8> according to <7> The aforementioned photosensitive transfer material, wherein,

[0031] The above-mentioned mass ratio Rd / Rc has a value of 0.03 or higher and 0.05 or lower.

[0032] <9> A method for manufacturing a resin pattern, comprising: making... <1> to <8> The process of bonding the outermost layer of the photosensitive transfer material having the photosensitive resin layer on the side opposite to the temporary support to the substrate; the process of pattern exposure of the photosensitive resin layer; and the process of developing the exposed photosensitive resin layer to form a resin pattern.

[0033] <10> according to <9> The method for manufacturing the resin pattern, wherein,

[0034] At least a portion of the resin pattern comprises line and space patterns, wherein the combined width of at least one set of lines and spaces in the line and space patterns is less than 20 μm.

[0035] <11> A method for manufacturing circuit wiring, comprising the following steps: making <1> to <8> The process of bonding the outermost layer of the photosensitive transfer material having a photosensitive resin layer on the side opposite to the temporary support to a substrate having a conductive layer; the process of pattern exposure of the photosensitive resin layer; the process of developing the exposed photosensitive resin layer to form a resin pattern; and the process of etching the substrate in the area where the resin pattern is not provided.

[0036] <12> A method for manufacturing a touch panel, comprising the following steps: making... <1> to <8> The process of bonding the outermost layer of the photosensitive transfer material having a photosensitive resin layer on the side opposite to the temporary support to a substrate having a conductive layer; the process of pattern exposure of the photosensitive resin layer; the process of developing the exposed photosensitive resin layer to form a resin pattern; and the process of etching the substrate in the area where the resin pattern is not provided.

[0037] Invention Effects

[0038] According to one embodiment of the present invention, a photosensitive transfer material in which the linewidth of the resin pattern changes little over time after exposure can be provided.

[0039] 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 a touch panel can be provided. Attached Figure Description

[0040] Figure 1 This is a schematic diagram illustrating an example of the structure of the photosensitive transfer material according to the first embodiment.

[0041] Figure 2 This is a schematic diagram illustrating an example of the structure of the photosensitive transfer material according to the second embodiment.

[0042] Figure 3 This is a schematic top view representing pattern A.

[0043] Figure 4 This is a schematic top view representing pattern B. Detailed Implementation

[0044] The present invention will now be described. Although the description is based on the accompanying drawings, symbols are sometimes omitted.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In the designation of groups (atomic groups) in this specification, the designations that do not indicate whether they are substituted or unsubstituted include groups without substituents and groups with substituents. For example, "alkyl" means not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0050] Unless otherwise specified, in this specification, "exposure" refers not only to exposure using light, but also to exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and activated light (active energy rays) such as electron beams.

[0051] Furthermore, the chemical structural formulas in this specification are sometimes described as simplified structural formulas with the hydrogen atom omitted.

[0052] In this invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0053] Furthermore, in this invention, a combination of two or more preferred methods is a more preferred method.

[0054] Furthermore, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this invention are as follows: measured using a gel permeation chromatography (GPC) analysis apparatus with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by TOSOHCORPORATION), using the solvent THF (tetrahydrofuran), a differential refractometer, and polystyrene as a standard substance for conversion.

[0055] 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.

[0056] (Photosensitive transfer material)

[0057] The photosensitive transfer material of the present invention comprises: a temporary support; and a photosensitive resin layer comprising an alkali-soluble resin, an olefinic unsaturated compound, and a photopolymerization initiator, wherein the photosensitive resin layer is used to... (mJ / cm) 2 After exposing 10μm / 10μm line and space patterns with an exposure dose Ep, the double bond reaction region width W3 after 3 hours and the double bond reaction region width W after 24 hours are compared. 24 Satisfy W 24 / W3≤1.05.

[0058] W3 and W 24 Let's assume the width of the double bond reaction region is obtained by secondary ion mass spectrometry analysis after bromine staining of the exposed photosensitive transfer material.

[0059] The above Ep satisfies Ep = 2 × Eb.

[0060] The above-mentioned Eb setting indicates that after the above-mentioned photosensitive resin layer is attached to the substrate, light passes through a 15-step stepped light wedge with an illuminance of 20mW / cm². 2 The high-pressure mercury lamp has an exposure of 180 mJ / cm 2 Exposure is performed, and the exposure level is set to the residual thickness of the developed photosensitive resin layer by ±1%.

[0061] As a result of detailed research, the inventors discovered that in photosensitive transfer materials formed from the photosensitive resin composition described in Patent Document 1, which have a conventional negative photosensitive resin layer, there is a problem that the linewidth of the resin pattern changes significantly over time after exposure.

[0062] In the photosensitive transfer material involved in this invention, the photosensitive resin layer is used with a concentration of mJ / cm 2 After exposing 10μm / 10μm line and space patterns with an exposure dose Ep, the double bond reaction region width W3 after 3 hours and the double bond reaction region width W after 24 hours are compared. 24 Satisfy W 24With / W3≤1.05, the photosensitive resin layer, as described above, exhibits minimal temporal variation in the width of the double bond reaction region. In the half-exposed portion at the end of the exposed region, the reaction is sufficiently suppressed, and the difference in polymerization reactivity between the exposed and unexposed regions increases. Therefore, it is estimated that even with slight variations in development conditions such as post-exposure resting time, dissolution during development in areas where polymerization is sufficiently suppressed results in minimal linewidth variation of the resin pattern over the post-exposure resting time (also known as "resting time linewidth variation").

[0063] In the photosensitive transfer material of the present invention, the above-mentioned photosensitive resin layer is used with a concentration of mJ / cm 2 After exposing 10μm / 10μm line and space patterns with an exposure dose Ep, the double bond reaction region width W3 after 3 hours and the double bond reaction region width W after 24 hours are compared. 24 Satisfy W 24 / W3≤1.05.

[0064] W3 and W 24 Let's assume the width of the double bond reaction region is obtained by secondary ion mass spectrometry analysis after bromine staining of the exposed photosensitive transfer material.

[0065] The above Ep satisfies Ep = 2 × Eb.

[0066] The above-mentioned Eb setting indicates that after the above-mentioned photosensitive resin layer is attached to the substrate, light passes through a 15-step stepped light wedge with an illuminance of 20mW / cm². 2 The high-pressure mercury lamp has an exposure of 180 mJ / cm 2 Exposure is performed, and the exposure level is set to the residual thickness of the developed photosensitive resin layer by ±1%.

[0067] From the viewpoint of changes in linewidth over placement time, changes in the linewidth of the resin pattern accompanying changes in developing temperature (also known as "developing temperature linewidth variation"), and sensitivity, the photosensitive transfer material involved in this invention preferably satisfies W. 24 / W3≤1.04, more preferably satisfying W 24 / W3≤1.03, with a particular preference given to 1.00≤W 24 / W3≤1.03.

[0068] Furthermore, in the photosensitive transfer material involved in this invention, from the viewpoint of changes in linewidth over time and changes in linewidth over development temperature, after exposing the aforementioned photosensitive resin layer with the aforementioned exposure amount Ep and a 10μm / 10μm line and space pattern, the width W3 of the double bond reaction region after 3 hours and the width W of the double bond reaction region after 72 hours are as follows: 72 Preferred to satisfy W 72 / W3≤1.15, more preferably satisfying W 72 / W3≤1.10, and preferably 1.00≤W 72 / W3≤1.10.

[0069] In addition, W 72 Let's say we define the width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining of the exposed photosensitive transfer material.

[0070] The following illustrates the method for determining Eb and the method for calculating Ep in this invention.

[0071] A photosensitive transfer material was laminated onto a substrate (a substrate formed by sputtering a 200nm thick copper layer onto a 100μm polyethylene terephthalate (PET) film) using a sheet laminator. The lamination conditions were set as follows: roller temperature 100℃, lamination speed 2m / min, and lamination pressure 0.5MPa.

[0072] A 15-step stepped optical wedge (made by Fujifilm Corporation) is placed on a temporary support of the laminated photosensitive transfer material, utilizing 20mW / cm² light. 2 High-pressure mercury lamp at 180mJ / cm 2 Exposure. After exposure, the support is peeled off, and development is performed using a 0.9% sodium carbonate aqueous solution at 25°C for 30 seconds. The Eb value is calculated based on the residual film thickness after each step (Eb represents the thickness of the photosensitive resin layer after it is attached to the substrate, through a 15-step stepped light wedge with an illuminance of 20 mW / cm²). 2 The high-pressure mercury lamp has an exposure of 180 mJ / cm 2 Exposure is performed, and the exposure level is the number of exposure steps that imparts the residual layer thickness ±1% of the developed photosensitive resin layer thickness.

[0073] Furthermore, through the calculated Eb(mJ / cm 2 ), calculate Ep (mJ / cm) using the following formula. 2 ).

[0074] Ep = 2 × Eb

[0075] The following shows the widths W3 and W4 of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining of the exposed photosensitive transfer material of the present invention. 24 and W 72 The determination method.

[0076] A photosensitive transfer material was laminated onto a substrate (a substrate formed by sputtering a 200nm thick copper layer onto a 100μm PET film) using a sheet laminator. The lamination conditions were set as follows: roller temperature 100℃, lamination speed 2m / min, and lamination pressure 0.5MPa.

[0077] A photomask with a line-to-space ratio of 10 μm / 10 μm is brought into contact with a temporary support, and Ep = 2 × Eb (mJ / cm²) is used. 2 The photosensitive transfer material laminated on the above substrate was exposed. After exposure, after 3 hours, 24 hours, or 72 hours, the temporary support, thermoplastic resin layer, and intermediate layer were peeled off with tape. 5 mL of bromine water (0.2%) was aliquoted into a 50 mL container, and the sample was fixed in the container without contact with the aliquoted liquid, and allowed to stand at room temperature (25°C) for 5 minutes. Afterward, it was stored under high vacuum for half a day to degas the residual bromine. Thus, a sample with bromine modification of the carbon-carbon double bond was prepared.

[0078] The sample was analyzed using secondary ion mass spectrometry (ION-TOF SIMS5, primary ion source: Bi). 3+ (30kV), Measurement range: 50mm, Area resolution: 512×512 pixels, Integration: 32 times, Measurement mode: High spatial resolution mode (Fast Imaging), Charge correction: using an electron gun), Evaluation of C2HBr - Width of the region. Measurements of C2HBr at three locations. - The width of the region with low intensity is calculated, and the average of three measured values ​​is taken as the width W3 and W4 of the polymerization region. 24 or W 72 .

[0079] From the viewpoints of variations in placement time linewidth, variations in development temperature linewidth, and sensitivity, the Eb value in the photosensitive transfer material involved in this invention is preferably 20 mJ / cm. 2 ~200mJ / cm 2 More preferably 30 mJ / cm 2 ~150mJ / cm 2 Further preferred is 35 mJ / cm 2 ~100mJ / cm 2 The preferred value is 35 mJ / cm. 2 ~70mJ / cm 2 .

[0080] Furthermore, from the viewpoints of changes in placement time linewidth, changes in development temperature linewidth, and sensitivity, the value of W3 in the photosensitive transfer material involved in the present invention is preferably 9.0 μm to 10.5 μm, more preferably 9.2 μm to 10.3 μm, and especially preferably 9.5 μm to 10.2 μm.

[0081] From the perspective of variations in placement time linewidth, variations in development temperature linewidth, and sensitivity, the W in the photosensitive transfer material involved in this invention...24 The value is preferably 9.0 μm to 11.0 μm, more preferably 9.3 μm to 10.7 μm, and especially preferably 9.5 μm to 10.5 μm.

[0082] From the perspective of variations in placement time linewidth, variations in development temperature linewidth, and sensitivity, the W in the photosensitive transfer material involved in this invention... 72 The value is preferably 9.0 μm to 12.0 μm, more preferably 9.5 μm to 11.5 μm, and especially preferably 9.7 μm to 11.0 μm.

[0083] The photosensitive transfer material involved in this invention has a temporary support and a photosensitive resin layer comprising an alkali-soluble resin, an olefinic unsaturated compound and a photopolymerization initiator.

[0084] In photosensitive transfer materials, the temporary support and the photosensitive resin layer can be directly laminated without any other layers in between, or they can be laminated with other layers in between. Furthermore, other layers can also be laminated on the side of the photosensitive resin layer opposite to the side facing the temporary support.

[0085] Other layers besides the temporary support and photosensitive resin layer include, for example, thermoplastic resin layer, intermediate layer and protective film.

[0086] The following illustrates one example of the photosensitive transfer material involved in the present invention, but is not limited thereto.

[0087] (1) "Temporary support / photosensitive resin layer / refractive index adjustment layer / protective film"

[0088] (2) "Temporary support / photosensitive resin layer / protective film"

[0089] (3) "Temporary support / intermediate layer / photosensitive resin layer / protective film"

[0090] (4) "Temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film"

[0091] Furthermore, in each of the above structures, the photosensitive resin layer is preferably a negative photosensitive resin layer. Moreover, the photosensitive resin layer is preferably a colored resin layer. As described below, the photosensitive transfer material according to the present invention can be used as a photosensitive transfer material for wiring protection films, and also as a photosensitive transfer material for etching resists.

[0092] When the material is designed as a photosensitive transfer material for wiring protection film, the structure of the photosensitive transfer material is preferably, for example, the structure described in (1) or (2) above.

[0093] Furthermore, when the photosensitive transfer material is used as an etch resist, the structure of the photosensitive transfer material is preferably, for example, the structure described in (2) to (4) above.

[0094] In a photosensitive transfer material, when there is a structure in which the photosensitive resin layer has other layers on the side opposite to the temporary support side, the total thickness of the other layers disposed on the side opposite to the temporary support side of the photosensitive resin layer is preferably 0.1% to 30% relative to the thickness of the photosensitive resin layer, more preferably 0.1% to 20%.

[0095] Hereinafter, an example of a specific embodiment will be given to describe the photosensitive transfer material according to the present invention. Furthermore, the photosensitive transfer material of the first embodiment described below has a structure that is preferably used as a photosensitive transfer material for etching resists, and the photosensitive transfer material of the second embodiment described below has a structure that is preferably used as a photosensitive transfer material for wiring protection films.

[0096] [Photosensitive transfer material according to the first embodiment]

[0097] The following example illustrates the photosensitive transfer material of the first embodiment.

[0098] 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 resin layer 17, and a protective film 19.

[0099] in addition, Figure 1 The photosensitive transfer material 320 shown is configured with a protective film 19, but it is also possible to omit the protective film 19.

[0100] 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.

[0101] The components constituting the photosensitive transfer material of the first embodiment will be described below.

[0102] [Temporary support]

[0103] The photosensitive transfer material used in this invention has a temporary support.

[0104] A temporary support is a support that supports a photosensitive resin layer or a laminate including a photosensitive resin layer and is peelable.

[0105] From the viewpoint that the photosensitive resin layer can be exposed through a temporary support during pattern exposure, the temporary support preferably has light transmittance. Furthermore, in this specification, "having light transmittance" means that the transmittance of light at the wavelength used in pattern exposure is 50% or more.

[0106] From the viewpoint of improving the exposure sensitivity of the photosensitive resin 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.

[0107] Furthermore, the transmittance of the so-called photosensitive transfer material layer is the ratio of the intensity of the emitted light that passes through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction). It is measured using an MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0108] Materials that constitute a temporary support include, for example, glass substrates, resin films and paper. From the viewpoints of strength, flexibility and light transmittance, resin films are preferred.

[0109] 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.

[0110] There are no particular restrictions on the thickness (layer thickness) of the temporary support. It can be selected based on the material, taking into account the strength of the support, the flexibility required for bonding with the substrate for circuit wiring, and the light transmittance required in the initial exposure process.

[0111] The thickness of the temporary support is preferably in the range of 5μm to 100μm. From the viewpoint of ease of operation and versatility, it is more preferably in the range of 10μm to 50μm, even more preferably in the range of 10μm to 20μm, and especially preferably in the range of 10μm to 16μm.

[0112] Furthermore, from the viewpoint of resolution and linearity when exposing through a support, the thickness of the temporary support is preferably 50 μm or less, and more preferably 25 μm or less.

[0113] Furthermore, it is preferable that the membrane used as a temporary support is free from deformations such as wrinkles, scratches, and defects.

[0114] From the perspective of pattern formation and transparency of the temporary support during pattern exposure, 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 further preferred: 3 per 10mm 2 The following is particularly preferred: 0 per 10mm 2 .

[0115] 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.

[0116] [Photosensitive resin layer]

[0117] The photosensitive transfer material involved in this invention has a photosensitive resin layer.

[0118] The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developer decreases upon exposure and the non-exposed portion is removed by development.

[0119] The photosensitive resin layer contains alkali-soluble resin, olefin unsaturated compound and photopolymerization initiator. From the viewpoint of changes in the placement time linewidth, changes in the development temperature linewidth and sensitivity, it is preferable to contain alkali-soluble resin, olefin unsaturated compound, biimidazole compound and benzophenone compound, and more preferably alkali-soluble resin, olefin unsaturated compound, hexaarylbiimidazole compound and benzophenone compound.

[0120] Furthermore, from the viewpoints of changes in placement time linewidth, changes in development temperature linewidth, and sensitivity, the photosensitive resin layer preferably also contains a polymerization inhibitor.

[0121] The photosensitive resin layer, relative to the total mass of the above-mentioned photosensitive resin layer, preferably comprises: 10% to 90% by mass of alkali-soluble resin; 5% to 70% by mass of olefinic unsaturated compound; and 0.01% to 20% by mass of photopolymerization initiator.

[0122] The following is a description of each component.

[0123] Alkali-soluble resins

[0124] The photosensitive resin layer contains an alkali-soluble resin.

[0125] In addition, in this specification, "alkali solubility" means that the solubility of sodium carbonate in 100g of a 1% by mass aqueous solution at 22°C is 0.1g or more.

[0126] There are no particular limitations on the alkali-soluble resin used; for example, well-known alkali-soluble resins used in etching resists can be preferred.

[0127] Furthermore, the alkali-soluble resin is preferably an adhesive polymer.

[0128] As an alkali-soluble resin, an alkali-soluble resin having acid groups is preferred.

[0129] Among them, polymer A, which will be described later, is preferred as an alkali-soluble resin.

[0130] -Polymer A-

[0131] As an alkali-soluble resin, it preferably contains polymer A.

[0132] From the viewpoint of achieving better resolution by suppressing the swelling of the photosensitive resin 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.

[0133] There is no particular limitation on the lower limit of the acid value of polymer A, but from the viewpoint of better developability, it is preferred to be 60 mg KOH / g or more, more preferably 120 mg KOH / g or more, even more preferably 150 mg KOH / g or more, and especially preferably 170 mg KOH / g or more.

[0134] Additionally, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1g of the sample.

[0135] 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.

[0136] 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.

[0137] 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 properties, 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 resin layer overflows from the end face of the roller when the photosensitive transfer material is rolled into a roll. Chipping property 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 particularly 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).

[0138] From the viewpoint of suppressing linewidth thickening or resolution degradation due to focus position shift during exposure, the photosensitive resin layer preferably contains a monomer 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 content percentage of the monomer component having aromatic hydrocarbons in polymer A, based on the total mass of the total monomer 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, when multiple polymers A are contained, the content percentage of the monomer component having aromatic hydrocarbons is calculated as a weight average.

[0139] 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 content ratio of the styrene monomer component, based on the total mass of the total monomer components, 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.

[0140] 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.

[0141] Examples of monomers containing phenyl alkyl groups include phenylethyl (meth)acrylate.

[0142] 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, based on the total mass of the total monomer components, 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] Regarding the content of the first monomer in polymer A, based on the total mass of the total monomer components, it is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass.

[0147] Regarding the copolymerization ratio of the first monomer, based on the total mass of the total monomer components, it is preferably 10% to 50% by mass. From the viewpoints of good developability and control of 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.

[0148] 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.

[0149] Regarding the proportion of the second monomer in polymer A, based on the total mass of the total monomer components, it is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] Polymer A may have a branched structure or an alicyclic structure in its side chains. Furthermore, polymer A may also have a straight-chain structure in its side chains. For example, a branched or alicyclic structure can be introduced into the side chains of polymer (A) by using monomers containing groups with branched structures in their side chains or monomers containing groups with alicyclic structures in their side chains. The groups with alicyclic structures can be monocyclic or polycyclic.

[0154] Examples of monomers containing a branched group in the side chain include isopropyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, tert-amyl methacrylate, sec-amyl methacrylate, 2-octyl methacrylate, 3-octyl methacrylate, and tert-octyl methacrylate. Of these, isopropyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate are more preferred.

[0155] Specific examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Furthermore, (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be cited. Examples of monomers containing a group having an alicyclic structure in the side chain include, for example, (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, 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-hydroxy-bicyclo[4.1.0]heptyl ester of (meth)acrylate, (nor)bornyl ester of (meth)acrylate, isobornyl ester of (meth)acrylate, fenofibrate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate and cyclohexyl ester of (meth)acrylate. Of the above, cyclohexyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 2-adamantyl methacrylate, fentanyl methacrylate, 1-menthyl methacrylate, and tricyclodecane methacrylate are preferred, and cyclohexyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, 2-adamantyl methacrylate, and tricyclodecane methacrylate are more preferred.

[0156] 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.

[0157] 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 resin 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.

[0158] The photosensitive resin layer may also contain resins other than alkali-soluble resins.

[0159] 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.

[0160] Alkali-soluble resins can be used alone or in combination with two or more.

[0161] The ratio of alkali-soluble resin to the total mass of the photosensitive resin 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 resin 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 resin layer to 10% by mass or more.

[0162] (Alkene unsaturated compounds)

[0163] The photosensitive resin layer contains olefinic unsaturated compounds.

[0164] In this specification, "olefinic unsaturated compound" refers to a compound polymerized by a photopolymerization initiator described later, and is a compound different from the alkali-soluble resins mentioned above.

[0165] As an olefinically unsaturated compound, it is preferred to be an olefinically unsaturated compound.

[0166] Unsaturated olefinic compounds are components that contribute to the photosensitivity (i.e., photocurability) of negative photosensitive resin layers and the strength of cured films.

[0167] Furthermore, olefinic unsaturated compounds are compounds having one or more olefinic unsaturated groups.

[0168] The photosensitive resin layer, being an olefin unsaturated compound, preferably contains olefin unsaturated compounds with two or more functions.

[0169] Here, "a 2 or more functional olefin unsaturated compounds" refers to compounds having two or more olefin unsaturated groups in one molecule.

[0170] As an olefinic unsaturated group, (meth)acryloyl group is more preferably used.

[0171] As an olefinic unsaturated compound, (meth)acrylate compounds are preferred.

[0172] Furthermore, from the viewpoints of changes in the placement time linewidth, changes in the development temperature linewidth, and sensitivity, the olefin unsaturated compound preferably includes an olefin unsaturated compound having a bisphenol structure.

[0173] As an olefinic unsaturated compound having a bisphenol structure, olefinic unsaturated compound B1 having a bisphenol structure, described later, is preferably exemplified.

[0174] The photosensitive resin layer preferably contains an olefinic unsaturated compound with polymerizable groups.

[0175] As a polymerizable group in an olefinic unsaturated compound, there are no particular restrictions as long as the group participates in the polymerization reaction. For example, groups with olefinic unsaturated groups such as vinyl, acryloyl, methacryloyl, styryl, and maleimide can be listed; as well as groups with cationic polymerizable groups such as epoxy and oxetane.

[0176] As a polymerizable group, it is preferred to have a group having an olefinic unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0177] From the viewpoint of superior photosensitivity of the photosensitive resin layer, compounds containing two or more olefinic unsaturated groups in one molecule (polyfunctional olefinic unsaturated compounds) are preferred as olefinic unsaturated compounds.

[0178] Furthermore, from the viewpoint of superior resolution and peelability, the number of olefinic unsaturated groups in one molecule of the olefinic unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0179] From the viewpoint of achieving a better balance between photosensitivity, resolution, and peelability of the photosensitive resin layer, the photosensitive resin layer preferably contains a difunctional or trifunctional olefin unsaturated compound having two or three olefin unsaturated groups in one molecule, and more preferably contains a difunctional olefin unsaturated compound having two olefin unsaturated groups in one molecule.

[0180] From the viewpoint of excellent peelability, the content of difunctional olefin unsaturated compounds in the photosensitive resin layer is preferably 60% by mass or more, more preferably more than 70% by mass, and even more preferably 90% by mass or more, relative to the content of olefin unsaturated compounds. There is no particular limit to the upper limit, and it can be 100% by mass. That is, all the olefin unsaturated compounds contained in the photosensitive resin layer can be difunctional olefin unsaturated compounds.

[0181] Furthermore, as an olefinic unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0182] -Alkene unsaturated compound B1-

[0183] The photosensitive resin layer preferably contains an olefin unsaturated compound B1 having an aromatic ring and two olefin unsaturated groups. The olefin unsaturated compound B1 is a difunctional olefin unsaturated compound among the aforementioned olefin unsaturated compounds that has one or more aromatic rings in one molecule.

[0184] From the viewpoint of superior resolution, the mass ratio of the content of the olefinically unsaturated compound B1 in the photosensitive resin layer to the total content of olefinically unsaturated compounds 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 viewpoint 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.

[0185] The aromatic rings present in the olefinically unsaturated compound 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.

[0186] Alkenes can have only one aromatic ring or more than two aromatic rings.

[0187] From the viewpoint of improving resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, the olefinic unsaturated compound preferably has a bisphenol structure.

[0188] 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.

[0189] Examples of olefinic unsaturated compounds having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.

[0190] 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.

[0191] For olefinic unsaturated compounds with a bisphenol structure, Japanese Patent Application Publication No. 2016-224162, paragraphs 0072 to 0080, the contents of which are incorporated into this specification.

[0192] As an olefinic unsaturated compound, a difunctional olefinic unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0193] 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.).

[0194] From the viewpoints of variations in the linewidth of the storage time, the variations in the linewidth of the development temperature, and sensitivity, compounds containing the following formula (Bis) are preferred as olefinic unsaturated compounds.

[0195] [Chemical Formula 1]

[0196]

[0197] 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.

[0198] 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.

[0199] The olefinic unsaturated compound B1 can be used alone or in combination with two or more compounds.

[0200] From the viewpoint of further improving resolution, the content of the olefinically unsaturated compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the photosensitive resin layer. There is no particular limit to the upper limit, but from the viewpoint of transferability and edge melting (the phenomenon of components in the photosensitive resin 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.

[0201] The photosensitive resin layer may also contain olefin unsaturated compounds other than the olefin unsaturated compound mentioned above.

[0202] There are no particular restrictions on olefin unsaturated compounds other than the olefin unsaturated compound β, 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.).

[0208] 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.

[0209] 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 resin layer preferably includes the above-mentioned olefin unsaturated compound B1 and olefin unsaturated compounds with more than three functions, more preferably it includes the above-mentioned olefin unsaturated compound B1 and two or more olefin unsaturated compounds with more than three functions. In this case, the mass ratio of olefin unsaturated compound B1 to olefin unsaturated compounds with more than three functions is preferably (total mass of olefin unsaturated compound B1) : (total mass of olefin unsaturated compounds with more than three functions) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0210] Furthermore, in one embodiment, the photosensitive resin layer preferably comprises the aforementioned olefin unsaturated compound and two or more trifunctional olefin unsaturated compounds.

[0211] 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.).

[0212] 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.

[0213] From the viewpoint of resolution and linearity, the ratio of the content of the olefinic unsaturated compound Mm in the photosensitive resin 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.

[0214] Furthermore, from the viewpoint of curability and resolution, the olefinic unsaturated compound in the photosensitive resin layer preferably includes (meth)propene oxide.

[0215] Furthermore, from the viewpoints of curability, resolution, and linearity, the olefinic unsaturated compound in the photosensitive resin 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 resin layer.

[0216] The molecular weight (in the case of a distribution, the weight-average molecular weight (Mw)) of the olefinic unsaturated compound containing the olefinic unsaturated compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0217] Alkenes can be used alone or in combination with two or more.

[0218] The content of olefinic unsaturated compounds in the photosensitive resin layer relative to the total mass of the photosensitive resin layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass.

[0219] Photopolymerization initiators

[0220] The photosensitive resin layer contains a photopolymerization initiator.

[0221] Photopolymerization initiators are compounds that initiate the polymerization of olefinic unsaturated compounds upon receiving activating light such as ultraviolet light, visible light, and X-rays. There are no particular limitations on the photopolymerization initiator; known photopolymerization initiators can be used. Furthermore, the photopolymerization initiator in this invention also contains a sensitizer.

[0222] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

[0223] 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.

[0224] From the perspective of changes in placement time linewidth, changes in development temperature linewidth, and sensitivity, the photopolymerization initiator preferably contains a biimidazole compound, and more preferably contains a biimidazole compound and a benzophenone compound.

[0225] Furthermore, hexaaryl biimidazole compounds are preferred as biimidazole compounds.

[0226] Examples of biimidazole compounds include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0227] The photosensitive resin layer may contain only one biimidazole compound as a photopolymerization initiator, or it may contain two or more.

[0228] From the viewpoints of variations in placement time linewidth, variations in development temperature linewidth, and sensitivity, the content of the above-mentioned biimidazole compound relative to the total mass of the above-mentioned photosensitive resin layer is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass to 10% by mass, and particularly preferably 5% by mass to 10% by mass.

[0229] From the viewpoints of variations in placement time linewidth, variations in development temperature linewidth, and sensitivity, the photopolymerization initiator preferably contains a benzophenone compound, and more preferably a dialkylaminobenzophenone compound.

[0230] Examples of benzophenone compounds include, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-phenylbenzophenone, isodibenzophenolphthalein, 4-benzoyl-4'-methylphenyl sulfide, etc.

[0231] The photosensitive resin layer may contain only one benzophenone compound as a photopolymerization initiator, or it may contain two or more compounds.

[0232] From the viewpoints of variations in placement time linewidth, variations in development temperature linewidth, and sensitivity, the content of the benzophenone compound relative to the total mass of the photosensitive resin layer is preferably 0.05% to 5% by mass, more preferably 0.1% to 2% by mass, even more preferably 0.2% to 1.5% by mass, and particularly preferably 0.4% to 0.8% by mass.

[0233] Furthermore, as a photopolymerization initiator, when containing both biimidazole and benzophenone compounds, from the viewpoints of changes in the standing time linewidth, changes in the development temperature linewidth, and sensitivity, the content of the benzophenone compound is preferably less than the content of the biimidazole compound.

[0234] 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.

[0235] 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.).

[0236] 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-morpholinophenyl)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 names: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade names: Omnired 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiators (trade names: Lunar 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.).

[0237] Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving activation light. Preferably, these initiators are compounds that generate acid upon receiving activation light with wavelengths of 300 nm or higher, and more preferably 300–450 nm, but their chemical structure is not limited. Furthermore, for photocationic polymerization initiators that do not directly respond to activation light with wavelengths of 300 nm or higher, as long as they are compounds that generate acid upon receiving activation light with wavelengths of 300 nm or higher in combination with a sensitizer, they can be used in combination with the sensitizer and are preferred.

[0238] 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.

[0239] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators.

[0240] Examples of ionic photocationic polymerization initiators include, for example, onium salts such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts.

[0241] 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.

[0242] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine derivatives, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazine 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, as oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640 can be used.

[0243] There are no particular restrictions on sensitizers; well-known sensitizers, dyes, and pigments can be used.

[0244] Examples of sensitizers include, for example, 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.

[0245] The photosensitive resin layer may contain one type of photopolymerization initiator or two or more types.

[0246] There is no particular limitation on the content of the photopolymerization initiator in the photosensitive resin 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 resin 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 resin layer.

[0247] Pigment

[0248] From the viewpoint of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, the photosensitive resin layer preferably contains pigment, and more preferably contains pigment with a maximum absorption wavelength of 450 nm or higher in the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes with acid, alkali, or free radicals (also simply referred to as "pigment N"). When pigment N is contained, although the detailed mechanism is not yet clear, the adhesion to adjacent layers (e.g., temporary supports and intermediate layers) is improved, and the resolution is superior.

[0249] In this specification, the phrase "the maximum absorption wavelength of a pigment changes due to acid, alkali, or free radicals" can refer to any one 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.

[0250] 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 resin layer through exposure, or a pigment that changes color or decolorizes by changing the state (e.g., pH) within the photosensitive resin layer through acids, bases, or free radicals. Furthermore, it can also be a pigment that changes color or decolorizes directly upon exposure to acids, bases, or free radicals without exposure.

[0251] 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.

[0252] From the perspective of visual recognition and resolution of the exposed and unexposed areas, the photosensitive resin layer preferably contains both a pigment N, which changes its maximum absorption wavelength through free radicals, and a photoradical polymerization initiator.

[0253] 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.

[0254] As an example of the color-developing mechanism for pigment N in this invention, one can exemplify the following method: adding a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photoalkali generator to a photosensitive resin layer, and developing the color of the free radical reactive pigment, acid reactive pigment, or alkali reactive pigment (e.g., colorless pigment) by the free radicals, acids, or bases generated by the photoradical polymerization initiator, photocationic polymerization initiator, or photoalkali generator after exposure.

[0255] From the viewpoint of visual recognition of the exposed and unexposed parts, the maximum absorption wavelength of pigment N in the wavelength range of 400nm to 780nm is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm.

[0256] 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.

[0257] 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.

[0258] As pigments that develop or fade color through exposure, colorless compounds can be cited as an example.

[0259] Examples of pigments that are decolorized by exposure include colorless compounds, diarylmethane pigments, oxazine pigments, xanthones, iminonaphthoquinone pigments, azomethyl alkaloid pigments, and anthraquinone pigments.

[0260] From the viewpoint of visual recognition of the exposed and unexposed areas, colorless compounds are preferred as pigment N.

[0261] 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).

[0262] 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.

[0263] 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, and whose color develops through ring-opening by a free radical or acid; more preferably, it is a compound having a lactone ring and whose color develops through ring-opening by a free radical or acid.

[0264] As pigment N, examples include the following dyes and colorless compounds.

[0265] 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.

[0266] 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.

[0267] From the perspective 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.

[0268] As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0269] One pigment can be used alone, or two or more pigments can be used.

[0270] From the viewpoint of visual recognition of the exposed and unexposed areas, visual recognition of the developed pattern, and resolution, the pigment content is preferably 0.1% by mass or more relative to the total mass of the photosensitive resin layer, 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.

[0271] 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 resin 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.

[0272] The content of pigment N refers to the amount of pigment that enables all pigments N contained in the photosensitive resin 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.

[0273] Two solutions were prepared, each containing 0.001 g or 0.01 g of pigment dissolved in 100 mL of methyl ethyl ketone. Irgacure OXE01 (trade name, BASF Japan Ltd.) was added to each solution as a photoradical polymerization initiator, and the solutions were irradiated with 365 nm light, thereby generating free radicals and causing all pigments to become colored. Then, under ambient 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.

[0274] Next, except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigment, the absorbance of the solution that caused all the pigment to develop color was measured using the same method as described above. Based on the absorbance of the obtained solution containing the photosensitive resin layer, the content of pigment contained in the photosensitive resin layer was calculated based on the calibration curve.

[0275] <Polymerization inhibitors>

[0276] From the viewpoints of storage stability, changes in storage time linewidth, and changes in development temperature linewidth, the photosensitive resin layer preferably further contains a polymerization inhibitor.

[0277] As a polymerization inhibitor, it is preferable to include a free radical polymerization inhibitor.

[0278] There are no particular restrictions on its use as a polymerization inhibitor; any known polymerization inhibitor can be used.

[0279] Examples of polymerization inhibitors include phenothiazine, phenoxazine, hydroquinone, tetrachlorobenzoquinone, sodium phenolindophenol, m-aminophenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine salts (ammonium salts, cerium salts, etc.), and 2,2,6,6-tetramethylpiperidin-1-oxy. In addition, polymerization inhibitors sometimes also function as antioxidants.

[0280] Furthermore, as a polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be cited.

[0281] Other polymerization inhibitors include naphthylamine, cuprous chloride, aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive resin layer, aluminum nitrosophenylhydroxylamine is preferably used as a free radical polymerization inhibitor.

[0282] Among them, as a polymerization inhibitor, from the viewpoint of storage stability, changes in storage time linewidth, changes in development temperature linewidth and sensitivity, it is preferable to include at least one compound selected from phenothiazine, phenothiazine and compounds having a hindered phenolic structure, more preferably to include at least one compound selected from phenothiazine and phenothiazine, and especially preferably to include phenothiazine.

[0283] A single polymerization inhibitor can be used alone, or two or more can be used together.

[0284] From the viewpoints of storage stability, changes in the length of time, changes in the length of time of development, and sensitivity, the content of the polymerization inhibitor relative to the total mass of the photosensitive resin layer is preferably 0.005% to 2% by mass, more preferably 0.01% to 1% by mass, even more preferably 0.05% to 0.5% by mass, and particularly preferably 0.2% to 0.4% by mass.

[0285] Furthermore, when the content of the photopolymerization initiator in the photosensitive resin layer is set to Rc and the content of the polymerization inhibitor is set to Rd, from the viewpoint of changes in the placement time linewidth, changes in the development temperature linewidth, and sensitivity, the mass ratio Rd / Rc is preferably 0.01 or more and 0.2 or less, more preferably 0.02 or more and 0.1 or less, and particularly preferably 0.03 or more and 0.05 or less.

[0286] <Thermocrosslinking compounds>

[0287] From the viewpoint of the strength of the cured film and the adhesion of the uncured film, the photosensitive resin layer preferably contains a thermally crosslinking compound. Furthermore, in this specification, the thermally crosslinking compound having the olefinically unsaturated groups described later is treated as a thermally crosslinking compound, not as an olefinically unsaturated compound.

[0288] 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.

[0289] Since the capped isocyanate compound reacts with hydroxyl and carboxyl groups, the hydrophilicity of the formed film decreases, for example, in the case of alkali-soluble resins and / or olefinic unsaturated compounds having at least one of hydroxyl and carboxyl groups, thereby enhancing the function of the film formed by curing the photosensitive resin layer as a protective film.

[0290] 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".

[0291] 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.

[0292] 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)".

[0293] 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.

[0294] 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 a structure represented by -C (=N-OH)- in the molecule).

[0295] 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 storage stability.

[0296] For example, from the viewpoint of improving the brittleness of the film and enhancing the adhesion with the substrate, the end-capped isocyanate compound preferably has an isocyanurate structure.

[0297] End-capped isocyanate compounds having an isocyanurate structure are obtained, for example, by isocyanuric acid esterification of hexamethylene diisocyanate.

[0298] Among the isocyanurate compounds with an isocyanurate structure, 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, compounds with an oxime structure that use an oxime compound as a capping agent are preferred.

[0299] End-capped isocyanate compounds can have polymerizable groups.

[0300] There are no particular restrictions on the polymerizable group; known polymerizable groups can be used, with free radical polymerizable groups being preferred.

[0301] 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.

[0302] Among them, as a polymerizable group, an olefinic unsaturated group is preferred, (meth)acryloyloxy is more preferred, and acryloyloxy is even more preferred.

[0303] As a capped isocyanate compound, it can be used in commercially available products.

[0304] 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).

[0305] Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0306] [Chemical Formula 2]

[0307]

[0308] One type of thermally crosslinking compound can be used alone, or two or more types can be used.

[0309] When the photosensitive resin layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive resin layer is preferably 1% to 50% by mass, more preferably 5% to 30% by mass.

[0310] <Other Ingredients>

[0311] The photosensitive resin layer may contain components other than the alkali-soluble resin, olefinic unsaturated compound, photopolymerization initiator, pigment, polymerization inhibitor and thermal crosslinking compound mentioned above.

[0312] -surfactant-

[0313] From the perspective of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

[0314] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.

[0315] 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.

[0316] Fluorinated surfactants or silicone surfactants are preferred as surfactants.

[0317] 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) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (all manufactured by Neos Company Limited), U-120E (Uni-chem Co., Ltd.), etc.

[0318] 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.

[0319] Furthermore, fluorinated surfactants are preferably polymers of vinyl ether compounds containing fluorine atoms and having fluorinated alkyl or fluorinated alkylene ether groups, as well as hydrophilic vinyl ether compounds.

[0320] 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).

[0321] 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).

[0322] 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, sorbitan fatty acid esters, 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), and Solsperse (trade name) 20000 (all manufactured by Lubrizol Japan). Limited), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako PureChemical Corporation), PIONIN (trade name) D-1105, D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by NissinChemical Co., Ltd.), etc.

[0323] From the viewpoint of improving environmental adaptability, surfactants derived from alternative materials of compounds having a straight-chain perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are preferred as fluorinated surfactants.

[0324] 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.

[0325] 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. manufactures and produces X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-10 5. KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-32 3. KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (the above are Shin-EtsuChemical (Manufactured by Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (all manufactured by BYK Chemie), 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] The photosensitive resin layer may contain one surfactant or two or more surfactants.

[0328] The surfactant content relative to the total mass of the photosensitive resin layer is preferably 0.001% to 10% by mass, more preferably 0.01% to 3% by mass.

[0329] -additive-

[0330] In addition to the above-mentioned components, the photosensitive resin layer may also contain known additives as needed.

[0331] Examples of additives include, for example, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and solvents. The photosensitive resin layer may contain one or more of these additives.

[0332] 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.

[0333] 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)aminoethyl carboxylated benzotriazole. Commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD., trade name) can also be used as carboxylated benzotriazoles.

[0334] The total content of benzotriazoles and carboxybenzotriazoles relative to the total mass of the photosensitive resin layer is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin layer, 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.

[0335] The photosensitive resin layer may contain at least one selected from plasticizers and heterocyclic compounds.

[0336] As plasticizers and heterocyclic compounds, examples include the compounds described in paragraphs 0097–0103 and 0111–0118 of International Publication No. 2018 / 179640.

[0337] The photosensitive resin layer may also contain solvent. In cases where the photosensitive resin layer is formed from a photosensitive resin composition containing solvent, the solvent may sometimes remain in the photosensitive resin layer.

[0338] Furthermore, the photosensitive resin 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.

[0339] The additives contained in the photosensitive resin 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.

[0340] <Impurities, etc.>

[0341] The photosensitive resin layer may contain a specified amount of impurities.

[0342] 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.

[0343] The impurity content in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, based on a mass basis. The impurity content can be set to 1 ppb or more, or 0.1 ppm or more, based on a mass basis.

[0344] 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 resin layer, and cleaning and removing impurities. By using these methods, the amount of impurities can be kept within the aforementioned range.

[0345] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) luminescence spectrophotometry, atomic absorption spectrometry, and ion chromatography.

[0346] The photosensitive resin 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 resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass.

[0347] The lower limit, based on the total mass of the photosensitive resin 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 the aforementioned metal impurities. Furthermore, quantification can be performed using known methods.

[0348] From the viewpoint of improving reliability and lamination, the water content in the photosensitive resin layer is preferably 0.01% to 1.0% by mass, more preferably 0.05% to 0.5% by mass.

[0349] <Residual Monomer>

[0350] The photosensitive resin layer sometimes contains residual monomers corresponding to the structural units of the aforementioned alkali-soluble resin.

[0351] From the viewpoint of patternability 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.

[0352] From the viewpoint of patternability and reliability, the residual monomer of each structural unit of the alkali-soluble resin relative to the total mass of the photosensitive resin 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.

[0353] 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.

[0354] The amount of residual monomers can be determined by known methods such as liquid chromatography and gas chromatography.

[0355] <Physical properties, etc.>

[0356] From the viewpoint of developability and resolution, the thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 1 μm or more and 5 μm or less.

[0357] 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.

[0358] Furthermore, from the viewpoint of superior adhesion, the transmittance of light with a wavelength of 365 nm in the photosensitive resin 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.

[0359] <Formation Method>

[0360] There are no particular restrictions on the method for forming the photosensitive resin layer, as long as it is a method that can form a layer containing the above-mentioned components.

[0361] As a method for forming a photosensitive resin 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 forming the layer by drying the coating of the photosensitive resin composition.

[0362] Examples of photosensitive resin compositions used in the formation of the photosensitive resin layer include compositions containing an alkali-soluble resin, an olefinic unsaturated compound, a photopolymerization initiator, any of the above-mentioned components, and a solvent.

[0363] In order to adjust the viscosity of the photosensitive resin composition to facilitate the formation of a photosensitive resin layer, the photosensitive resin composition preferably contains a solvent.

[0364] -solvent-

[0365] As a solvent contained in the photosensitive resin composition, there are no particular restrictions as long as it is a solvent capable of dissolving or dispersing alkali-soluble resins, olefinic unsaturated compounds, photopolymerization initiators, and any of the above-mentioned components; any known solvent can be used.

[0366] Examples of solvents include, for example, 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.

[0367] When manufacturing a photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, 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 selected from 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 at least one mixed solvent selected from at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

[0368] 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.

[0369] 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.

[0370] 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.

[0371] The photosensitive resin composition may contain one solvent alone or two or more solvents.

[0372] 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.

[0373] There are no particular limitations on the preparation method of the photosensitive resin composition. The following method can be used as an example: 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.

[0374] Before forming the photosensitive resin layer, it is preferable to filter the photosensitive resin composition using a filter with a pore size of 0.2 μm to 30 μm.

[0375] 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 printing, spraying, roller coating, bar coating, curtain coating, spin coating, and stencil coating (i.e., slot coating).

[0376] Furthermore, the photosensitive resin layer can also be formed by coating the photosensitive resin composition onto the protective film described later and then drying it.

[0377] As a drying method for the coating film of the photosensitive resin composition, heating drying and vacuum drying are preferred.

[0378] The preferred drying temperature is 80°C or higher, more preferably 90°C or higher. Furthermore, the upper limit is preferably 130°C or lower, more preferably 120°C or lower. The drying process can also be achieved by continuously changing the temperature.

[0379] Furthermore, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular limitation on the upper limit, but it is preferably 600 seconds or less, more preferably 300 seconds or less.

[0380] [Thermoplastic resin layer]

[0381] Photosensitive transfer materials can also have a thermoplastic resin layer.

[0382] The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. This is because having a thermoplastic resin layer between the temporary support and the photosensitive resin layer improves the substrate-to-substrate conformability during the bonding process, thereby suppressing the incorporation of air bubbles between the substrate and the photosensitive transfer material, and improving the adhesion to adjacent layers (e.g., the temporary support).

[0383] Alkali-soluble resins

[0384] The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

[0385] 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.

[0386] From the viewpoint of developability and adhesion to adjacent layers, acrylic resin is preferred as an alkali-soluble resin.

[0387] Acrylic resin refers to a resin having at least one structural unit selected from structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide.

[0388] As an 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.

[0389] The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylate relative to the total mass of acrylic resin is preferably 30% to 100% by mass, more preferably 50% to 100% by mass.

[0390] Furthermore, the alkali-soluble resin is preferably a polymer with acid groups.

[0391] Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups, with carboxyl being the most preferred.

[0392] From the viewpoint of developability, alkali-soluble resins are more preferably alkali-soluble resins with an acid value of 60 mg KOH / g or higher, and even more preferably acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher.

[0393] There is no particular limit to the upper limit of the acid value of alkali-soluble resins, but it is preferably below 200 mg KOH / g, and more preferably below 150 mg KOH / g.

[0394] There are no particular restrictions on the use of carboxyl-containing acrylic resins with an acid value of 60 mg KOH / g or higher, and they can be appropriately selected from known resins.

[0395] For example, examples include the alkali-soluble resin containing carboxyl groups in the polymer described in paragraph 0025 of Japanese Patent Application Publication No. 2011-95716, the alkali-soluble resin containing carboxyl groups in the polymer described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and the alkali-soluble resin containing carboxyl groups in the polymer described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0396] The copolymerization ratio of the carboxyl-containing structural units in the above-mentioned carboxyl-containing acrylic resin relative to the total mass of the acrylic resin is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 12% to 30% by mass.

[0397] From the viewpoint of developability and adhesion to adjacent layers, acrylic resins having structural units derived from (meth)acrylic acid are particularly preferred as alkali-soluble resins.

[0398] Alkali-soluble resins can possess reactive groups. Any group capable of addition polymerization can be considered a reactive group; examples include olefinic unsaturated groups; condensation groups such as hydroxyl and carboxyl groups; and addition polymerization reactive groups such as epoxy and (block) isocyanate groups.

[0399] 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 even more preferably 20,000 to 50,000.

[0400] The thermoplastic resin layer may contain one type of alkali-soluble resin or two or more types.

[0401] From the viewpoint of developability and adhesion to adjacent layers, 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, even more preferably 40% to 80% by mass, and especially preferably 50% to 70% by mass.

[0402] Pigment

[0403] The thermoplastic resin layer preferably contains a pigment (also referred to as "pigment B"). The maximum absorption wavelength of this pigment in the wavelength range of 400nm to 780nm is above 450nm, and the maximum absorption wavelength changes due to acids, bases or free radicals.

[0404] The preferred method for pigment B is the same as that for pigment N, except for the points described later.

[0405] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, 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.

[0406] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, the thermoplastic resin layer preferably contains both a pigment (as pigment B) whose maximum absorption wavelength changes with acid and a compound that generates acid with light (described later).

[0407] Pigment B can be used alone or in combination with two or more pigments.

[0408] From the viewpoint of visual distinguishability of the exposed and unexposed areas, the content 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% by mass to 6% by mass, even more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.

[0409] Here, the content of pigment B refers to the amount of pigment that makes all pigments B contained in the thermoplastic resin layer appear 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 B.

[0410] Solutions were prepared by dissolving 0.001 g and 0.01 g of pigment in 100 mL of methyl ethyl ketone. Irgacure OXE0 1 (trade name, BASF Japan Ltd.) as a photoradical polymerization initiator was added to each solution, and the solutions were irradiated with 365 nm light, thereby generating free radicals and causing all pigments to become colored. Then, under ambient 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.

[0411] Next, 0.1 g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. Otherwise, the absorbance of the solution that caused the pigment to fully develop color was measured using the same method as described above. Based on the absorbance of the obtained solution containing the thermoplastic resin layer and based on the calibration curve, the amount of pigment contained in the thermoplastic resin layer was calculated.

[0412] <Compounds that produce acids, bases, or free radicals through light>

[0413] The thermoplastic resin layer may contain compounds that generate acids, bases, or free radicals upon exposure to light (also referred to as "compound C").

[0414] As compound C, it is preferably a compound that generates an acid, base or free radical by accepting activating light such as ultraviolet light and visible light.

[0415] Compound C can be made from known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical generators). Among these, photoacid generators are preferred.

[0416] -Photogenerating Acid Agent-

[0417] From a resolution perspective, the thermoplastic resin layer preferably contains a photoacid-generating agent.

[0418] As photoacid generators, examples of photocationic polymerization initiators that can be contained in the aforementioned photosensitive resin layer are as follows, except for the points described later.

[0419] As a photoacid generator, from the viewpoint of sensitivity and resolution, it is preferable to contain at least one compound selected from onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is more preferable to contain oxime sulfonate compounds.

[0420] Furthermore, photoacid generators having the following structure are preferred as photoacid generators.

[0421] [Chemical Formula 3]

[0422]

[0423] -Photoradical polymerization initiator-

[0424] The thermoplastic resin layer may contain a photoradical polymerization initiator.

[0425] As photoradical polymerization initiators, examples of photoradical polymerization initiators that can be contained in the aforementioned photosensitive resin layer are given, and the preferred methods are also the same.

[0426] -Photo-alkali-producing agent-

[0427] Thermoplastic resin layers may also contain photoalkali-generating agents.

[0428] As a photoalkali-generating agent, there are no particular restrictions as long as it is a well-known photoalkali-generating agent. For example, 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, (4-morpholinylbenzoyl) )-1-benzyl-1-dimethylaminopropane, 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.

[0429] The thermoplastic resin layer may contain one or more compounds C.

[0430] From the viewpoint of visual recognition and resolution of the exposed and unexposed areas, 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.

[0431] <Plasticizer>

[0432] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

[0433] Preferably, the molecular weight (in the case of oligomers or polymers, weight-average molecular weight (Mw)) of the plasticizer is less than that of the alkali-soluble resin. The molecular weight (weight-average molecular weight (Mw)) of the plasticizer is preferably between 200 and 2,000.

[0434] Regarding plasticizers, there are no particular limitations as long as they are compounds that exhibit plasticizing properties when miscible with alkali-soluble resins. From the viewpoint of imparting plasticizing properties, plasticizers preferably have alkylene oxides in their molecules, and more preferably are polyalkylene glycol compounds. The alkylene oxides contained in the plasticizer are more preferably polyvinyloxy or polyacryloxy structures.

[0435] Furthermore, 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 adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0436] Examples of (meth)acrylate compounds used as plasticizers include (meth)acrylate compounds described as olefinic unsaturated compounds contained in the aforementioned photosensitive resin layer.

[0437] In photosensitive transfer materials, when a thermoplastic resin layer and a photosensitive resin layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. This is because, by having the same (meth)acrylate compound in both the thermoplastic resin layer and the photosensitive resin layer, interlayer diffusion is suppressed, and storage stability is improved.

[0438] When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesion to adjacent layers, it is preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure.

[0439] Furthermore, from the viewpoints of resolution, adhesion to adjacent layers, and developability, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in one molecule are preferred as (meth)acrylate compounds used as plasticizers.

[0440] Furthermore, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

[0441] The thermoplastic resin layer may contain one type of plasticizer or two or more types.

[0442] From the viewpoints of resolution, adhesion to adjacent layers, and developability, the content of plasticizer 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.

[0443] <surfactants>

[0444] From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant.

[0445] As surfactants, examples of surfactants that can be contained in the aforementioned photosensitive resin layer can be cited, and the preferred methods are also the same.

[0446] The thermoplastic resin layer may contain one surfactant or two or more surfactants.

[0447] 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.

[0448] <Sensitizer>

[0449] The thermoplastic resin layer may contain sensitizers.

[0450] There are no particular restrictions on what a sensitizer can be; examples of sensitizers that can be contained in the aforementioned photosensitive resin layers can be cited.

[0451] The thermoplastic resin layer may contain one type of sensitizer or two or more types.

[0452] The content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity relative to the light source and the visual recognition of the exposed and unexposed parts, it is preferably in the range of 0.01% to 5% by mass relative to the total mass of the thermoplastic resin layer, and more preferably in the range of 0.05% to 1% by mass.

[0453] <Additives, etc.>

[0454] In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives as needed.

[0455] Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated into this specification.

[0456] <Physical properties, etc.>

[0457] There is no particular limitation on the thickness of the thermoplastic resin layer, but from the viewpoint of adhesion to adjacent layers, it is preferably 1 μm or more, more preferably 2 μm or more. There is no particular limitation on the upper limit, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0458] <Formation Method>

[0459] There are no particular restrictions on the method for forming the thermoplastic resin layer, as long as it is a method that can form a layer containing the above-mentioned components.

[0460] As a method for forming a thermoplastic resin layer, for example, the following method can be used: a thermoplastic resin composition containing the above-mentioned components and solvent is prepared, the thermoplastic composition is coated on a surface such as a support, and the coating film of the thermoplastic resin composition is dried to form the layer.

[0461] In order to adjust the viscosity of the thermoplastic resin composition to facilitate the formation of a thermoplastic resin layer, the thermoplastic resin composition preferably contains a solvent.

[0462] -solvent-

[0463] As a solvent contained in a thermoplastic resin composition, there are no particular limitations as long as it can dissolve or disperse the aforementioned components contained in the thermoplastic resin layer.

[0464] Examples of solvents that can be contained in the thermoplastic resin composition include those found in the above-mentioned photosensitive resin composition, and the preferred method is also the same.

[0465] The solvent contained in the thermoplastic resin composition may be a single type or two or more types.

[0466] The solvent content when coating 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.

[0467] The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be carried out by simply following the above-described methods for preparing the photosensitive resin composition and forming the photosensitive resin layer.

[0468] For example, a solution is prepared in advance in which each component contained in the thermoplastic resin layer is dissolved in the solvent. The resulting solution is mixed in a specified ratio to prepare a thermoplastic resin composition. The obtained thermoplastic resin composition is then coated on the surface of a temporary support and the coating of the thermoplastic resin composition is dried to form a thermoplastic resin layer.

[0469] Furthermore, a thermoplastic resin layer can be formed on the surface of the intermediate layer after a photosensitive resin layer and an intermediate layer are formed on the protective film described later.

[0470] [Intermediate layer]

[0471] The preferred photosensitive transfer material has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. By having an intermediate layer, it is possible to suppress the mixing of components during multi-layer coating and storage after coating.

[0472] From the viewpoint of developability and the inhibition of mixing of components during multi-layer coating and storage after coating, the intermediate layer is preferably a water-soluble layer.

[0473] In addition, in this specification, "water solubility" means that the solubility of 100g of water at pH 7.0 with a liquid temperature of 22°C is greater than 0.1g.

[0474] As an intermediate layer, an oxygen barrier layer with oxygen barrier function described as a "separation layer" in Japanese Patent Application Publication No. 5-72724 can be cited as an example. If the intermediate layer is an oxygen barrier layer, the sensitivity during exposure will be improved, the time load of the exposure machine will be reduced, and thus the productivity will be improved, so it is preferred.

[0475] The oxygen barrier layer used as the intermediate layer can be appropriately selected from the known layers described in the aforementioned publications, etc. Among them, an oxygen barrier layer 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) is preferred.

[0476] The intermediate layer preferably contains resin.

[0477] Examples of resins contained 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.

[0478] The resin contained in the intermediate layer is preferably a water-soluble resin.

[0479] Furthermore, 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 the polymer A contained in the photosensitive resin layer and the thermoplastic resin (e.g., alkali-soluble resin) contained in the thermoplastic resin layer.

[0480] 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 both polyvinyl alcohol and polyvinylpyrrolidone.

[0481] The intermediate layer may contain one of the above-mentioned resins alone, or it may contain two or more of them.

[0482] There are no particular limitations on the resin content in the intermediate layer, but from the viewpoint of oxygen barrier properties and suppressing the mixing of components during multi-layer coating and storage after coating, it 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.

[0483] Furthermore, the intermediate layer may contain additives such as surfactants, depending on the requirements.

[0484] There are no particular restrictions on the thickness of the intermediate layer, but it is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm.

[0485] This is because if the thickness of the intermediate layer is within the above range, it will not reduce the oxygen barrier properties and can suppress the mixing of components when coating multiple layers and when storing after coating, and can also suppress the increase in intermediate layer removal time during development.

[0486] There are no particular limitations on the method of forming the intermediate layer. For example, the following method can be used: prepare an intermediate layer composition containing the above-mentioned resin and any additives, coat it on the surface of a thermoplastic resin layer or a photosensitive resin layer, and dry the coating of the intermediate layer composition to form the intermediate layer.

[0487] To facilitate the formation of the intermediate layer composition by adjusting its viscosity, the intermediate layer composition preferably contains a solvent.

[0488] The solvent contained in the intermediate layer composition is not particularly limited as long as it can dissolve or disperse the resin. It is preferably selected from at least one of water and water-mixed organic solvents, and more preferably water or a mixture of water and water-mixed organic solvents.

[0489] Examples of water-mixable organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0490] [Protective film]

[0491] The photosensitive transfer material preferably has a protective film that is in contact with the surface of the photosensitive resin layer that is not in contact with the surface opposite to the temporary support.

[0492] As materials for forming the protective film, resin films and paper can be cited as examples. From the point of view of strength and flexibility, resin films are preferred.

[0493] 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.

[0494] There are no particular limitations on the thickness (layer thickness) of the protective film, but it is preferably 5μm to 100μm, and more preferably 10 to 50μm.

[0495] Furthermore, from the viewpoint of superior resolution, the arithmetic mean roughness Ra value of the surface of the protective film in contact with the photosensitive resin layer (hereinafter, also simply referred to as the "surface of the protective film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less. This is because, with the Ra value of the protective film surface within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern is improved.

[0496] There is no particular limitation on the lower limit of the Ra value of the protective film surface, but it is preferably 0.001 μm or higher.

[0497] The Ra value of the protective film surface was determined using the following method.

[0498] Using a three-dimensional optical profilometer (New View 7300, manufactured by Zygo), the surface profile of the protective film was measured under the following conditions to obtain the surface profile of the optical film.

[0499] 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, thereby obtaining the Ra value of the protective film surface.

[0500] When the protective film is attached to the photosensitive transfer material, the protective film can be peeled off from the photosensitive transfer material, and the Ra value of the surface of the peeled side can be measured.

[0501] There are no particular restrictions on the method of attaching the protective film to the photosensitive resin layer, etc., and well-known methods can be cited.

[0502] As a device for attaching a protective film to a photosensitive resin layer, well-known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0503] The laminator is preferably equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heating.

[0504] 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.

[0505] 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.

[0506] 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.

[0507] Furthermore, from the viewpoint of further maximizing the effects of the present invention, the total thickness of the photosensitive resin 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.

[0508] The photosensitive transfer material of this invention is preferably used in various applications requiring precision microfabrication based on photolithography. After patterning the photosensitive resin 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.

[0509] [Manufacturing method of photosensitive transfer material]

[0510] There are no particular limitations on the manufacturing method of the photosensitive transfer material used in this invention, and known manufacturing methods, such as known methods for forming the layers, can be used.

[0511] The following is for reference. Figure 1The 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.

[0512] 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, a water-soluble resin layer 15, a photosensitive resin layer 17, and a protective film 19 stacked sequentially.

[0513] 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 13; after coating a water-soluble resin layer composition on the surface of the thermoplastic resin layer 13, drying the coating of the water-soluble resin layer composition to form a water-soluble resin layer 15; and after coating a photosensitive resin composition containing an alkali-soluble resin and an olefinically unsaturated compound on the surface of the water-soluble resin layer 15, drying the coating of the photosensitive resin composition to form a photosensitive resin layer 17.

[0514] In the above manufacturing method, it is preferable to use the following composition: a thermoplastic resin composition containing at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents; a water-soluble resin layer composition containing at least one selected from water and water-miscible organic solvents; and a photosensitive resin composition containing an alkali-soluble resin, an olefinic unsaturated compound, and at least one selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. This suppresses the coating of the water-soluble resin layer composition onto the surface of the thermoplastic resin layer 13 and / or the mixing of components contained in the thermoplastic resin layer 13 with components contained in the water-soluble resin layer 15 during storage of the laminate containing the water-soluble resin layer composition, and also suppresses the coating of the photosensitive resin composition onto the surface of the water-soluble resin layer 15 and / or the mixing of components contained in the water-soluble resin layer 15 with components contained in the photosensitive resin layer 17 during storage of the laminate containing the photosensitive resin composition.

[0515] Photosensitive transfer material 20 is manufactured by pressing a protective film 19 onto a photosensitive resin layer 17 of a laminate manufactured using the above-described manufacturing method.

[0516] 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, a water-soluble resin layer 15, a photosensitive resin 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 resin layer 17.

[0517] 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.

[0518] The photosensitive transfer material of this invention is preferably used in various applications requiring precision microfabrication based on photolithography. After patterning the photosensitive resin 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.

[0519] Furthermore, the photosensitive transfer material of the first embodiment may preferably be a coloring resin layer in which the photosensitive resin layer includes pigment.

[0520] In addition to the above, the coloring resin layer is suitable for forming color pixels or black matrices such as color filters for liquid crystal display devices (LCDs) and solid-state imaging elements (e.g., CCDs and CMOS).

[0521] The same applies to the methods described above, excluding pigments, in the coloring resin layer.

[0522] Pigments

[0523] The photosensitive resin layer can be a colored resin layer containing pigments.

[0524] 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.

[0525] 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.

[0526] 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.

[0527] 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.

[0528] Particle size refers to the diameter of a circle whose area is calculated from a photograph of pigment particles taken with an electron microscope and whose area is the same as that of the pigment particles. 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.

[0529] Regarding white pigments other than black pigments, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Publication No. 2005-007765 can be used. Specifically, among white pigments, the preferred inorganic pigments are titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon, 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.

[0530] Furthermore, the surface of titanium oxide can be treated with silica, alumina, titanium dioxide, zirconium dioxide, or organic substances, or even two or more of these treatments. This inhibits the catalytic activity of titanium oxide and improves its heat resistance and fading properties.

[0531] From the viewpoint of reducing the thickness of the heated photosensitive resin layer, at least one of aluminum oxide treatment and zirconium dioxide treatment is preferred as a surface treatment for the surface of titanium oxide, and both aluminum oxide treatment and zirconium dioxide treatment are particularly preferred.

[0532] Furthermore, when the photosensitive resin layer is a colored resin layer, from the viewpoint of transferability, it is preferable that the photosensitive resin layer also contains colored pigments other than black and white pigments. When colored pigments are included, from the viewpoint of better dispersibility, the particle size of the colored pigments is preferably 0.1 μm or less, more preferably 0.08 μm or less.

[0533] 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 Monastella Fast. 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.

[0534] When the photosensitive resin layer contains pigment, the pigment content is preferably more than 3% by mass and less than 40% by mass relative to the total mass of the photosensitive resin layer, 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.

[0535] When the photosensitive resin 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.

[0536] In addition, when the photosensitive resin layer contains a black pigment and the photosensitive resin 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.

[0537] 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.

[0538] 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).

[0539] [Photosensitive transfer material according to the second embodiment]

[0540] The following example illustrates the photosensitive transfer material of the second embodiment.

[0541] Figure 2 The photosensitive transfer material 10 shown has a temporary support 1, a transfer layer 2 comprising a photosensitive resin layer 3 and a refractive index adjustment layer 5, and a protective film 7.

[0542] and, Figure 2 The photosensitive transfer material 10 shown is configured with a refractive index adjustment layer 5, but it is also possible to omit the refractive index adjustment layer 5.

[0543] The components constituting the photosensitive transfer material of the second embodiment will be described below.

[0544] The temporary support and protective film used in the photosensitive transfer material of the second embodiment are the same as those used in the photosensitive transfer material of the first embodiment, and the preferred embodiments are also the same.

[0545] [Photosensitive resin layer]

[0546] Photosensitive transfer materials have a photosensitive resin layer.

[0547] After the photosensitive resin layer is transferred onto the substrate, it is exposed and developed, thereby forming a pattern on the substrate.

[0548] The following is a detailed description of the components that may be included in a photosensitive resin layer.

[0549] Alkali-soluble resins

[0550] The photosensitive resin layer contains an alkali-soluble resin.

[0551] Examples of alkali-soluble resins include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reacting epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting epoxy acrylate resins with acid anhydrides.

[0552] As one of the preferred types of alkali-soluble resins, (meth)acrylic resins can be cited from the viewpoint of excellent alkali developability and film-forming properties.

[0553] Furthermore, in this specification, (meth)acrylic resin refers to a resin having structural units derived from (meth)acrylic acid compounds. The content of structural units derived from (meth)acrylic acid compounds relative to all structural units of the (meth)acrylic acid resin is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0554] (Meth)acrylic resins can consist solely of structural units derived from (meth)acrylic acid compounds, or they can contain structural units derived from polymerizable monomers other than (meth)acrylic acid compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic acid compounds is less than 100% by mass relative to all structural units of the (meth)acrylic resin.

[0555] Examples of (meth)acrylic acid compounds include, for example, (meth)acrylic acid, (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile.

[0556] Examples of (meth)acrylates include, for example, alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, with alkyl (meth)acrylates being preferred.

[0557] Examples of (meth)acrylamides include, for example, diacetone acrylamide and other acrylamides.

[0558] Examples of alkyl methacrylates include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, and dodecyl methacrylate, which are alkyl methacrylates having alkyl groups having 1 to 12 carbon atoms.

[0559] As a (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0560] (Meth)acrylic resins can have structural units other than those derived from (meth)acrylic acid compounds.

[0561] As the polymerizable monomer that forms the above-mentioned structural unit, there are no particular restrictions as long as it is a compound other than (meth)acrylic acid compound that can copolymerize with (meth)acrylic acid compound. Examples include styrene compounds such as styrene, vinyltoluene and α-methylstyrene that can have substituents at the α-position or on the aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, maleic acid monoesters such as fumaric acid, cinnamic acid, α-cyanocinonic acid, itaconic acid and crotonic acid.

[0562] These polymerizable monomers can be used in one or in combination of two or more.

[0563] Furthermore, from the viewpoint of improving alkaline developability, (meth)acrylic resins preferably contain structural units having acid groups. Examples of acid groups include carboxyl, sulfonyl, phosphate, and phosphonic acid groups.

[0564] The (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

[0565] From the viewpoint of excellent developability, the content of acid-containing structural units (preferably structural units derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more relative to the total mass of the (meth)acrylic resin. Furthermore, there is no particular upper limit, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, more preferably 40% by mass or less.

[0566] Furthermore, the (meth)acrylic resin is more preferably composed of structural units derived from the aforementioned alkyl (meth)acrylic esters.

[0567] The content of structural units derived from alkyl methacrylates in the (meth)acrylic resin is preferably 50% to 90% by mass relative to all structural units of the (meth)acrylic resin, more preferably 60% to 90% by mass, and even more preferably 65% ​​to 90% by mass.

[0568] As a (meth)acrylic resin, a resin having both structural units derived from (meth)acrylic acid and structural units derived from alkyl methacrylates is preferred, and a resin consisting only of structural units derived from (meth)acrylic acid and structural units derived from alkyl methacrylates is more preferred.

[0569] Furthermore, as a (meth)acrylic resin, an acrylic resin having structural units derived from methacrylic acid, structural units derived from methyl methacrylate, and structural units derived from ethyl acrylate is preferred.

[0570] Furthermore, from the viewpoint of achieving better results with the present invention, the (meth)acrylic resin preferably has at least one of the structural units selected from methacrylic acid and structural units selected from alkyl methacrylates, and preferably has both structural units selected from methacrylic acid and structural units selected from alkyl methacrylates.

[0571] From the viewpoint of achieving better results with the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates in the (meth)acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, relative to all structural units of the (meth)acrylic resin. There is no particular limitation on the upper limit; it can be 100% by mass or less, preferably 80% by mass or less.

[0572] Furthermore, from the viewpoint of achieving better results with the present invention, the (meth)acrylic resin preferably has at least one structural unit selected from methacrylic acid and structural units selected from alkyl methacrylates, and at least one structural unit selected from acrylic acid and structural units selected from alkyl acrylates.

[0573] From the viewpoint of achieving better results from the present invention, the total content of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates is preferably 60 / 40 to 80 / 20 by mass relative to the total content of structural units derived from acrylic acid and structural units derived from alkyl acrylates.

[0574] From the viewpoint of excellent developability of the transferred photosensitive resin layer, (meth)acrylic resin preferably has ester groups at the ends.

[0575] Furthermore, the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used for synthesis. (Meth)acrylic resins with ester groups at the terminals can be synthesized using a polymerization initiator that generates free radicals containing ester groups.

[0576] Furthermore, from the viewpoint of developability, alkali-soluble resins are preferably, for example, alkali-soluble resins with an acid value of 60 mg KOH / g or higher.

[0577] Furthermore, from the viewpoint that a strong film can be easily formed by thermal crosslinking with the crosslinking components through heating, for example, the alkali-soluble resin is more preferably a carboxyl-containing resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing resin), and even more preferably a carboxyl-containing (meth)acrylic resin with an acid value of 60 mg KOH / g or higher (so-called carboxyl-containing (meth)acrylic resin).

[0578] If the alkali-soluble resin is a carboxyl-containing resin, then thermal crosslinking can be performed, for example, by adding a thermally crosslinking compound such as a capped isocyanate compound, thereby increasing the three-dimensional crosslinking density. Furthermore, if the carboxyl groups of the resin are dehydrated and hydrophobized, the resistance to damp heat can be improved.

[0579] As for carboxyl-containing (meth)acrylic resins with an acid value of 60 mg KOH / g or higher, there are no particular restrictions as long as the above acid value condition is met, and appropriate selection can be made from known (meth)acrylic resins.

[0580] For example, acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher in polymers described in paragraph 0025 of Japanese Patent Application Publication No. 2011-095716, and acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher in polymers described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, are preferred.

[0581] As another preferred option for alkali-soluble resins, styrene-acrylic acid copolymers can be cited. Furthermore, in this specification, styrene-acrylic acid copolymer refers to a resin having structural units derived from styrene compounds and structural units derived from (meth)acrylic acid compounds, wherein the total content of the structural units derived from the aforementioned styrene compounds and the structural units derived from the aforementioned (meth)acrylic acid compounds is preferably 30% by mass or more, and more preferably 50% by mass or more, relative to all structural units of the copolymer.

[0582] Furthermore, the content of structural units derived from styrene compounds relative to all structural units of the aforementioned copolymer is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5% by mass to 80% by mass.

[0583] Furthermore, the content of structural units derived from the above-mentioned (meth)acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass to 95% by mass, relative to all structural units of the above-mentioned copolymer.

[0584] From the viewpoint of achieving better results in this invention, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably has a structural unit containing an aromatic ring structure.

[0585] Examples of monomers that form structural units with aromatic ring structures include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, as well as benzyl methacrylate.

[0586] Among them, styrene compounds are preferred, and styrene is more preferred.

[0587] Furthermore, from the viewpoint of achieving better results in this invention, alkali-soluble resins are more preferably those having the structural unit represented by the following formula (S) (a structural unit derived from styrene).

[0588] [Chemical Formula 4]

[0589]

[0590] In cases where the alkali-soluble resin contains structural units having aromatic ring structures, from the viewpoint of achieving better results in this invention, the content of structural units having aromatic ring structures relative to all structural units of the alkali-soluble resin is preferably 5% to 90% by mass, more preferably 10% to 70% by mass, and even more preferably 20% to 60% by mass.

[0591] Furthermore, from the viewpoint of achieving better results in this invention, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all structural units of the alkali-soluble resin, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 60 mol%.

[0592] Furthermore, from the viewpoint of achieving better results in this invention, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all structural units of the alkali-soluble resin, more preferably 10 mol% to 60 mol%, further preferably 20 mol% to 60 mol%, and especially preferably 20 mol% to 50 mol%.

[0593] Furthermore, in this specification, when the content of "structural unit" is specified in molar ratio, the term "structural unit" has the same meaning as "monomer unit." Also, in this specification, the "monomer unit" can be modified after polymerization through polymer reactions, etc. The same applies below.

[0594] From the viewpoint of achieving better results in this invention, the alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure. That is, the alkali-soluble resin preferably contains structural units having an aliphatic hydrocarbon ring structure. More preferably, the alkali-soluble resin has a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings.

[0595] Examples of rings that constitute aliphatic hydrocarbon ring structures include tricyclic decane rings, cyclohexane rings, cyclopentane rings, norbornane rings, and isoborane rings.

[0596] From the viewpoint of achieving better results in this invention, the ring preferably consists of fused aliphatic hydrocarbon rings of two or more rings, more preferably a tetrahydrodicyclopentadiene ring (tricyclic [5.2.1.0]). 2，6 [decane ring].

[0597] Examples of monomers that form structural units with aliphatic hydrocarbon ring structures include dicyclopentyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.

[0598] Furthermore, from the viewpoint of achieving better results in this invention, the alkali-soluble resin is more preferably having the structural unit represented by the following formula (Cy), and more preferably having the structural unit represented by the above formula (S) and the structural unit represented by the following formula (Cy).

[0599] [Chemical Formula 5]

[0600]

[0601] In equation (Cy), R M R represents a hydrogen atom or a methyl group. Cy This indicates a monovalent group having an aliphatic hydrocarbon ring structure.

[0602] R in equation (Cy) M Methyl is preferred.

[0603] From the viewpoint of achieving better results in this invention, R in formula (Cy) Cy Preferably, it is a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms.

[0604] R of equation (Cy) Cy The aliphatic hydrocarbon ring structure can be either a monocyclic or a polycyclic structure.

[0605] Furthermore, from the viewpoint of achieving superior results in this invention, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in the cyclopentane ring structure is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornene ring structure, or an isoborane ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.

[0606] Furthermore, from the viewpoint of achieving superior effects in this invention, the R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in the sample is preferably a ring structure formed by the fusion of two or more aliphatic hydrocarbon rings, and more preferably a ring structure formed by the fusion of two to four aliphatic hydrocarbon rings.

[0607] Furthermore, from the viewpoint of achieving superior results in this invention, R in formula (Cy) Cy Preferably, the oxygen atom of -C(=O)O- in formula (Cy) is a group that is directly bonded to the aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon cyclic group, more preferably cyclohexyl or dicyclopentyl, and even more preferably dicyclopentyl.

[0608] Alkali-soluble resins can have one structural unit with an aliphatic hydrocarbon ring structure, or they can have two or more structural units.

[0609] In the case where the alkali-soluble resin contains structural units having an aliphatic hydrocarbon ring structure, from the viewpoint of achieving better results in the present invention, the content of structural units having an aliphatic hydrocarbon ring structure is preferably 5% to 90% by mass relative to all structural units of the alkali-soluble resin, more preferably 10% to 80% by mass, and even more preferably 20% to 70% by mass.

[0610] Furthermore, from the viewpoint of achieving better results in this invention, the content of structural units having aliphatic hydrocarbon ring structures in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all structural units of the alkali-soluble resin, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 50 mol%.

[0611] Furthermore, from the viewpoint of achieving better results in this invention, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all structural units of the alkali-soluble resin, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 50 mol%.

[0612] In the case where the alkali-soluble resin contains structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures, from the viewpoint of having better effects in the present invention, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures relative to all structural units of the alkali-soluble resin is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 40% to 75% by mass.

[0613] Furthermore, from the viewpoint of achieving better results in this invention, the total content of structural units having aromatic ring structures and structural units having aliphatic hydrocarbon ring structures in the alkali-soluble resin is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol% relative to all structural units of the alkali-soluble resin.

[0614] Furthermore, from the viewpoint of achieving better results in this invention, the total content of the structural units represented by the above formula (S) and the structural units represented by the above formula (Cy) in the alkali-soluble resin is preferably 10 mol% to 80 mol% relative to all structural units of the alkali-soluble resin, more preferably 20 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol%.

[0615] Furthermore, from the viewpoint of achieving better results in the present invention, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the alkali-soluble resin preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the following formula (SCy-1), and even more preferably satisfy the following formula (SCy-2).

[0616] 0.2≤nS / (nS+nCy)≤0.8 Formula (SCy)

[0617] 0.30≤nS / (nS+nCy)≤0.75 Formula (SCy-1)

[0618] 0.40≤nS / (nS+nCy)≤0.70 Formula (SCy-2)

[0619] From the viewpoint of achieving better results in this invention, the alkali-soluble resin preferably contains structural units having acid groups.

[0620] Examples of acid groups include carboxyl, sulfonyl, phosphonic acid, and phosphate groups, with carboxyl being the most preferred.

[0621] As the above-mentioned structural unit having an acid group, the structural unit derived from (meth)acrylic acid as shown below is preferred, and the structural unit derived from methacrylic acid is more preferred.

[0622] [Chemical Formula 6]

[0623]

[0624] Alkali-soluble resins can have one type of structural unit with an acid group, or they can have two or more types.

[0625] In cases where the alkali-soluble resin contains structural units having acid groups, from the viewpoint of achieving better results in this invention, the content of structural units having acid groups relative to all structural units of the alkali-soluble resin is preferably 5% to 50% by mass, more preferably 5% to 40% by mass, and even more preferably 10% to 30% by mass.

[0626] Furthermore, from the viewpoint of achieving better results in this invention, the content of the structural units having acid groups in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all structural units of the alkali-soluble resin, more preferably 10 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%.

[0627] Furthermore, from the viewpoint of achieving better results in this invention, the content of structural units derived from (meth)acrylic acid in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all structural units of the alkali-soluble resin, more preferably 10 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%.

[0628] From the viewpoint of achieving better results in this invention, alkali-soluble resins preferably have reactive groups, and more preferably contain structural units having reactive groups.

[0629] As a reactive group, a free radical polymerizable group is preferred, and an olefinically unsaturated group is more preferred. Furthermore, when the alkali-soluble resin has an olefinically unsaturated group, the alkali-soluble resin preferably contains structural units having olefinically unsaturated groups in its side chains.

[0630] In this specification, "main chain" refers to the longest connecting chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to the atomic group that branches off from the main chain.

[0631] As an olefinic unsaturated group, allyl or (meth)acryloyloxy is preferred.

[0632] Examples of structural units with reactive groups include the structural units shown below, but are not limited to these.

[0633] [Chemical Formula 7]

[0634]

[0635] Alkali-soluble resins can have one type of structural unit with a reactive group, or they can have two or more types.

[0636] In cases where the alkali-soluble resin contains structural units having reactive groups, from the viewpoint of achieving better results in this invention, the content of structural units having reactive groups relative to all structural units of the alkali-soluble resin is preferably 5% to 70% by mass, more preferably 10% to 50% by mass, and even more preferably 20% to 40% by mass.

[0637] Furthermore, from the viewpoint of achieving better results with the present invention, the content of the structural unit having reactive groups in the alkali-soluble resin is preferably 5 mol% to 70 mol% relative to all structural units of the alkali-soluble resin, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 50 mol%.

[0638] As a method for introducing reactive groups into alkali-soluble resins, one example is to react compounds such as epoxy compounds, terminal isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, hydroxymethyl compounds, and carboxylic anhydrides with functional groups such as hydroxyl, carboxyl, primary amino, secondary amino, acetoacetyl group, and sulfonyl groups.

[0639] As a preferred example of a method for introducing reactive groups into an alkali-soluble resin, a method can be described that after synthesizing a polymer having carboxyl groups through a polymerization reaction, (meth)acryloyloxy groups are introduced into the polymer by reacting glycidyl (meth)acrylate with a portion of the carboxyl groups of the resulting resin through a polymer reaction. This method enables the production of an alkali-soluble resin having (meth)acryloyloxy groups in its side chains.

[0640] The polymerization reaction described above is preferably carried out at a temperature of 70°C to 100°C, and more preferably at a temperature of 80°C to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo initiator is preferred, for example, more preferably V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation. The above polymer reaction is preferably carried out at a temperature of 80°C to 110°C. In the above polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0641] From the viewpoint of achieving better results in this invention, the resin shown below is preferred as an alkali-soluble resin. Furthermore, the content ratios (a to d) and weight-average molecular weight Mw of each structural unit shown below can be appropriately changed according to the intended purpose.

[0642] [Chemical Formula 8]

[0643]

[0644] [Chemical Formula 9]

[0645]

[0646] Furthermore, the alkali-soluble resin may contain polymers comprising structural units having a carboxylic anhydride structure (hereinafter also referred to as "polymer X").

[0647] The carboxylic anhydride structure can be either a chain-like carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but a cyclic carboxylic anhydride structure is preferred.

[0648] The ring in the cyclic carboxylic anhydride structure is preferably a 5-membered to 7-membered ring, more preferably a 5-membered or 6-membered ring, and even more preferably a 5-membered ring.

[0649] The structural unit having a carboxylic anhydride structure is preferably a structural unit in which a divalent group formed by removing two hydrogen atoms from a compound represented by the following formula P-1 is included in the main chain, or a structural unit in which a monovalent group formed by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded directly to the main chain or via a divalent linking group.

[0650] [Chemical Formula 10]

[0651]

[0652] In equation P-1, R A1a Indicates substituent, n 1a R A1a They can be the same or different, Z 1a This indicates a divalent group that forms a ring containing -C(=O)-OC(=O)-, n1a Represents integers greater than or equal to 0.

[0653] As R A1a The substituents represented, for example, include alkyl groups.

[0654] As Z 1a Preferably, it is an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms.

[0655] n 1a Represents integers greater than or equal to 0. In Z... 1a In the case of alkylene groups having 2 to 4 carbon atoms, n 1a Preferably, it is an integer from 0 to 4, more preferably an integer from 0 to 2, and even more preferably 0.

[0656] In n 1a When representing integers greater than 2, there exist multiple R values. A1a They can be the same or different. Furthermore, there can be multiple R values. A1a They can bond together to form a ring, but it is preferable that they do not bond together to form a ring.

[0657] As a structural unit having a carboxylic anhydride structure, it is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, even more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, especially preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

[0658] The following are specific examples of structural units having a carboxylic anhydride structure, but structural units having a carboxylic anhydride structure are not limited to these specific examples. In the structural units described below, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0659] [Chemical Formula 11]

[0660]

[0661] [Chemical Formula 12]

[0662]

[0663] The structural units with carboxylic anhydride structures in polymer X can be a single type or two or more types.

[0664] The total content of structural units having a carboxylic anhydride structure relative to all structural units of polymer X is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and even more preferably 10 mol% to 35 mol%.

[0665] The photosensitive resin layer may contain only one polymer X, or it may contain two or more polymers.

[0666] When the photosensitive resin layer contains polymer X, from the viewpoint of achieving better results in this invention, the content of polymer X relative to the total mass of the photosensitive resin layer is preferably 0.1% to 30% by mass, more preferably 0.2% to 20% by mass, even more preferably 0.5% to 20% by mass, and even more preferably 1% to 20% by mass.

[0667] From the viewpoint of achieving better results in this invention, the weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

[0668] The acid value of the alkali-soluble resin is preferably 10 mg KOH / g to 200 mg KOH / g, more preferably 60 mg KOH / g to 200 mg KOH / g, even more preferably 60 mg KOH / g to 150 mg KOH / g, and especially preferably 60 mg KOH / g to 110 mg KOH / g.

[0669] In addition, the acid value of the alkali-soluble resin is determined according to the method described in JIS K0070:1992.

[0670] The photosensitive resin layer may contain only one type of alkali-soluble resin, or it may contain two or more types.

[0671] From the viewpoint of achieving better results in this invention, the content of alkali-soluble resin relative to the total mass of the photosensitive resin layer is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 30% to 70% by mass.

[0672] <Alkene unsaturated compounds>

[0673] The photosensitive resin layer contains olefinic unsaturated compounds.

[0674] As an olefinic unsaturated group, (meth)acryloyloxy is preferred.

[0675] In addition, the olefinic unsaturated compounds in this specification are compounds other than the alkali-soluble resins mentioned above, and preferably have a molecular weight of less than 5,000.

[0676] Furthermore, as a preferred embodiment of the olefin unsaturated compound used in the second embodiment, the preferred embodiment of the olefin unsaturated compound used in the first embodiment described above can be cited.

[0677] One of the preferred methods for olefinic unsaturated compounds is the compound represented by the following formula (M) (also simply referred to as "compound M").

[0678] Q 2 -R 1 -Q 1 Formula (M)

[0679] In formula (M), Q 1 and Q 2 Each independently represents (meth)acryloyloxy, R 1 This indicates a divalent linker group with a chain-like structure.

[0680] Regarding Q in equation (M) 1 and Q 2 From the viewpoint of ease of synthesis, it is preferable to use the same functional groups.

[0681] Furthermore, from a reactivity perspective, Q in equation (M) 1 and Q 2 Acryloyloxy is preferred.

[0682] As R in equation (M) 1 From the viewpoint of achieving better results in this invention, alkylene or alkoxyalkylene (-L) is preferred. 1 -OL 1 -) or polyalkoxyalkylene (-(L 1 -O) p -L 1 -), more preferably a hydrocarbon group or a polyalkoxyalkylene group having 2 to 20 carbon atoms, even more preferably an alkylene group having 4 to 20 carbon atoms, and especially preferably a straight-chain alkylene group having 6 to 18 carbon atoms.

[0683] The aforementioned hydrocarbon group only needs to have a chain structure in at least a portion. There are no particular restrictions on the portion other than the aforementioned chain structure. For example, it can be any one of branched, cyclic, or straight-chain alkylene, aryl, ether bond, and combinations thereof with 1 to 5 carbon atoms. Preferably, it is an alkylene group or a group formed by combining 2 or more alkylene groups and 1 or more aryl groups. More preferably, it is an alkylene group, and even more preferably, it is a straight-chain alkylene group.

[0684] In addition, the above L 1 Each alkylene group is represented independently, preferably ethylene, propylene, or butylene, more preferably ethylene or 1,2-propylene.

[0685] p represents an integer greater than 2, preferably an integer between 2 and 10.

[0686] Furthermore, from the viewpoint of achieving superior effects in this invention, the linker Q in compound M...1 With Q 2 The shortest linking chain between atoms preferably has 3 to 50 atoms, more preferably 4 to 40 atoms, even more preferably 6 to 20 atoms, and particularly preferably 8 to 12 atoms.

[0687] In this specification, "Connect Q" 1 With Q 2 The number of atoms in the shortest link chain between Q and Q is the number of atoms in the link chain. 1 Linked R 1 Atoms in Q 2 Linked R 1 The shortest number of atoms in the atom.

[0688] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. These ester monomers can also be used as mixtures.

[0689] Among the above-mentioned compounds, from the viewpoint of achieving better effects in this invention, it is preferable to select at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate, more preferably at least one compound selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate, and even more preferably at least one compound selected from 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

[0690] Furthermore, as one of the preferred methods for olefin unsaturated compounds, olefin unsaturated compounds with more than two functions can be cited.

[0691] In this specification, "a 2 or more functional olefin unsaturated compound" refers to a compound having two or more olefin unsaturated groups in one molecule.

[0692] As an olefinic unsaturated group in an olefinic unsaturated compound, (meth)acryloyl group is preferred.

[0693] As an olefinic unsaturated compound, (meth)acrylate compounds are preferred.

[0694] As a difunctional olefinic unsaturated compound, there are no particular restrictions, and it is possible to appropriately select from known compounds.

[0695] Examples of difunctional olefinic unsaturated compounds other than compound M mentioned above include tricyclodecanediethanol di(meth)acrylate and tricyclodecanediethanol di(meth)acrylate.

[0696] Examples of commercially available difunctional olefinic unsaturated compounds include tricyclodecanediethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0697] As an olefinic unsaturated compound with more than three functions, there are no particular restrictions, and it is possible to appropriately select from known compounds.

[0698] Examples of olefinic unsaturated compounds with more than three functions include pentaerythritol (tris / tetra / penta / hexa)methacrylate, pentaerythritol (tris / tetra)methacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and glycerol tri(meth)acrylate skeletons.

[0699] 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.

[0700] Examples of olefinically 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.), epoxy-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.), and ethoxylated glycerol triacrylates (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0701] Other examples of olefinic unsaturated compounds include urethane (meth)acrylate compounds.

[0702] Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.

[0703] Furthermore, examples of urethane (meth)acrylates include those with 3 or more functional groups. As a lower limit for the number of functional groups, 6 or more functional groups are more preferred, and 8 or more functional groups are even more preferred. Additionally, as an upper limit for the number of functional groups, 20 or fewer functional groups are preferred. Examples of urethane (meth)acrylates with three or more functions include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., as well as UA-306H, UA-306T, UA-306I, UA-51OH and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0704] One preferred approach for olefinic unsaturated compounds is to olefinic unsaturated compounds having an acid group.

[0705] Examples of acid groups include phosphate, sulfonate, and carboxyl groups.

[0706] Among these, the carboxyl group is preferred as an acid group.

[0707] Examples of olefinic unsaturated compounds with acid groups include trifunctional to quadrifunctional olefinic unsaturated compounds with acid groups (olefinic unsaturated compounds with carboxyl groups introduced into the pentaerythritol tri- and tetraacrylate (PETA) backbone (acid value: 80 mg KOH / g to 120 mg KOH / g)) and pentafunctional to hexafunctional olefinic unsaturated compounds with acid groups (olefinic unsaturated compounds with carboxyl groups introduced into the dipentaerythritol penta- and hexaacrylate (DPHA) backbone (acid value: 25 mg KOH / g to 70 mg KOH / g)).

[0708] These trifunctional or more olefinic unsaturated compounds with acid groups can be used in combination with difunctional olefinic unsaturated compounds with acid groups as needed.

[0709] As an olefinic unsaturated compound having an acid group, it is preferably selected from at least one of olefinic unsaturated compounds having a carboxyl group and a carboxylic anhydride thereof.

[0710] If the olefinic unsaturated compound with an acidic group is selected from at least one of olefinic unsaturated compounds with two or more functions having a carboxyl group and their carboxylic anhydrides, the reproducibility and film strength are further improved.

[0711] There are no particular restrictions on olefinic unsaturated compounds with more than two functions having a carboxyl group; appropriate selection can be made from known compounds.

[0712] Examples of olefinic unsaturated compounds with more than two functions, including a carboxyl group, include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

[0713] As an olefinic unsaturated compound having an acid group, the preferred polymeric compound having an acid group is the one described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942, the contents of which are incorporated herein by reference.

[0714] Examples of olefinically unsaturated compounds include, for instance, compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols, compounds obtained by reacting α,β-unsaturated carboxylic acids with compounds containing glycidyl groups, urethane monomers such as (meth)acrylate compounds having urethane bonds, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, as well as alkyl (meth)acrylates.

[0715] These can be used individually or in combination of two or more.

[0716] Examples of compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols include, for example, bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate with 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate with 2 to 14 propylene oxide groups; and polyethylene glycol di(meth)acrylate with 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. (Meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane)tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0717] Preferably, the compounds are olefinic unsaturated compounds having a tetrahydroxymethylmethane structure or a trihydroxymethylpropane structure, and more preferably tetrahydroxymethylmethane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate or di(trihydroxymethylpropane)tetraacrylate.

[0718] Examples of olefinically unsaturated compounds include caprolactone-modified olefinically unsaturated compounds (e.g., KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), epoxide-modified olefinically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL 135 manufactured by DAICEL-ALLNEX LTD., etc.), and ethoxylated glycerol triacrylates (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0719] From the viewpoint of excellent developability of the photosensitive resin layer after transfer, olefinic unsaturated compounds containing ester bonds are preferred as olefinic unsaturated compounds.

[0720] As an olefinic unsaturated compound containing an ester bond, there are no particular limitations as long as the ester bond is contained within the molecule. However, from the viewpoint of superior effect in the present invention, olefinic unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate are more preferred.

[0721] From the viewpoint of imparting reliability, olefinic unsaturated compounds containing aliphatic groups having 6 to 20 carbon atoms and the aforementioned olefinic unsaturated compounds having a tetrahydroxymethylmethane structure or a trihydroxymethylpropane structure are preferred as olefinic unsaturated compounds.

[0722] Examples of olefinic unsaturated compounds with an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecanediethanol di(meth)acrylate.

[0723] As one of the preferred methods for olefin unsaturated compounds, olefin unsaturated compounds having an aliphatic hydrocarbon ring structure (preferably 2-functional olefin unsaturated compounds) can be cited.

[0724] As the above-mentioned olefinic unsaturated compounds, preferably are olefinic unsaturated compounds having a ring structure with fused aliphatic hydrocarbon rings of two or more rings (preferably structures selected from tricyclodecane and tricyclodecene structures), more preferably are difunctional olefinic unsaturated compounds having a ring structure with fused aliphatic hydrocarbon rings of two or more rings, and even more preferably are tricyclodecanediethanol di(meth)acrylate.

[0725] From the viewpoint of achieving better results in this invention, the preferred aliphatic hydrocarbon ring structures are cyclopentane, cyclohexane, tricyclodecane, tricyclodecene, norcamphene, or isoborane.

[0726] The molecular weight of the olefinic unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, and especially preferably 300 to 2,200.

[0727] The proportion of olefinic unsaturated compounds with a molecular weight of 300 or less among the olefinic unsaturated compounds contained in the photosensitive resin layer is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, relative to the total content of all olefinic unsaturated compounds contained in the photosensitive resin layer.

[0728] As one of the preferred methods for a photosensitive resin layer, the photosensitive resin layer preferably contains olefin unsaturated compounds with two or more functions, more preferably contains olefin unsaturated compounds with three or more functions, and even more preferably contains olefin unsaturated compounds with three or four functions.

[0729] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably comprises a difunctional olefinic unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin comprising structural units having an aliphatic hydrocarbon ring.

[0730] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably includes compounds represented by formula (M) and olefinic unsaturated compounds having acid groups, more preferably including 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate and polyfunctional olefinic unsaturated compounds having carboxylic acid groups, and even more preferably a succinic acid modified form including 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate and dipentaerythritol pentaacrylate.

[0731] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably includes the compound represented by formula (M), an olefinic unsaturated compound having an acid group, and a thermally crosslinking compound described later, and more preferably includes the compound represented by formula (M), an olefinic unsaturated compound having an acid group, and a capped isocyanate compound described later.

[0732] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a difunctional olefin unsaturated compound (preferably a difunctional (meth)acrylate compound) or a trifunctional or higher olefin unsaturated compound (preferably a trifunctional or higher (meth)acrylate compound).

[0733] Furthermore, as one of the preferred methods for the photosensitive resin layer, from the viewpoint of rust prevention, the photosensitive resin layer preferably contains compound M and a difunctional olefinic unsaturated compound having an aliphatic hydrocarbon ring structure.

[0734] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive resin layer preferably comprises compound M and an olefin unsaturated compound having an acid group; more preferably, it comprises compound M, a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, and an olefin unsaturated compound having an acid group; even more preferably, it comprises compound M, a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher olefin unsaturated compound, and an olefin unsaturated compound having an acid group; and especially preferably, it comprises compound M, a difunctional olefin unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher olefin unsaturated compound, an olefin unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

[0735] Furthermore, as one of the preferred embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention, the photosensitive resin layer preferably comprises 1,9-nonanediol diacrylate and a polyfunctional olefin unsaturated compound having a carboxylic acid group; more preferably, it comprises 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, and a polyfunctional olefin unsaturated compound having a carboxylic acid group; even more preferably, it comprises 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and an olefin unsaturated compound having a carboxylic acid group; and particularly preferably, it comprises 1,9-nonanediol diacrylate, tricyclodecanediethanol diacrylate, an olefin unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0736] The photosensitive resin layer may contain monofunctional olefin unsaturated compounds as olefin unsaturated compounds.

[0737] The content of the olefinic unsaturated compounds with more than two functions in the above-mentioned olefinic unsaturated compounds is preferably 60% to 100% by mass relative to the total content of all olefinic unsaturated compounds contained in the photosensitive resin layer, more preferably 80% to 100% by mass, and even more preferably 90% to 100% by mass.

[0738] Alkenes can be used alone or in combination with two or more.

[0739] The content of olefinic unsaturated compounds in the photosensitive resin layer relative to the total mass of the photosensitive resin layer is preferably 1% to 70% by mass, more preferably 5% to 70% by mass, even more preferably 5% to 60% by mass, and particularly preferably 5% to 50% by mass.

[0740] Photopolymerization initiators

[0741] The photosensitive resin layer contains a photopolymerization initiator.

[0742] As a preferred embodiment of the photopolymerization initiator used in the second embodiment, the preferred embodiment of the photopolymerization initiator used in the first embodiment described above can be cited.

[0743] Photopolymerization initiators can be used alone or in combination with two or more.

[0744] The content of the photopolymerization initiator relative to the total mass of the photosensitive resin layer 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. Furthermore, as an upper limit, it is preferably 10% by mass or less relative to the total mass of the photosensitive resin layer, more preferably 5% by mass or less.

[0745] <Heterocyclic compounds>

[0746] The photosensitive resin layer may contain heterocyclic compounds.

[0747] Heterocyclic compounds can have any heterocyclic ring, whether it is a monocyclic or polycyclic heterocyclic ring.

[0748] Examples of heteroatoms in heterocyclic compounds include nitrogen, oxygen, and sulfur atoms. Heterocyclic compounds preferably have at least one atom selected from nitrogen, oxygen, and sulfur atoms, and more preferably have a nitrogen atom.

[0749] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0750] In the above, the heterocyclic compound is preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably selected from at least one compound selected from triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0751] Preferred examples of heterocyclic compounds are shown below. The following compounds can be cited as examples of triazole and benzotriazole compounds.

[0752] [Chemical Formula 13]

[0753]

[0754] [Chemical Formula 14]

[0755]

[0756] The following compounds can be cited as examples of tetrazolium compounds.

[0757] [Chemical Formula 15]

[0758]

[0759] [Chemical Formula 16]

[0760]

[0761] The following compounds can be cited as examples of thiadiazole compounds.

[0762] [Chemical Formula 17]

[0763]

[0764] The following compounds can be cited as examples of triazine compounds.

[0765] [Chemical Formula 18]

[0766]

[0767] The following compounds can be cited as examples of rhodanine compounds.

[0768] [Chemical Formula 19]

[0769]

[0770] The following compounds can be cited as examples of thiazole compounds.

[0771] [Chemical Formula 20]

[0772]

[0773] The following compounds can be cited as examples of benzothiazole compounds.

[0774] [Chemical Formula 21]

[0775]

[0776] The following compounds can be cited as examples of benzimidazole compounds.

[0777] [Chemical Formula 22]

[0778]

[0779] [Chemical Formula 23]

[0780]

[0781] The following compounds can be cited as examples of benzoxazole compounds.

[0782] [Chemical Formula 24]

[0783]

[0784] Heterocyclic compounds can be used alone or in combination with two or more.

[0785] When the photosensitive resin layer contains heterocyclic compounds, the content of the heterocyclic compounds relative to the total mass of the photosensitive resin layer is preferably 0.01% to 20.0% by mass, more preferably 0.10% to 10.0% by mass, even more preferably 0.30% to 8.0% by mass, and particularly preferably 0.50% to 5.0% by mass.

[0786] <Aliphatic thiols>

[0787] The photosensitive resin layer may contain aliphatic thiol compounds.

[0788] By including aliphatic thiol compounds in the photosensitive resin layer, an olefin-thiol reaction occurs between the aliphatic thiol compounds and olefin unsaturated compounds, thereby suppressing the curing shrinkage of the resulting film and relaxing the stress.

[0789] As aliphatic thiols, monofunctional aliphatic thiols or polyfunctional aliphatic thiols (i.e., aliphatic thiols with two or more functions) are preferred.

[0790] Of the above, from the viewpoint of the adhesion of the formed pattern (especially the adhesion after exposure), a multifunctional aliphatic thiol compound is more preferred as an aliphatic thiol compound.

[0791] In this specification, "multifunctional aliphatic thiols" refers to aliphatic compounds having two or more thiol groups (also called "mercapto groups") within their molecules.

[0792] As a multifunctional aliphatic thiol compound, a low molecular weight compound with a molecular weight of 100 or more is preferred. Specifically, the molecular weight of the multifunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0793] The number of functional groups in a multifunctional aliphatic thiol compound is preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and even more preferably 2 to 6 functional groups, from the viewpoint of the tightness of the formed pattern.

[0794] Examples of multifunctional aliphatic thiols include, for instance, trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetra(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, and trimethylolpropane tris(3-mercaptobutyrate). (3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

[0795] In the above, the multifunctional aliphatic thiol compound is preferably selected from at least one compound selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0796] Examples of monofunctional aliphatic thiols include, for example, 1-octylthiol, 1-dodecylthiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and octadecyl-3-mercaptopropionate.

[0797] The photosensitive resin layer may contain a single aliphatic thiol compound or two or more aliphatic thiol compounds.

[0798] When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound relative to the total mass of the photosensitive resin layer is preferably 5% by mass or more, more preferably 5% to 50% by mass, even more preferably 5% to 30% by mass, and particularly preferably 8% to 20% by mass.

[0799] <Thermocrosslinking compounds>

[0800] From the viewpoint of the strength of the cured film and the adhesion of the uncured film, the photosensitive resin layer preferably contains a thermally crosslinking compound.

[0801] The thermal crosslinking compound used in the photosensitive resin layer of the second embodiment is preferably the same thermal crosslinking compound used in the photosensitive resin layer of the first embodiment.

[0802] A single thermally crosslinking compound can be used alone, or two or more can be used together.

[0803] When the photosensitive resin layer contains a thermally crosslinking compound, the content of the thermally crosslinking compound relative to the total mass of the photosensitive resin layer is preferably 1% to 50% by mass, more preferably 5% to 30% by mass.

[0804] <surfactants>

[0805] The photosensitive resin layer may contain surfactants.

[0806] The surfactant used in the photosensitive resin layer of the second embodiment is preferably the surfactant described above in the photosensitive resin layer of the first embodiment.

[0807] Surfactants can be used alone or in combination with two or more.

[0808] When the photosensitive resin layer contains a surfactant, the surfactant content relative to the total mass of the photosensitive resin layer is preferably 0.01% to 3.0% by mass, more preferably 0.01% to 1.0% by mass, and even more preferably 0.05% to 0.80% by mass.

[0809] <Polymerization inhibitors>

[0810] The photosensitive resin layer may contain a polymerization inhibitor.

[0811] A polymerization inhibitor is a compound that has the function of delaying or inhibiting a polymerization reaction. For example, known compounds that are used as polymerization inhibitors can be used as such.

[0812] Examples of polymerization inhibitors include phenothiazine compounds such as bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurothio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine and... Hindered phenolic compounds such as pentaerythritol tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxyamine and N-nitrosophenylhydroxyamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and tert-butylcatechol; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate.

[0813] From the viewpoint of achieving better results in this invention, the polymerization inhibitor is preferably selected from at least one of phenothiazine compounds, nitroso compounds or their salts, and hindered phenolic compounds, more preferably phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurothio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxyamine aluminum salt.

[0814] A single polymerization inhibitor can be used alone, or two or more can be used in combination.

[0815] When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total mass of the photosensitive resin layer is preferably 0.01% to 10.0% by mass, more preferably 0.01% to 5.0% by mass, and even more preferably 0.04% to 3.0% by mass.

[0816] <Hydrogen-donating compounds>

[0817] The photosensitive resin layer may contain hydrogen-donating compounds.

[0818] Hydrogen-donating compounds can further enhance the sensitivity of photopolymerization initiators to active light and inhibit the polymerization hindrance of olefinic unsaturated compounds caused by oxygen.

[0819] Examples of hydrogen-donating compounds include, for example, amines and amino acid compounds.

[0820] Examples of amines include compounds described in, for instance, the Journal of Polymer Society, Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-020189, Japanese Patent Application Publication No. 51-082102, Japanese Patent Application Publication No. 52-134692, Japanese Patent Application Publication No. 59-138205, Japanese Patent Application Publication No. 60-084305, Japanese Patent Application Publication No. 62-018537, Japanese Patent Application Publication No. 64-033104, and Research Disclosure No. 33825. More specifically, examples include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0821] From the viewpoint of achieving better results in this invention, the amine is preferably selected from at least one of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0822] Examples of amino acid compounds include, for example, N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0823] From the viewpoint of achieving better results in this invention, N-phenylglycine is preferred as the amino acid compound.

[0824] Furthermore, examples of hydrogen-donating compounds include, for instance, organometallic compounds (such as tributyltin acetate) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds (such as trithianes) described in Japanese Patent Application Publication No. 6-308727.

[0825] Hydrogen-donating compounds can be used alone or in combination with two or more.

[0826] When the photosensitive resin layer contains a hydrogen-donating compound, from the viewpoint of improving the curing speed by balancing the polymerization growth rate and chain transfer, the content of the hydrogen-donating compound relative to the total mass of the photosensitive resin layer is preferably 0.01% to 10.0% by mass, more preferably 0.01% to 8.0% by mass, and even more preferably 0.03% to 5.0% by mass.

[0827] <Impurities, etc.>

[0828] The photosensitive resin layer may contain a specified amount of impurities.

[0829] The impurities in the photosensitive resin layer of the second embodiment are the same as those in the photosensitive resin layer of the first embodiment.

[0830] <Residual Monomer>

[0831] The photosensitive resin layer sometimes contains residual monomers corresponding to the structural units of the aforementioned alkali-soluble resin.

[0832] The preferred manner for residual monomers corresponding to each structural unit of the alkali-soluble resin in the photosensitive resin layer of the second embodiment is the same as that for residual monomers corresponding to each structural unit of the alkali-soluble resin in the photosensitive resin layer of the first embodiment.

[0833] <Other Ingredients>

[0834] The photosensitive resin layer may contain components other than those already described (hereinafter also referred to as "other components"). Examples of other components include, for example, colorants, antioxidants, and particles (e.g., metal oxide particles). Furthermore, examples of other components include other additives described in paragraphs 0058 to 0071 of Japanese Patent Application Publication No. 2000-310706.

[0835] -particle-

[0836] As particles, metal oxide particles are preferred.

[0837] The metals in the metal oxide particles also include half-metals such as B, Si, Ge, As, Sb, and Te.

[0838] For example, from the viewpoint of the transparency of the cured film, the average primary particle size is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm.

[0839] The average first-order particle size was calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Additionally, in cases where the particle shape is not spherical, the longest side was used as the particle size.

[0840] When the photosensitive resin layer contains particles, it may contain only one type of metal and different particles of different sizes, or it may contain two or more types.

[0841] Preferably, the photosensitive resin layer does not contain particles, or if the photosensitive resin layer contains particles, the particle content is more than 0% by mass and less than 35% by mass relative to the total mass of the photosensitive resin layer. More preferably, it does not contain particles or the particle content is more than 0% by mass and less than 10% by mass relative to the total mass of the photosensitive resin layer. Even more preferably, it does not contain particles or the particle content is more than 0% by mass and less than 5% by mass relative to the total mass of the photosensitive resin layer. Even more preferably, it does not contain particles or the particle content is more than 0% by mass and less than 1% by mass relative to the total mass of the photosensitive resin layer. Particularly preferably, it does not contain particles.

[0842] -Coloring agents-

[0843] The photosensitive resin layer may contain colorants (pigments, dyes, etc.), but from the point of view of transparency, it is preferable that it does not contain colorants in substance.

[0844] When the photosensitive resin layer contains a colorant, the content of the colorant relative to the total mass of the photosensitive resin layer is preferably less than 1% by mass, more preferably less than 0.1% by mass.

[0845] -Antioxidants-

[0846] As antioxidants, examples include 3-pyrazolone derivatives such as 1-phenyl-3-pyrazolone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; and p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0847] From the viewpoint of achieving better results in this invention, 3-pyrazolones are preferred as antioxidants, and 1-phenyl-3-pyrazolones are more preferred.

[0848] When the photosensitive resin layer contains an antioxidant, the antioxidant content relative to the total mass of the photosensitive resin layer is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more. There is no particular limitation on the upper limit, but it is preferably 1% by mass or less.

[0849] <Thickness of the photosensitive resin layer>

[0850] There is no particular limitation on the thickness of the photosensitive resin layer, but it is often below 30 μm. From the viewpoint of achieving better results in this invention, it is preferable to be below 20 μm, more preferably below 15 μm, even more preferably below 10 μm, and especially preferably below 5.0 μm. As a lower limit, from the viewpoint of achieving excellent strength of the film obtained by curing the photosensitive resin layer, it is preferable to be 0.60 μm or more, more preferably 1.5 μm or more.

[0851] The thickness of the photosensitive resin layer can be calculated, for example, as the average of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0852] <Refractive index of the photosensitive resin layer>

[0853] The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[0854] <Color of the photosensitive resin layer>

[0855] The photosensitive resin layer is preferably colorless. Specifically, total internal reflection (8° incident angle, light source: D-65 (2° field of view)) meets CIE1976 (L * a * b * In the color space, L * The preferred value is 10 to 90, a * The preferred value is -1.0 to 1.0, b * The preferred value is -1.0 to 1.0.

[0856] Furthermore, the pattern obtained by curing the photosensitive resin layer (the cured film of the photosensitive resin layer) is preferably colorless.

[0857] Specifically, total internal reflection (8° incident angle, light source: D-65 (2° field of view)) is defined in CIE 1976 (L... * a * b * In the color space, the L of the pattern * The preferred value is 10 to 90, and the a value of the pattern is... * The preferred value is -1.0 to 1.0, and the b value of the pattern is... * The preferred value is -1.0 to 1.0.

[0858] [Refractive index adjustment layer]

[0859] The photosensitive transfer material preferably has a refractive index adjustment layer.

[0860] As a refractive index adjusting layer, known refractive index adjusting layers can be used. Examples of materials included in the refractive index adjusting layer include alkali-soluble resins, olefinic unsaturated compounds, metal salts, and particles.

[0861] There are no particular limitations on the methods for controlling the refractive index of the refractive index adjustment layer. For example, methods such as using a resin with a specified refractive index alone, using a resin and particles, and using a composite of a metal salt and a resin can be cited.

[0862] Examples of alkali-soluble resins and olefinic unsaturated compounds include those described in the section on "photosensitive resin layer" above.

[0863] As particles, examples include metal oxide particles and metal particles.

[0864] There are no particular restrictions on the types of metal oxide particles; any well-known metal oxide particles can be cited. Metals in metal oxide particles also include half-metals such as B, Si, Ge, As, Sb, and Te.

[0865] For example, from the viewpoint of the transparency of the cured film, the average primary particle size is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm.

[0866] The average first-order particle size was calculated by measuring the particle size of any 200 particles using an electron microscope and then arithmetically averaging the results. Additionally, in cases where the particle shape is not spherical, the longest side was used as the particle size.

[0867] As a metal oxide particle, it is preferably selected from at least one of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof.

[0868] Among these, metal oxide particles, for example, from the viewpoint of easy adjustment of refractive index, are more preferably selected from at least one of zirconium oxide particles and titanium oxide particles.

[0869] Commercially available metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (NanoUse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconia particles (NanoUse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0870] One type of particle can be used alone, or two or more types can be used together.

[0871] The particle content in the refractive index adjustment layer relative to the total mass of the refractive index adjustment layer is preferably 1% to 95% by mass, more preferably 20% to 90% by mass, and even more preferably 40% to 85% by mass.

[0872] When titanium oxide is used as the metal oxide particle, the content of titanium oxide particles relative to the total mass of the refractive index adjustment layer is preferably 1% to 95% by mass, more preferably 20% to 90% by mass, and even more preferably 40% to 85% by mass.

[0873] The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive resin layer.

[0874] The refractive index of the refractive index adjustment layer is preferably 1.50 or higher, more preferably 1.55 or higher, even more preferably 1.60 or higher, and especially preferably 1.65 or higher. Regarding the upper limit of the refractive index of the refractive index adjustment layer, it is preferably 2.10 or lower, more preferably 1.85 or lower, even more preferably 1.78 or lower, and especially preferably 1.74 or lower.

[0875] The thickness of the refractive index adjustment layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.

[0876] <Method for manufacturing photosensitive transfer material according to the second embodiment>

[0877] There are no particular limitations on the method for manufacturing the photosensitive transfer material of the second embodiment, and known methods can be used.

[0878] As Figure 2 The manufacturing method of the photosensitive transfer material 10 shown may include, for example, a method comprising the following steps: coating a photosensitive resin composition onto the surface of a temporary support 1 to form a coating film, further drying the coating film to form a photosensitive resin layer 3; and coating a refractive index adjusting layer forming composition onto the surface of the photosensitive resin layer 3 to form a coating film, further drying the coating film to form a refractive index adjusting layer 5.

[0879] A protective film 7 is pressed onto the refractive index adjustment layer 5 of the laminate manufactured by the above manufacturing method, thereby manufacturing a photosensitive transfer material 10.

[0880] The method for manufacturing a photosensitive transfer material according to the first embodiment preferably involves manufacturing a photosensitive transfer material 10 having a temporary support 1, a photosensitive resin layer 3, a refractive index adjustment layer 5, and a protective film 7 by a process including setting a protective film 7 in such a way that the surface of the refractive index adjustment layer 5 is in contact with the side opposite to the side having the temporary support 1.

[0881] After manufacturing the photosensitive transfer material 10 using the above-described manufacturing method, the photosensitive transfer material 10 can be wound up to produce and store 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.

[0882] Furthermore, as a method for manufacturing the aforementioned photosensitive transfer material 10, it can be a method of forming a photosensitive resin layer 3 on the surface of the refractive index adjustment layer 5 after forming a refractive index adjustment layer 5 on the protective film 7.

[0883] Furthermore, as a method for manufacturing the aforementioned photosensitive transfer material 10, it can be formed by forming a photosensitive resin layer 3 on a temporary support 1, forming a refractive index adjustment layer 5 on a protective film 7, and bonding the photosensitive resin layer 3 and the refractive index adjustment layer 5 together.

[0884] The method for forming the photosensitive resin composition and photosensitive resin layer in the second embodiment is the same as the method for forming the photosensitive resin composition and photosensitive resin layer described in the first embodiment, and the preferred method is also the same.

[0885] <Composition for forming a refractive index adjusting layer and method for forming a refractive index adjusting layer>

[0886] The composition for forming the refractive index adjustment layer preferably includes various components and solvents used to form the aforementioned refractive index adjustment layer. Furthermore, in the composition for forming the refractive index adjustment layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjustment layer.

[0887] As a solvent, there are no particular limitations as long as it can dissolve or disperse the components contained in the refractive index adjustment layer. It is preferred to be selected from at least one of water and water-mixed organic solvents, and more preferably water or a mixture of water and water-mixed organic solvents.

[0888] Examples of water-mixable organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, with alcohols with 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

[0889] One solvent can be used alone, or two or more solvents can be used.

[0890] The solvent content is preferably 50 to 2,500 parts by mass relative to 100 parts by mass of the total solids of the composition, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass.

[0891] Regarding the method for forming the refractive index adjustment layer, there are no particular limitations as long as the method can form a layer containing the above-mentioned components. For example, well-known coating methods (slit coating, spin coating, curtain coating, and inkjet coating, etc.) can be cited.

[0892] Furthermore, by attaching the protective film to the refractive index adjustment layer, the photosensitive transfer material of the second embodiment can be manufactured.

[0893] There are no particular restrictions on the method of attaching the protective film to the refractive index adjustment layer; any well-known method can be cited.

[0894] As a device for attaching a protective film to a refractive index adjustment layer, known laminators such as vacuum laminators and automatic cutting laminators can be cited.

[0895] The laminator preferably has any heatable rollers such as rubber rollers, and is capable of applying pressure and heating.

[0896] (Methods for manufacturing resin patterns and laminates)

[0897] The resin pattern manufacturing method of the present invention is a method for forming a resin pattern on a substrate using a photosensitive transfer material having a temporary support and a photosensitive resin layer.

[0898] As a method for manufacturing a resin pattern, a preferred method includes the following steps in sequence: a step of bonding the outermost layer of the photosensitive transfer material according to the present invention, on the side having the photosensitive resin layer relative to the temporary support, to a substrate (hereinafter also referred to as the "bonding step"); a step of exposing the photosensitive resin layer to a pattern (hereinafter also referred to as the "exposure step"); and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter also referred to as the "development step").

[0899] Furthermore, regarding the method for manufacturing resin patterns according to the present invention, from the viewpoint of further maximizing the effects of the present invention, it is preferable that at least a portion of the resin pattern includes line and space patterns, more preferably that at least a portion of the resin pattern includes line and space patterns, and the total width of at least one group of lines and spaces in the line and space patterns is 20 μm or less.

[0900] 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.

[0901] As a method for manufacturing a laminate, a method that sequentially includes the above-described protective film peeling process, the above-described lamination process, the above-described exposure process, and the above-described development process is preferred.

[0902] <Lamination Process>

[0903] The method for manufacturing resin patterns or laminates preferably includes a bonding process.

[0904] In the bonding process, it is preferable to bring the outermost layer of the photosensitive transfer material, on the side having the photosensitive resin layer relative to the temporary support, into contact with the substrate (or, if a conductive layer is provided on the surface of the substrate), thereby pressing the photosensitive transfer material onto the substrate. If this is done, the adhesion between the outermost layer of the photosensitive transfer material, on the side having the photosensitive resin layer relative to the temporary support, and the substrate will be improved. Therefore, it can be preferably used as an etch resist when etching the conductive layer of the photosensitive resin layer formed after exposure and development.

[0905] In addition, if the photosensitive transfer material has a protective film, the protective film can be removed from the surface of the photosensitive resin layer before lamination.

[0906] 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 resin layer that does not face the temporary support, then the side of the photosensitive resin layer that does not have the temporary support is bonded to the substrate through this layer.

[0907] 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.

[0908] 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 resin 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.

[0909] There are no particular limitations on the lamination temperature; for example, 70°C to 130°C is preferred.

[0910] Regarding the manufacturing method of the resin pattern including the bonding process and the manufacturing method of the circuit wiring, it is preferable to carry out them by roll-to-roll method.

[0911] The following explains the roll-to-roll method.

[0912] The term "roll-to-roll" refers to a method in which a roll-to-roll substrate is used as the substrate, and a process of rolling out the substrate or a structure containing the substrate is included before any step in the resin pattern manufacturing method or the circuit wiring manufacturing method (also called a "roll-out process"), and a process of winding the substrate or a structure containing the substrate is included after any step (also called a "wind-up process"), and at least one step (preferably all steps, or all steps except the heating step) is performed while the substrate or the structure containing the substrate is being transported.

[0913] 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.

[0914] <Substrate>

[0915] As the substrate used in the method for manufacturing the resin pattern or the method for manufacturing the laminate involved in 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.

[0916] The substrate can have any layer other than the conductive layer, as needed.

[0917] Examples of substrates include resin substrates, glass substrates, and semiconductor substrates.

[0918] 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.

[0919] Examples of substrates that form a substrate include glass, silicon, and films.

[0920] 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.

[0921] Furthermore, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

[0922] 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.

[0923] 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.

[0924] 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.

[0925] As a conductive layer in a substrate, examples include the conductive layers used in typical circuit wiring or touch panel wiring.

[0926] From the viewpoint of conductivity and fine line formation, the conductive layer is preferably selected from at least one layer selected from metal layers, conductive metal oxide layers, graphene layers, carbon nanotube layers and conductive polymer layers, more preferably metal layers, and even more preferably copper or silver layers.

[0927] 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.

[0928] Materials that can be used as conductive layers include metals and conductive metal oxides.

[0929] Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0930] Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO2.

[0931] 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.

[0932] 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.

[0933] 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.

[0934] 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.

[0935] 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 be preferably used as a substrate for a touch panel.

[0936] 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.

[0937] 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.

[0938] Metal is the preferred material for circuitous wiring.

[0939] 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.

[0940] 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.

[0941] <Exposure Process>

[0942] The method for manufacturing the resin pattern or the method for manufacturing the laminate preferably includes a process of exposing the photosensitive resin layer to the pattern (exposure process) after the above-mentioned bonding process.

[0943] In addition, "pattern exposure" here refers to exposure in a patterned manner, that is, exposure in a manner that has exposed and unexposed areas.

[0944] There are no particular restrictions on the positional relationship between the exposed and unexposed areas in the pattern exposure; it can be adjusted appropriately.

[0945] 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 a circuit wiring manufacturing 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 portion of the lead wiring 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.

[0946] Regarding the light source used in the exposure, any light source that illuminates the photosensitive resin layer at a wavelength capable of exposing the light (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).

[0947] The preferred exposure level is 5 mJ / cm². 2 ~200mJ / cm 2 More preferably 10 mJ / cm 2 ~100mJ / cm 2 .

[0948] 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.

[0949] In the exposure process, pattern exposure can be performed after the temporary support is peeled off from the photosensitive resin 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 resin 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 resin layer and the mask, and to avoid the influence of foreign matter adhering 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 resin layer can be directly drawn, or the photosensitive resin 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, and even with a liquid such as water between the light source and the photosensitive resin layer.

[0950] <Stripping Process>

[0951] The method for manufacturing resin patterns or laminates can be between the bonding process and the exposure process or between the exposure process and the development process, including a peeling process for removing temporary supports.

[0952] 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.

[0953] <Developing Process>

[0954] In the method for manufacturing resin patterns, it is preferable to include a step (development step) after the above-mentioned exposure step, in which the exposed photosensitive resin layer is developed to form a resin pattern.

[0955] When the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and intermediate layer of the non-exposed area are removed together with the photosensitive resin layer of the non-exposed area during the developing process. Furthermore, during the developing process, the thermoplastic resin layer and intermediate layer of the exposed area can also be removed by dissolving or dispersing them in the developing solution.

[0956] It can be used to develop the exposed photosensitive resin layer in the developing process using a developing solution.

[0957] As for the developer, there are no particular limitations as long as it can remove the non-image part (non-exposed part) of the photosensitive resin layer. For example, known developers such as the developer described in Japanese Patent Application Publication No. 5-72724 can be used.

[0958] 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.

[0959] 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).

[0960] 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.

[0961] 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 unexposed areas by spraying the developer solution onto the exposed photosensitive resin layer.

[0962] Preferably, after the developing process, the developing residue is removed by spraying a cleaning agent and wiping with a brush.

[0963] There are no particular restrictions on the temperature of the developer solution, but it is preferably 20℃~40℃.

[0964] <Protective film peeling process>

[0965] When the photosensitive transfer material has a protective film, 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. There are no limitations on the method for peeling off the protective film; known methods can be used.

[0966] <Post-exposure and post-drying processes>

[0967] The method for manufacturing a resin pattern or a laminate may include a step of exposing the resin pattern obtained by the above-described developing step (post-exposure step) and / or a step of heating (post-drying step).

[0968] In cases where both post-exposure and post-drying processes are included, post-drying is preferably performed after post-exposure.

[0969] <Other processes>

[0970] The method for manufacturing resin patterns or laminates may include any steps other than those described above (other steps). Examples include, but are not limited to, the steps described in the method for manufacturing circuit wiring or the method for manufacturing touch panels shown below.

[0971] <Application>

[0972] The resin pattern manufactured by the resin pattern manufacturing method according to the present invention and the laminate manufactured by the laminate manufacturing method according to the present invention can be applied to various devices. Examples of devices equipped with the above-mentioned laminate 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 electroluminescent display devices and liquid crystal display devices.

[0973] When the laminate is suitable for a touch panel, the formed resin pattern is preferably used as a protective film for the electrodes or wiring of the touch panel. That is, the photosensitive transfer material involved in the present invention is preferably used to form a protective film for the electrodes or wiring of the touch panel.

[0974] (Methods for manufacturing circuit wiring)

[0975] 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.

[0976] As a method for manufacturing circuit wiring according to the present invention, it preferably includes the following steps in sequence: a step of bonding the outermost layer of the photosensitive transfer material according to the present invention, on the side having a photosensitive resin layer relative to the temporary support, to a substrate having a conductive layer; a step of pattern exposure of the photosensitive resin layer; a step of developing the exposed photosensitive resin layer to form a resin pattern; and a step of etching the substrate in the area where the resin pattern is not disposed (hereinafter also referred to as the "etching step").

[0977] The following describes each step in the method for manufacturing circuit wiring. However, unless otherwise specified, the description of each step in the method for manufacturing resin patterns also applies to each step in the method for manufacturing circuit wiring.

[0978] <Etching Process>

[0979] 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).

[0980] In the etching process, the resin pattern formed by the photosensitive resin layer is used as the etching resist, and the conductive layer is etched.

[0981] 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.

[0982] The etching solution used in wet etching can be appropriately selected as acidic or alkaline depending on the object being etched.

[0983] 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.

[0984] 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.

[0985] <Removal Process>

[0986] In the manufacturing method of circuit wiring, it is preferable to perform a process to remove residual resin patterns (removal process).

[0987] 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.

[0988] 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.

[0989] As a method for removing the photosensitive resin 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.

[0990] 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.

[0991] Furthermore, a removal liquid can be used to remove it by known methods such as spraying, rinsing, and immersion.

[0992] <Other processes>

[0993] The manufacturing method of circuit wiring may include any steps other than those described above (other steps). For example, the following steps can be cited, but are not limited to these steps.

[0994] 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.

[0995] 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.

[0996] -Processes to reduce visible light reflectivity-

[0997] 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 the substrate.

[0998] 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.

[0999] 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.

[1000] -The process of forming an insulating film, and the process of forming a new conductive layer on the surface of the insulating film-

[1001] 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.

[1002] Through the above-described process, a second electrode pattern that is insulated from the first electrode pattern can be formed.

[1003] 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.

[1004] 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.

[1005] 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.

[1006] <Applications of Circuit Wiring>

[1007] The circuit wiring manufactured using the circuit wiring manufacturing method can be applied to various devices. For example, an input device can be described as having circuit wiring manufactured using the above-described method, preferably a touch panel, and more preferably a capacitive touch panel. Furthermore, the above-described input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[1008] (Manufacturing method of touch panel)

[1009] There are no particular limitations on the manufacturing method of the touch panel involved in this invention, as long as the method uses the photosensitive transfer material involved in this invention.

[1010] As a method for manufacturing a touch panel according to the present invention, it preferably includes the following steps in sequence: a step of bonding the outermost layer of the photosensitive transfer material according to the present invention, on the side having a photosensitive resin layer relative to the temporary support, to a substrate having a conductive layer; a step of pattern exposure of the photosensitive resin layer; a step of developing the exposed photosensitive resin layer to form a resin pattern; and a step of etching the substrate in the area where the resin pattern is not provided.

[1011] Regarding the specific methods and order of each step in the manufacturing method of the touch panel, the preferred methods are the same as those described in the sections on "Manufacturing Method of Resin Pattern" and "Manufacturing Method of Circuit Wiring" above.

[1012] Regarding the manufacturing method of touch panels, in addition to forming the wiring for touch panels using the methods described above, known manufacturing methods for touch panels can also be referred to.

[1013] Furthermore, the manufacturing method of the touch panel may include any other process besides those mentioned above (other processes).

[1014] exist Figure 3 and Figure 4 The image shows an example of a mask pattern used in the manufacture of a touch panel.

[1015] exist Figure 3 Pattern A shown Figure 4 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 using a [missing information - likely a device or structure] with [missing information - likely a device or structure]... Figure 3 By exposing the photosensitive resin layer to a mask showing pattern A, a touch panel with circuit wiring corresponding to pattern A corresponding to EX 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.

[1016] A touch panel with at least touch panel wiring is manufactured using the above-described touch panel manufacturing method. The touch panel preferably has a transparent substrate, electrodes, an insulating layer, or a protective layer.

[1017] 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.

[1018] 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).

[1019] As a touch panel, for example, the touch panel described in paragraph 0229 of Japanese Patent Application Publication No. 2017-120435 can be cited.

[1020] Example

[1021] 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.

[1022] The following details the abbreviations of the compounds used in the examples and comparative examples.

[1023] Alkali-soluble resins

[1024] A-1: Styrene / Methacrylic Acid / Methyl Methacrylate = 32 / 28 / 40 (wt%), Mw = 40,000

[1025] A-2: Styrene / Methacrylic Acid / Methyl Methacrylate = 52 / 29 / 19 (wt%), Mw = 60,000

[1026] A-3: Benzyl methacrylate / methacrylic acid = 81 / 19 (wt%), Mw = 40,000

[1027] A-4: Propylene glycol monomethyl ether acetate solution of a copolymer of benzyl methacrylate / methacrylic acid / acrylic acid = 75 / 10 / 15 (solids concentration 30.0%, Mw = 30,000, acid value 153 mg KOH / g).

[1028] A-5: Kuraray Poval PVA-205 (Polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

[1029] A-6: Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.)

[1030] <Alkene unsaturated compounds>

[1031] B-1: NK ester BPE-500 (2,2-bis(4-(methacryloyloxypentethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1032] B-2: NK ester BPE-200 (2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1033] B-3: Dimethacrylate of polyethylene glycol with an average of 1.5 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A.

[1034] B-4: Light Acrylate DPE-6A (Dipentaerythritol hexaacrylate, manufactured by Kyoeisha Chemical Co., Ltd.)

[1035] B-5: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.)

[1036] B-6: NK ester A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1037] B-7: Sartomer SR-454 (ethoxylated (3)trimethylolpropane triacrylate, manufactured by Arkema)

[1038] B-8: Sartomer SR-502 (ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema)

[1039] B-9: NK ester A-9300-CL1 (ε-caprolactone-modified tri-(2-acryloyloxyethyl)isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1040] B-10: NK ester A-DCP (tricyclodecanedimethyl diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[1041] B-11: 8UX-015A (Carbamate acrylate, manufactured by TAISEI FINE CHEMICAL CO., LTD.)

[1042] B-12: ARONIX TO-2349 (a polyfunctional olefinic unsaturated compound with a carboxylic acid group, manufactured by TOAGOSEI CO., LTD.)

[1043] Photopolymerization initiators

[1044] C-1: B-CIM (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer, manufactured by KUROGANE KASEI Co., Ltd.)

[1045] C-2: SB-PI 701 (4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd.)

[1046] C-3: Omnifad 907 (2-Methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, manufactured by IGM Resins B.V.)

[1047] C-4: Irgacure OXE02 (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetophenone-1-(o-acetyl oxime), manufactured by BASF),

[1048] C-5: 4,4'-bis(diethylamino)benzophenone (manufactured by KANTO CHEMICAL CO., INC.)

[1049] <Polymerization inhibitors>

[1050] D-1: TDP-G (Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., LTD.)

[1051] D-2: Phenyxazine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[1052] D-3: Irganox 245 (hindered phenolic polymerization inhibitor, manufactured by BASF)

[1053] D-4: N-Nitrophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[1054] D-5: MQ (4-methoxyphenol, manufactured by Kawaguchi Chemical Industry Co., LTD.)

[1055] <Other Additives>

[1056] E-1: Colorless crystal violet (color developer, manufactured by Tokyo Chemical Industry Co., Ltd.)

[1057] E-2: N-Phenylacetylcarbamoylmethyl-N-carboxymethylaniline (color developer, manufactured by FUJIFILM Wako PureChemical Corporation)

[1058] E-3: Brilliant Green (Developer, manufactured by Tokyo Chemical Industry Co., Ltd.)

[1059] E-4: CBT-1 (Rust inhibitor, carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD)

[1060] E-5: A 1:1 (mass ratio) mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole, a rust inhibitor.

[1061] E-6: Phenylidene (antioxidant, manufactured by Tokyo Chemical Industry Co., Ltd.)

[1062] E-7: Megafac F-552 (Fluoropolymer surfactant, manufactured by DIC Corporation)

[1063] E-8: Megafac F-444 (Fluoropolymer surfactant, manufactured by DIC Corporation)

[1064] Solvent

[1065] F-1: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[1066] F-2: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[1067] F-3: Ion-exchanged water

[1068] F-4: Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.)

[1069] <Preparation of Thermoplastic Resin Compositions>

[1070] A thermoplastic resin composition was prepared by mixing the following components.

[1071] • A-4: 42.85 copies

[1072] • B-10: 4.63 copies

[1073] B-11: 2.31 copies

[1074] • B-12: 0.77 copies

[1075] E-7: 0.03 copies

[1076] F-1: 39.50 copies

[1077] F-2: 9.51 copies

[1078] • A compound with the structure shown below (a photoacid generator, synthesized according to the method described in paragraph 0227 of Japanese Patent Application Publication No. 2013-47765): 0.32 parts

[1079] [Chemical Formula 25]

[1080]

[1081] • Compounds with the structure shown below (pigments that develop color via acid): 0.08 parts

[1082] [Chemical Formula 26]

[1083]

[1084] <Preparation of the Intermediate Layer Composition>

[1085] The intermediate layer composition was prepared by mixing the following components.

[1086] • A-5: 3.22 copies

[1087] • A-6: 1.49 copies

[1088] E-8: 0.0015 copies

[1089] F-3: 38.12 copies

[1090] F-4: 57.17 copies

[1091] <Preparation of Photosensitive Resin Composition>

[1092] The photosensitive resin compositions used in the examples and comparative examples were prepared according to the compositions described in Table 1 below.

[1093] (Examples 1-16 and Comparative Examples 1-3)

[1094] <Preparation of Photosensitive Transfer Materials>

[1095] A polyethylene terephthalate (PET) film with a thickness of 30 μm was prepared as a temporary support. The aforementioned thermoplastic resin composition was coated onto the surface of the temporary support using a slit nozzle, with a coating width of 1.0 μm and a dried layer thickness of 4.0 μm. The resulting thermoplastic resin composition coating was dried at 80°C for 40 seconds to form a thermoplastic resin layer.

[1096] The aforementioned intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle, with a coating width of 1.0 μm and a dried layer thickness of 1.2 μm. The intermediate layer composition film was dried at 80°C for 40 seconds to form the intermediate layer.

[1097] On the surface of the formed intermediate layer, a slit nozzle was used to coat the photosensitive resin composition with the composition described in Table 1, with a coating width of 1.0 μm and a dried layer thickness as specified in Table 1. The coating of the photosensitive resin composition was dried at 80°C for 40 seconds to form a photosensitive resin layer.

[1098] On the surface of the formed photosensitive resin layer, a PET film (TORAY INDUSTRIES, INC., Lumirror 16QS62) was laminated as a protective film to produce photosensitive transfer materials for the examples and comparative examples, respectively.

[1099] <Evaluation of Photosensitive Transfer Materials>

[1100] -laminated-

[1101] The protective film was peeled off from the obtained photosensitive transfer material, and the peeled photosensitive transfer material was laminated onto a substrate (a 200nm thick copper layer was sputtered onto a 100μm PET film) using a sheet laminator. The lamination conditions were set as follows: roller temperature 100℃, lamination speed 2m / min, and lamination pressure 0.5MPa.

[1102] -Eb determination and sensitivity evaluation-

[1103] A 15-step stepped optical wedge (made by Fujifilm Corporation) is placed on a temporary support of the laminated photosensitive transfer material, utilizing 20mW / cm² light. 2 High-pressure mercury lamp at 180mJ / cm 2 Exposure. After exposure, the support is peeled off, and the film is developed in a 0.9% by mass sodium carbonate aqueous solution at 25°C for 30 seconds. Eb is calculated based on the residual film thickness at each step.

[1104] Furthermore, from the viewpoint of adaptability to general photolithography processes, there exists a range of preferred values ​​for Eb. For example, if Eb is 25 mJ / cm²... 2 The above indicates moderate sensitivity and excellent tracking performance of the device. Furthermore, if Eb is 90 mJ / cm², the sensitivity is moderate. 2 The following methods can shorten exposure time and improve productivity.

[1105] Regarding sensitivity, based on Eb(mJ / cm) 2 The value of ) was evaluated according to the following criteria. As a photosensitive transfer material, A to C are preferred, and A or B are more preferred.

[1106] A: 35≤Eb(mJ / cm) 2 ≤70

[1107] B: 25≤Eb(mJ / cm) 2 ) < 35 or 70 < Eb (mJ / cm 2 )≤90

[1108] C: 90 < Eb (mJ / cm) 2 )

[1109] D: Eb(mJ / cm) 2 <25

[1110] -W3 determination-

[1111] A photomask with a line-to-space ratio of 10 μm / 10 μm is brought into contact with a temporary support, and an Ep = 2 × Fb (mJ / cm) is applied. 2 The photosensitive transfer material laminated on the above substrate was exposed. After exposure, and after 3 hours, the temporary support, thermoplastic resin layer, and intermediate layer were peeled off using tape. 5 mL of bromine water (0.2%) was aliquoted into a 50 mL container, and the sample was fixed inside the container without contacting the aliquoted solution. The sample was then allowed to stand at room temperature (25°C) for 5 minutes. Afterward, it was stored under high vacuum for half a day to degas the residual bromine. Thus, a sample with bromine-modified carbon-carbon double bonds was prepared.

[1112] The sample was analyzed using secondary ion mass spectrometry (ION-TOF SIMS5, primary ion source: Bi).3+ (30kV), Measurement range: 50mm, Area resolution: 512×512 pixels, Integration: 32 times, Measurement mode: High spatial resolution mode (Fast Imaging), Charge correction: using an electron gun), evaluated C2HBr - The width of the region. (The last part, "C2HBr", appears to be unrelated and likely refers to a separate topic.) - The region with lower intensity is defined as the width of the polymerization area. The width of the polymerization area was measured at three locations, and the average value was defined as W3.

[1113] -W 24 Determination -

[1114] The exposure time was changed; otherwise, the aggregation area width W was determined 24 hours after pattern exposure, using the same method as W3. 24 Furthermore, W was calculated. 24 The value of / W3.

[1115] -W 72 Determination -

[1116] The exposure time was changed; otherwise, the aggregation area width W was determined 72 hours after pattern exposure, using the same method as W3. 72 Furthermore, W was calculated. 72 The value of / W3.

[1117] <Linewidth changes after exposure and 24 hours>

[1118] A photomask with a line-to-space ratio of 10 μm / 10 μm is brought into contact with a temporary support, and an Ep = 2 × Fb (mJ / cm) is applied. 2 The photosensitive transfer material laminated on the substrate was exposed. After exposure, after 3 or 24 hours, the temporary support was peeled off, and a 1% sodium carbonate aqueous solution at 25°C was sprayed to dissolve the unexposed areas, thus obtaining a resist pattern. The linewidth of the portion in contact with the substrate was measured using a scanning electron microscope (SEM) image of the cross-section of the obtained resist pattern. The linewidth developed 3 hours after exposure was defined as Wr3, and the linewidth developed 24 hours after exposure was defined as Wr. 24 Wr was calculated 24 / Wr3. The closer this ratio is to 1, the smaller the linewidth change during post-exposure placement, indicating optimal performance. Wr is compared to the following benchmarks. 24 / Wr3 was evaluated. As a photosensitive transfer material, A or B are preferred.

[1119] A: Wr 24 / Wr3<1.03

[1120] B: 1.03≤Wr 24 / Wr3<1.05

[1121] C: 1.05≤Wr 24 / Wr3<1.1

[1122] D: 1.1≤Wr 24 / Wr3

[1123] <Linewidth variation due to changes in developing temperature>

[1124] A photomask with a line-to-space ratio of 10 μm / 10 μm is brought into contact with a temporary support, and Ep = 2 × Eb (mJ / cm²) is used. 2 The photosensitive transfer material laminated on the above substrate was exposed. After exposure, and after 3 hours, the temporary support was peeled off, and a 1% sodium carbonate aqueous solution at 30°C was sprayed to dissolve the unexposed areas, thus obtaining the resist pattern. The linewidth Wr was measured based on the cross-sectional SEM image of the obtained resist pattern. 3b Wr was calculated 3b / Wr3. The closer this ratio is to 1, the smaller the linewidth variation with changes in developing temperature, and the wider the process robustness; it can be considered optimal. Wr 3b / Wr3 was evaluated based on the following criteria. As a photosensitive transfer material, A or B is preferred.

[1125] A: Wr 3b / Wr3<1.03

[1126] B: 1.03≤Wr 3b / Wr3<1.05

[1127] C: 1.05≤Wr 3b / Wr3

[1128] The measurement and evaluation results are summarized and shown in Table 2.

[1129] [Table 1]

[1130]

[1131] [Table 2]

[1132]

[1133] As shown in Tables 1 and 2 above, the photosensitive transfer materials of Examples 1 to 16 showed less change in the linewidth of the resin pattern as the exposure time passed.

[1134] Furthermore, in the photosensitive transfer materials of Examples 1 to 16, the linewidth of the resin pattern changes little with the development temperature and the sensitivity is also excellent.

[1135] (Example 101 (Second: PET peeling exposure))

[1136] A circuit board was fabricated by sputtering an ITO film to a thickness of 150 nm on a 100-micron-thick PET substrate as a second conductive layer, and then forming a copper film to a thickness of 200 nm on top of it as a first conductive layer by vacuum evaporation.

[1137] The photosensitive transfer material obtained in Example 1 was laminated onto the copper layer (lamination roller temperature 120°C, linear pressure 0.8 MPa, linear speed 1.0 m / min). A device equipped with... Figure 3 The photomask of pattern A shown exposes the contact pattern of the laminated stack. Pattern A has a structure in which conductive layer pads are connected in one direction without peeling off the temporary support. Afterwards, the temporary support is peeled off, and the substrate is developed and washed to obtain pattern A. Next, the copper layer is etched using a copper etchant (KANTOCHEMICAL CO., INC. Cu-02), and then the ITO layer is etched using an ITO etchant (KANTO CHEMICAL CO., INC. ITO-02), thereby obtaining a substrate where both copper and ITO are depicted using pattern A.

[1138] The residual photosensitive resin layer (pattern A) was removed using a stripping solution (KANTO CHEMICAL CO., INC., KP-301), and the photosensitive transfer material obtained in Example 1 was laminated again on the copper layer (lamination roller temperature 120°C, linear pressure 0.8 MPa, linear speed 1.0 m / min).

[1139] Next, while in alignment, use Figure 4 The photomask for pattern B was exposed, developed, and washed. Then, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer (pattern B) was removed using a stripping solution (KANTO CHEMICAL CO., INC. KP-301) to obtain the circuit wiring substrate.

[1140] The circuit wiring board obtained by microscopic observation showed no peeling or defects, and was a perfect pattern.

[1141] in addition, Figure 3 In the pattern A shown, the gray area GR is the light-blocking area, EX is the exposure area, and the dashed area DL virtually represents the alignment frame.

[1142] and, Figure 4 In pattern B shown, and Figure 3 Similarly, the gray area, GR, represents the light-blocking area, EX represents the exposure area, and the dashed area, DL, virtually represents the alignment frame.

[1143] The entire contents of Japanese Patent Application No. 2020-156353, filed on September 17, 2020, are incorporated herein by reference.

[1144] All documents, patent applications and technical standards described in this specification, and the specific and separately described documents, patent applications and technical standards incorporated herein by reference, are incorporated herein by reference to the same extent.

[1145] Symbol Explanation

[1146] 1, 11 - Temporary support; 2, 12 - Transfer layer; 3, 17 - Photosensitive resin layer; 5 - Refractive index adjustment layer; 13 - Thermoplastic resin layer; 15 - Intermediate layer; 10, 20 - Photosensitive transfer material; GR - Light-shielding part (non-image part); EX - Exposure part (image part); DL - Alignment frame.

Claims

1. A photosensitive transfer material, comprising: Temporary support structure; and A photosensitive resin layer comprising an alkali-soluble resin, an olefinic unsaturated compound, and a photopolymerization initiator. The photosensitive resin layer also contains a polymerization inhibitor. When the content of the photopolymerization initiator in the photosensitive resin layer is set to Rc and the content of the polymerization inhibitor is set to Rd, the mass ratio Rd / Rc is 0.02 or more and 0.1 or less. The photosensitive resin layer is used at mJ / cm 2 After exposing 10μm / 10μm line and space patterns with an exposure dose Ep, the double bond reaction region width W3 after 3 hours and the double bond reaction region width W after 24 hours are compared. 24 Satisfy W 24 / W3≤1.05, W3 and W 24 Let's assume the width of the double bond reaction region is obtained by secondary ion mass spectrometry analysis after bromine staining of the exposed photosensitive transfer material. The Ep satisfies Ep = 2 × Eb. Eb represents the light passing through a 20mW / cm² illuminance source after the photosensitive resin layer is attached to the substrate, separated by a 15-step stepped light wedge. 2 The high-pressure mercury lamp has an exposure of 180 mJ / cm 2 Exposure is performed, and the exposure level is set to the residual thickness of the developed photosensitive resin layer by ±1%.

2. The photosensitive transfer material according to claim 1, wherein, After exposing the photosensitive resin layer to the exposure amount Ep with a 10μm / 10μm line and space pattern, the width W3 of the double bond reaction region after 3 hours and the width W after 72 hours are compared. 72 Satisfy W 72 / W3≤1.10, W 72 Let's say we define the width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining of the exposed photosensitive transfer material.

3. The photosensitive transfer material according to claim 1 or 2, wherein, The olefinic unsaturated compounds include olefinic unsaturated compounds having a bisphenol structure.

4. The photosensitive transfer material according to claim 1 or 2, wherein, The photopolymerization initiator comprises a bimidazole compound and a benzophenone compound.

5. The photosensitive transfer material according to claim 1 or 2, wherein, The polymerization inhibitor comprises at least one compound selected from phenothiazine, phenothiazine, and compounds having a hindered phenolic structure.

6. The photosensitive transfer material according to claim 1 or 2, wherein, The mass ratio Rd / Rc is greater than or equal to 0.03 and less than or equal to 0.

05.

7. A method for manufacturing a resin pattern, comprising the following steps: A process of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 6, on the side having a photosensitive resin layer relative to the temporary support, to a substrate; The process of patterning the photosensitive resin layer; and The process of developing the exposed photosensitive resin layer to form a resin pattern.

8. The method for manufacturing a resin pattern according to claim 7, wherein, At least a portion of the resin pattern comprises line and space patterns, wherein the combined width of at least one group of lines and spaces in the line and space patterns is less than 20 μm.

9. A method for manufacturing circuit wiring, comprising the following steps: A process of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 6, on the side having a photosensitive resin layer relative to the temporary support, to a substrate having a conductive layer. The process of patterning the photosensitive resin layer; The process of developing the exposed photosensitive resin layer to form a resin pattern; and The process of etching the substrate in areas where the resin pattern is not configured.

10. A method for manufacturing a touch panel, comprising the following steps: A process of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 6, on the side having a photosensitive resin layer relative to the temporary support, to a substrate having a conductive layer. The process of patterning the photosensitive resin layer; The process of developing the exposed photosensitive resin layer to form a resin pattern; and The process of etching the substrate in areas where the resin pattern is not configured.

Images