TWI904311B - Transfer material and method for producing laminate - Google Patents

Abstract

This disclosure provides a transfer material and its application, the transfer material comprising a temporary support and a photosensitive layer in contact with the temporary support, wherein the surface roughness Ra of the photosensitive layer exposed when the photosensitive layer is peeled off from the temporary support is 2 nm or more.

Description

Manufacturing method of transfer materials and laminates

This disclosure relates to a transfer material and a method for manufacturing a laminate.

Patent document 1 discloses a photosensitive transfer material having a photosensitive layer, an adhesive layer and a temporary support in sequence on a cover film. The photosensitive layer contains particles, the photosensitive layer is in contact with the adhesive layer, the photosensitive layer and the adhesive layer are peelable, and the surface of the photosensitive layer after peeling off the photosensitive layer and the adhesive layer has an unevenness formed by the particles.

[Patent Document 1] Japanese Patent Application Publication No. 2019-128445

In conventional pattern-forming methods using photosensitive transfer materials such as those described in Patent 1, a method of peeling off a temporary support before exposure of the photosensitive layer is sometimes employed to improve resolution and reduce defects in the pattern. However, during transport after the temporary support is peeled off, the exposed photosensitive layer adheres to the transport device, such as rollers, sometimes causing a decrease in transportability. This phenomenon is prone to occur when a temporarily stationary transported object is moved again. Furthermore, when exposing the photomask to the photosensitive layer exposed by the peeling off of the temporary support, the photosensitive layer sometimes adheres to the photomask, making it difficult to align the photomask.

The purpose of one embodiment of this disclosure is to provide a transfer material comprising a photosensitive layer having excellent smoothness. The purpose of another embodiment of this disclosure is to provide a method for manufacturing a laminate using a transfer material comprising a photosensitive layer having excellent smoothness.

This disclosure includes the following: <1> A transfer material comprising a temporary support and a photosensitive layer in contact with the temporary support, wherein the surface roughness Ra of the photosensitive layer exposed when the photosensitive layer is peeled off from the temporary support is 2 nm or more. <2> The transfer material as described in <1>, wherein the surface roughness Ra of the temporary support exposed when the photosensitive layer is peeled off from the temporary support is 2 nm or more. <3> The transfer material as described in <1> or <2>, wherein the surface roughness Ra of the photosensitive layer exposed when the photosensitive layer is peeled off from the temporary support is 1,000 nm or less. <4> The transfer material as described in any one of <1> to <3>, wherein the surface roughness Ra of the temporary support exposed when the photosensitive layer is peeled off from the temporary support is 1,000 nm or less. <5> The transfer material as described in any one of <1> to <4>, wherein the static friction coefficient of the surface of the photosensitive layer exposed when the photosensitive layer is peeled off from the temporary support is 1.0 or less. <6> The transfer material as described in any one of <1> to <5>, wherein the photosensitive layer comprises a polymer compound having a weight average molecular weight of 10,000 or more, and the glass transition temperature of the polymer compound is 50°C or more. <7> The transfer material as described in <6>, wherein the photosensitive layer comprises a polymeric compound having a molecular weight of 1,500 or less, and the mass ratio of the polymeric compound contained in the photosensitive layer to the mass ratio of the polymeric compound contained in the photosensitive layer is 50% or less. <8> The transfer material as described in <7>, wherein the polymeric compound comprises a polymeric compound having two or more polymeric groups. <9> The transfer material as described in <7>, wherein the polymeric compound comprises a polymeric compound having two or more polymeric groups and a polymeric compound having three or more polymeric groups. <10> The transfer material as described in any one of <7> to <9>, wherein the polymeric compound is an ethoxylated methacrylate compound. <11> The transfer material as described in any one of <1> to <10>, wherein the photosensitive layer comprises a surfactant. <12> The transfer material as described in any one of <1> to <11>, wherein the thickness of the photosensitive layer is 5 μm or less. <13> A method for manufacturing a laminate, comprising the following steps in sequence: bonding a transfer material including a temporary support and a photosensitive layer in contact with the temporary support to a substrate, thereby sequentially disposing the photosensitive layer and the temporary support on the substrate; peeling the temporary support from the photosensitive layer; and performing exposure processing and development processing on the photosensitive layer exposed by the peeling of the temporary support to form a pattern, wherein the surface roughness Ra of the photosensitive layer exposed by peeling the temporary support from the photosensitive layer is 2 nm or more. <14> The method for manufacturing a laminate as described in <13>, wherein the surface roughness Ra of the photosensitive layer exposed by peeling it from the temporary support is 1,000 nm or less. <15> The method for manufacturing a laminate as described in <13> or <14>, wherein the exposure processing includes the step of exposing the photosensitive layer to a photomask. [Invention Effects]

According to one embodiment of the present invention, a transfer material comprising a photosensitive layer having excellent smoothness can be provided. According to another embodiment of the present invention, a method for manufacturing a laminate using a method for manufacturing a transfer material comprising a photosensitive layer having excellent smoothness can be provided.

The contents of this disclosure are explained below. Refer to the accompanying figures for further explanation, although symbols are sometimes omitted. In this disclosure, the numerical range indicated by “~” refers to the range encompassed by the values recorded before and after “~” as lower and upper limits. In this disclosure, “(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)acrylyl” means either or both of acrylyl and methacrylyl. In this disclosure, regarding the amount of each component in the composition, when multiple substances corresponding to each component are present in the composition, unless otherwise specified, it refers to the aggregate amount of the corresponding multiple substances present in the composition. In this disclosure, the term "step" includes not only independent steps, but also steps that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In the marking of bases (atomic groups) in this disclosure, the markings without "substituted" and "unsubstituted" include those without substituents, and also those with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this disclosure, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Furthermore, the light used in exposure generally includes bright-line light from mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and active light rays (active energy rays) such as electron beams. The chemical structural formulas in this disclosure are sometimes written using simplified formulas omitting the hydrogen atom. In this disclosure, "mass%" and "weight%" are synonymous, as are "parts by mass" and "parts by weight." In this disclosure, a combination of two or more preferred states is considered a better state. In this disclosure, "transparent" refers to an average transmittance of 80% or more for visible light with wavelengths of 400 nm to 700 nm, preferably 90% or more. In this disclosure, the average transmittance of visible light is a value measured using a spectrophotometer, such as the Hitachi, Ltd. U-3310 spectrophotometer. Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this disclosure are calculated using a gel osmosis chromatography (GPC) analyzer with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) and detected by solvent THF (tetrahydrofuran) and a differential refractometer, using polystyrene as a standard substance. In this disclosure, unless otherwise specified, the content of metallic elements is the value measured using an inductively coupled plasma (ICP) spectrophotometer. In this disclosure, unless otherwise specified, the refractive index is the value measured using an elliptical polarimeter at a wavelength of 550 nm. In this disclosure, unless otherwise specified, the hue is the value measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.). In this disclosure, "alkaline solubility" refers to a solubility of 0.1 g or more in 100 g of a 1% (w/w) aqueous solution of sodium carbonate at a liquid temperature of 22°C. In this disclosure, "solid composition" refers to all components other than the solvent. In this disclosure, unless otherwise specified, the thickness of each layer of the transfer material is determined by the following steps: a cross-section perpendicular to the main surface of the transfer material is observed using a scanning electron microscope (SEM), and the thickness of each layer is measured at any 5 or more points based on the obtained observation image, and the average value is calculated.

<Transfer Material> One embodiment of the transfer material disclosed herein includes a temporary support and a photosensitive layer in contact with the temporary support. The surface roughness Ra of the photosensitive layer exposed when it is peeled off from the temporary support is 2 nm or more. According to the above embodiment, a transfer material including a photosensitive layer with excellent smoothness can be provided. The reason for the improved smoothness of the photosensitive layer is presumably as follows: If the surface roughness Ra of the photosensitive layer exposed when it is peeled off from the temporary support is 2 nm or more, the friction generated on the surface of the photosensitive layer is reduced. Therefore, it is presumed that the smoothness of the photosensitive layer surface is improved. The transfer material will be specifically described below. In the following description, the surface of the temporary support in the transfer material facing the photosensitive layer is sometimes referred to as the "first surface of the temporary support," and the surface of the photosensitive layer in the transfer material facing the temporary support is referred to as the "first surface of the photosensitive layer." The first surface of the temporary support faces the first surface of the photosensitive layer.

In one embodiment of the transfer material disclosed herein, other layers may be layered on the side of the photosensitive layer opposite to the face of the temporary support. Examples of other layers include, for example, a refractive index adjusting layer and a protective film. Furthermore, each layer may be a single layer or multiple layers of two or more. Examples of the structure of the transfer material are shown below. However, the structure of the transfer material is not limited to the following examples. In the following structures, it is preferable that the photosensitive layer is a negative photosensitive layer. Furthermore, it is also preferable that the photosensitive layer is a colored resin layer. (1) "Temporary support/photosensitive layer/refractive index adjusting layer/protective film" (2) "Temporary support/photosensitive layer/protective film"

The composition of the transfer material is explained with reference to Figure 1. Figure 1 is a schematic diagram showing the composition of a transfer material in a certain embodiment. The transfer material 100 shown in Figure 1 includes, in sequence, a temporary support 10, a photosensitive layer 20, and a protective film 30. Alternatively, the protective film 30 of the transfer material 100 may not be provided.

When the transfer material includes other layers on the side of the photosensitive layer opposite to the temporary support, the total thickness of the other layers relative to the thickness of the photosensitive layer is preferably 0.1% to 30%, and even more preferably 0.1% to 20%.

From the viewpoint of suppressing the generation of air bubbles in the bonding step described later, it is preferable that the maximum width of the transfer material's corrugations is 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. It is preferable that the maximum width of the transfer material's corrugations is 0 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more. The maximum width of the transfer material's corrugations is measured by the following steps: First, test samples are prepared by cutting the transfer material into dimensions of 20 cm long × 20 cm wide along a direction perpendicular to the main surface. Additionally, if the transfer material includes a protective film, the protective film is peeled off. Next, the test sample is placed statically on a smooth and level platform with the surface of the temporary support facing the platform. After standing, a 10cm square area around the center of the test sample is scanned with a laser microscope (e.g., a VK-9700SP manufactured by KEYENCE CORPORATION) to obtain a three-dimensional surface image. The maximum convex height observed in the obtained three-dimensional surface image is subtracted from the minimum concave height. This operation is performed on 10 test samples, and the arithmetic mean is taken as the "maximum width of the transfer material's ripples".

The temporary support body is disclosed in one embodiment of the transfer material. The temporary support body is a support that at least supports the photosensitive layer and is peelable. The temporary support body is in contact with the photosensitive layer. In the transfer material, the surface of the temporary support body facing the photosensitive layer, i.e., the first surface of the temporary support body, is in contact with the photosensitive layer and can be exposed by peeling the temporary support body from the photosensitive layer.

The roughness of the first surface of the temporary support can affect the roughness of the first surface of the photosensitive layer, which will be described later. For example, during the manufacturing process of the transfer material, if the roughness of the first surface of the temporary support decreases, the roughness of the first surface of the photosensitive layer tends to decrease as well. On the other hand, if the roughness of the first surface of the temporary support increases, the roughness of the first surface of the photosensitive layer tends to increase as well. From the above perspective, it is preferable that the surface roughness Ra of the temporary support exposed when the photosensitive layer is peeled off from the temporary support, i.e., the first surface of the temporary support, is 1,000 nm or less, more preferably 500 nm or less, and even more preferably 200 nm or less. The surface roughness Ra of the first surface of the temporary support is preferably 2 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. If the surface roughness Ra of the first surface of the temporary support is 1,000 nm or less, the straightness of the wiring pattern formed, for example, using a transfer material, is improved. The surface roughness Ra of the first surface of the temporary support is preferably 2 nm to 1,000 nm, more preferably 50 nm to 500 nm, and even more preferably 100 nm to 200 nm. The method for adjusting the surface roughness of the first surface of the temporary support is not limited. One method for adjusting the roughness Ra of the first surface of a temporary support is to bring a matte-finished roller (hereinafter sometimes referred to as a "matte roller") into contact with the first surface of the temporary support. In this method, the roughness Ra of the first surface of the temporary support is adjusted according to the surface roughness of the matte-finished roller. Another method for adjusting the roughness Ra of the first surface of a temporary support is to project fine sand onto the first surface of the temporary support to give it an uneven surface (e.g., sandblasting). In this method, the roughness Ra of the first surface of the temporary support is adjusted according to the size and intensity of the projected sand.

In this disclosure, the roughness Ra of the first surface of the temporary support was measured using a surface roughness and surface shape measuring machine (NewView 6300, manufactured by Zygo Corporation). First, the temporary support was peeled off from the photosensitive layer. Next, using a 50x objective lens, the "Image Zoom" of the "Mesurement Control" was set to x0.5, the "Scan Length" was set to 40 μm, and "Cylynder" was selected in "Remove" of "Analyze Control". The average roughness Ra of the center surface shown in the "Surface map" was used as the roughness Ra.

The temporary support can be a single-layer or multi-layer structure. A thin film is preferred, and a resin film is even more preferred. As a temporary support, a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat is preferred. Examples of such films include polyethylene terephthalate (PET) films (e.g., biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films. Polyethylene terephthalate films are preferred as temporary supports. Furthermore, it is preferable that the film used as the temporary support is free from deformations such as wrinkles and scratches. In the case of a multilayer structure, it is preferable that the first layer constituting the temporary support comprises a thermoplastic resin. In other words, it is preferable that the temporary support includes a thermoplastic resin layer in contact with the photosensitive layer. The fact that the temporary support includes a thermoplastic resin layer in contact with the photosensitive layer, i.e., the first surface of the temporary support is composed of a thermoplastic resin layer, is preferable from the perspective of easily controlling the roughness of the first surface of the temporary support. Examples of thermoplastic resins include polyolefin resins (e.g., polyethylene, polypropylene, ethylene-(meth)acrylate copolymers, ethylene-(meth)acrylate metal salt copolymers, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers), polyester resins, styrene-butadiene copolymers, acrylic resins, amine resins, epoxy resins, and polyamide resins. Polyolefin resins are preferred as they readily peel from the photosensitive layer. The ease with which the photosensitive layer peels off can be attributed to intermolecular interactions between the thermoplastic resin layer and the photosensitive layer. This can be inferred to be due to the suppression of hydrogen bond and dipole interactions by using polyolefin resins in the thermoplastic process. Among polyolefin resins, polyethylene, with its low hydrogen bond and dipole interactions and low softening temperature, is the optimal choice.

High transparency of the temporary support is preferable. For light with a wavelength of 365nm, a transmittance of 60% or higher is preferable, and 70% or higher is even better. From the perspective of transparency, low haze is preferable. A haze value of 2% or less is preferable, 0.5% or less is even better, and 0.1% or less is even better. From the perspective of transparency, a low number of coarse particles, foreign objects, and defects contained in the temporary support is preferable. The number of particles, foreign objects and defects with a diameter of 1 μm or larger in the temporary support is preferably 50 or less per 10 ^mm² , more preferably 10 or less per 10 ^mm² , even more preferably 3 or less per 10 ^mm² , ^and best of all 0 per 10 mm².

The thickness of the temporary support is preferably 5μm to 200μm. From the perspective of ease of operation and versatility, 10μm to 150μm is better, and 10μm to 50μm is even better. The thickness of the temporary support is calculated as the average of the thicknesses measured at any 5 points using cross-sectional observation with a scanning electron microscope (SEM).

Examples of temporary supports include biaxially stretched polyethylene terephthalate (PET) films with a thickness of 16 μm, 12 μm, and 9 μm.

Preferred examples of 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.

From the perspective of providing operability, a layer containing microparticles (also known as a "lubricant layer") can be provided on the surface of the temporary support. The lubricant layer can be provided on one side of the temporary support or on both sides. It is preferable that the diameter of the particles contained in the lubricant layer is 0.05 μm to 0.8 μm. Furthermore, it is preferable that the thickness of the lubricant layer is 0.05 μm to 1.0 μm.

The photosensitive layer disclosed herein is a transfer material comprising a photosensitive layer in contact with a temporary support. After being transferred, for example, onto a substrate, the photosensitive layer can form a pattern by exposure and development. In the transfer material, the surface of the photosensitive layer facing the temporary support, i.e., the first surface of the photosensitive layer, is in contact with the temporary support and can be exposed by peeling the photosensitive layer from the temporary support.

[Roughness Ra] The surface roughness Ra of the photosensitive layer exposed when the temporary support is peeled off from the photosensitive layer, i.e., the first surface of the photosensitive layer, is 2 nm or more. If the roughness Ra of the first surface of the photosensitive layer is 2 nm or more, the smoothness of the photosensitive layer surface is improved. It is preferable that the roughness Ra of the first surface of the photosensitive layer is 10 nm or more, more preferable that is 50 nm or more, and even more preferable that is 100 nm or more. It is preferable that the roughness Ra of the first surface of the photosensitive layer is less than 1,000 nm, more preferable that is less than 500 nm, even more preferable that is less than 200 nm, and best preferred that is less than 100 nm. If the roughness Ra of the first surface of the photosensitive layer is less than 1,000 nm, the straightness of the pattern formed by the photosensitive layer is improved. From the perspective of the smoothness of the photosensitive layer and the straightness of the pattern, a roughness Ra of 2 nm to 1,000 nm on the first surface of the photosensitive layer is preferred, 50 nm to 500 nm is even better, and 100 nm to 200 nm is even better. The roughness Ra of the first surface of the photosensitive layer is measured by following the method for measuring the roughness Ra of the first surface of a temporary support as described in the section on "Temporary Supports".

[Coefficient of Friction] It is preferable that the static friction coefficient of the surface of the photosensitive layer exposed when the photosensitive layer is peeled off from the temporary support, i.e., the first surface of the photosensitive layer, is less than 2.0, preferably less than 1.0, and even more preferably less than 0.6. If the static friction coefficient of the first surface of the photosensitive layer is less than 2.0, the smoothness of the photosensitive layer surface is improved. For example, a reduction in the static friction coefficient of the first surface of the photosensitive layer can prevent the photosensitive layer exposed during the transport process after the temporary support is peeled off from adhering to the exposure mask and conveying devices such as conveyor rollers, and allow temporarily stationary transported items to move smoothly again. The static friction coefficient of the first surface of the photosensitive layer is preferably 0.1 or higher, more preferably 0.2 or higher, and even more preferably 0.3 or higher. If the static friction coefficient of the first surface of the photosensitive layer is 0.1 or higher, the holding force on conveying devices such as conveyor rollers is improved, and the occurrence of snake-like movement and winding deviation is suppressed. The static friction coefficient of the first surface of the photosensitive layer is preferably 0.1 or higher but not exceeding 2.0, more preferably 0.2 to 1.0, and even more preferably 0.3 to 0.6.

It is preferable that the coefficient of dynamic friction of the surface of the photosensitive layer exposed when the temporary support is peeled off from the photosensitive layer, i.e., the first surface of the photosensitive layer, is less than 1.5, even better is less than 1.0, and further preferably less than 0.5. If the coefficient of dynamic friction of the first surface of the photosensitive layer is less than 1.5, the smoothness of the photosensitive layer surface is improved. It is preferable that the coefficient of dynamic friction of the first surface of the photosensitive layer is 0.05 or higher, even better is 0.1 or higher, and further preferably is 0.2 or higher. If the coefficient of dynamic friction of the first surface of the photosensitive layer is 0.05 or higher, the holding force on conveying devices such as conveyor rollers is improved, and the occurrence of snake-like movement and winding deviation is suppressed. It is preferable for the coefficient of dynamic friction of the first surface of the photosensitive layer to be 0.05 or higher but not more than 1.5, 0.1 to 1.0 is even better, and 0.2 to 0.5 is even better.

In this disclosure, the static and dynamic coefficients of friction of the first surface of the photosensitive layer are measured by the following method: A transfer material is laminated onto a copper-coated polyethylene terephthalate (PET) substrate under lamination conditions of 0.6 MPa linear pressure and 0.5 m/min linear speed (lamination speed). By laminating the transfer material onto the copper-coated PET substrate, a photosensitive layer and a temporary support are sequentially disposed on the copper layer of the copper-coated PET substrate. When the transfer material includes a protective film, the protective film is peeled off before lamination. The temporary support was removed, exposing the photosensitive layer to contact a 5mm thick transparent sodium glass (200x200mm□). The static and dynamic coefficients of friction were determined using a Tensilon universal testing machine (RTF1210, manufactured by A&D Company, Limited) and a plastic friction coefficient measuring fixture (J-PZ2-50N, manufactured by A&D Company, Limited) according to the Plastics-Film and Sheet Friction Coefficient Test Method (JIS K7125:1999). The test conditions are shown in sequence: Load: 200g; Contact area: 63mm × 63mm; Test speed: 100mm/min.

[Types and Composition] The photosensitive layer can be a negative photosensitive layer or a positive photosensitive layer. A negative photosensitive layer is preferred. When the photosensitive layer is a negative photosensitive layer, the resulting pattern corresponds to the hardened layer. When the photosensitive layer is a negative photosensitive layer, it is preferable that the negative photosensitive layer contains resin, a polymerizable compound, and a polymerization initiator. Furthermore, when the photosensitive layer is a negative photosensitive layer, it is also preferable that it contains, as part or entirely, an alkali-soluble resin as part of the resin. That is, in one state, it is preferable that the photosensitive layer contains an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. The photosensitive layer preferably contains 10% to 90% by mass of an alkali-soluble resin, 5% to 70% by mass of an ethylene-unsaturated compound, and 0.01% to 20% by mass of a photopolymerization initiator relative to the total mass of the photosensitive layer.

(Polymer Compound) It is preferable that the photosensitive layer contains a polymer compound. "Polymer compound" refers to a compound having a weight average molecular weight of 5,000 or more. A weight average molecular weight of 10,000 or more is preferable. A weight average molecular weight of 5,000 to 500,000 is preferable, and 10,000 to 500,000 is preferable. If the weight average molecular weight of the polymer compound increases, the hardness of the photosensitive layer increases. If the hardness of the photosensitive layer increases, for example, the strength of the photosensitive layer increases. Furthermore, the smoothness of the photosensitive layer surface improves.

For polymer compounds, a glass transition temperature above 30°C is preferred, above 40°C is even better, above 50°C is further preferred, above 60°C is exceptionally good, and above 70°C is optimal. Higher glass transition temperatures of the polymer compound increase the hardness of the photosensitive layer. Increased hardness of the photosensitive layer improves the smoothness of its surface. A glass transition temperature below 135°C is preferred for the polymer compound.

As a polymer, alkali-soluble resins, for example, can be cited as described later.

(Alkali-soluble resin) It is preferable that the photosensitive layer contains an alkali-soluble resin. For example, known alkali-soluble resins used as etching resists are preferably examples of alkali-soluble resins. Furthermore, it is preferable that the alkali-soluble resin is an adhesive polymer. It is preferable that the alkali-soluble resin has acid groups. As an alkali-soluble resin, polymer A, described later, is preferred.

-Polymer A- It is preferable that the photosensitive layer contains Polymer A as an alkali-soluble resin. From the viewpoint of improving resolution by suppressing swelling of the photosensitive layer caused by the developer, an acid value of Polymer A of 220 mg KOH/g or less is preferable, less than 200 mg KOH/g is more preferable, and less than 190 mg KOH/g is even more preferable. The lower limit of the acid value of Polymer A is not particularly limited. From the viewpoint of improving development performance, an acid value of Polymer A of 60 mg KOH/g or more is preferable, 120 mg KOH/g or more is more preferable, 150 mg KOH/g or more is even more preferable, and 170 mg KOH/g or more is particularly preferable. The acid value is the mass of potassium hydroxide [mg] required to neutralize 1g of the sample, and the unit is expressed as mgKOH/g in this disclosure. The acid value can be calculated, for example, based on the average content of acid groups in the compound. The acid value of polymer A can be adjusted using the types of constituent units that make up polymer A and the content of constituent units containing acid groups.

The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developing properties, a weight-average molecular weight of 500,000 or less is preferred. A weight-average molecular weight of 100,000 or less is even more preferred, 60,000 or less is further preferred, and 50,000 or less is particularly preferred. On the other hand, from the viewpoint of controlling the properties of the developing aggregate and the properties of the unexposed film, such as edge melting and chipping in the photosensitive layer, a weight-average molecular weight of 5,000 or more is preferred. A weight-average molecular weight of 10,000 or more is more preferred, 20,000 or more is further preferred, and 30,000 or more is particularly preferred. Edge melting refers to the degree to which the photosensitive layer easily overflows from the end face of the roller when the transfer material is rolled into a roller shape. Chipping refers to the degree to which chips easily scatter when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive layer, they will be transferred to the mask in subsequent exposure steps, resulting in defective products. A dispersion of polymer A of 1.0 to 6.0 is preferred, 1.0 to 5.0 is more preferred, 1.0 to 4.0 is further preferred, and 1.0 to 3.0 is especially preferred. In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values determined using gel permeation chromatography. Furthermore, dispersion is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight/number-average molecular weight).

From the perspective of suppressing the degradation of linewidth and resolution due to focal point deviation during exposure, it is preferable that polymer A contains aromatic hydrocarbons, and even more preferable that it contains aromatic hydrocarbon constituent units. Examples of aromatic hydrocarbons include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The proportion of aromatic hydrocarbon constituent units in polymer A 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 best preferably 50% by mass or more, based on the total mass of polymer A. As an upper limit, it is not particularly limited, but preferably 95% by mass or less, and more preferably 85% by mass or less. In addition, the proportion of aromatic hydrocarbon constituent units when multiple polymers A are contained is calculated as a weight average.

Examples of monomers forming aromatic hydrocarbon units include aralkyl monomers, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tributoxystyrene, acetylated styrene, 4-vinylbenzoic acid, styrene dimers, styrene trimers, etc.). Aralkyl monomers or styrene are preferred. In one phase, when the monomer forming the aromatic hydrocarbon unit in polymer A is styrene, the proportion of the styrene unit is preferably 20% to 50% by mass, more preferably 25% to 45% by mass, further preferably 30% to 40% by mass, and especially preferably 30% to 35% by mass, based on the total mass of polymer A.

Aryl groups can be exemplified by substituted or unsubstituted phenylalkyl groups, with substituted or unsubstituted benzyl groups being preferred.

Examples of monomers having a phenyl alkyl group other than a substituted or unsubstituted benzyl group include phenyl ethyl (meth)acrylate.

Examples of monomers having substituted or unsubstituted benzyl groups include (meth)acrylates (e.g., benzyl (meth)acrylate, benzyl chloro (meth)acrylate, etc.) and vinyl monomers having benzyl groups (e.g., vinylbenzyl chloride, vinylbenzyl alcohol, etc.). Among these, benzyl (meth)acrylate is preferred. In one phase, when the monomer forming the aromatic hydrocarbon unit in polymer A is benzyl (meth)acrylate, the content of the (meth)acrylate unit is preferably 50% to 95% by mass based on the total mass of polymer A, more preferably 60% to 90% by mass, further preferably 70% to 90% by mass, and especially preferably 75% to 90% by mass.

Polymer A having an aromatic hydrocarbon constituent unit is preferably obtained by polymerizing the aromatic hydrocarbon monomer with at least one of the first monomers described later and/or at least one of the second monomers described later.

Polymer A, which does not have a constituent unit having an aromatic hydrocarbon group, is preferably obtained by polymerizing at least one of the first monomers described later, and even more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

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

The proportion of the constituent units derived from the first monomer in polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass, based on the total mass of polymer A.

The proportion of the constituent unit derived from the first monomer is preferably 10% to 50% by mass based on the total mass of polymer A. From the viewpoints of exhibiting good development properties and controlling edge melting, it is preferable to set the above proportion 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 of the resist pattern and the shape of the bottom edge, and further from the viewpoint of chemical resistance of the resist pattern, it is preferable to set the above proportion to 50% by mass or less, and from these viewpoints, 35% by mass or less is more preferable, 30% by mass or less is even more preferable, and 27% by mass or less is particularly preferred.

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

The proportion of the constituent units derived from the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass, based on the total mass of polymer A.

Furthermore, from the viewpoint of suppressing the deterioration of linewidth and resolution when the focal position deviates during exposure, polymer A is preferably composed of aralkyl constituent units and at least one constituent unit selected from the group including constituent units derived from styrene. For example, polymer A is preferably a copolymer comprising methacrylic acid, benzyl methacrylate, and styrene, or a copolymer comprising methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene.

In one state, polymer A is preferably a polymer comprising 25% to 40% by mass of a constituent unit having an aromatic hydrocarbon group, 20% to 35% by mass of a constituent unit derived from a first monomer, and 30% to 45% by mass of a constituent unit derived from a second monomer. In another state, polymer is preferably a polymer comprising 70% to 90% by mass of a constituent unit having an aromatic hydrocarbon group and 10% to 25% by mass of a constituent unit derived from a first monomer.

Polymer A may have branched structures and/or alicyclic structures in its side chains. Branched or alicyclic structures can be introduced into the side chains of polymer A by using monomers containing groups with branched structures in the side chains or monomers containing groups with alicyclic structures in the side chains. The alicyclic structure can be a monocyclic or polycyclic structure.

Specific examples of monomers containing branched groups in a side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, tributyl (meth)acrylate, isoamyl (meth)acrylate, tripentyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and trioctyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tributyl (meth)acrylate is preferred, and isopropyl (meth)acrylate or tributyl (meth)acrylate is even more preferred.

Specific examples of monomers containing alicyclic groups in their side chains include monomers with monocyclic aliphatic hydrocarbon groups and monomers with polycyclic aliphatic hydrocarbon groups. Additionally, (meth)acrylates with alicyclic hydrocarbon groups having 5 to 20 carbon atoms can be cited. As more specific examples, one could cite (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylate-1-dalcanyl ester, (meth)acrylate-2-dalcanyl ester, (meth)acrylate-3-methyl-1-dalcanyl ester, (meth)acrylate-3,5-dimethyl-1-dalcanyl ester, (meth)acrylate-3-ethyldalcanyl ester, (meth)acrylate-3-methyl-5-ethyl-1-dalcanyl ester, (meth)acrylate-3,5,8-triethyl-1-dalcanyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-dalcanyl ester, (meth)acrylate-2-methyl-2-dalcanyl ester, (meth)acrylate-2-ethyl-2-dalcanyl ester. 3-hydroxy-1-dalcenic ester of (meth)acrylate, octahydro-4,7-methanoinden-5-yl ester of (meth)acrylate, octahydro-4,7-methanoinden-1-yl methyl ester of (meth)acrylate, 1-mentholyl ester of (meth)acrylate, tricyclodecane of (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-biscyclic [3.1.1]heptyl ester of (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-biscyclic [4.1.0]heptyl ester of (meth)acrylate, (nor)camphenyl ester of (meth)acrylate, isocamphenyl ester of (meth)acrylate, fumarate of (meth)acrylate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate, and cyclohexyl ester of (meth)acrylate, etc.

Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)camphenyl (meth)acrylate, (isocamphenyl (meth)acrylate, 1-dalcanyl (meth)acrylate, 2-dalcanyl (meth)acrylate, fumarate, 1-mentholyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, with cyclohexyl (meth)acrylate, (nor)camphenyl (meth)acrylate, (isocamphenyl (meth)acrylate, 2-dalcanyl (meth)acrylate, or tricyclodecane (meth)acrylate being even more preferred.

The photosensitive layer may contain only one polymer A, or it may contain two or more polymers. When it contains two or more polymers, it is preferable to use a mixture of two polymers A containing aromatic hydrocarbons or a mixture of polymer A containing aromatic hydrocarbons and polymer A without aromatic hydrocarbons. In the latter case, it is preferable that the proportion of polymer A containing aromatic hydrocarbons relative to the total mass of polymer A is 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more.

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

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 below 135°C in the photosensitive layer, the degradation of linewidth and resolution due to focal point deviation during exposure can be suppressed. From this perspective, a Tg of polymer A below 130°C is more preferable, below 120°C is even better, and below 110°C is particularly desirable. Furthermore, from the viewpoint of improving edge melt resistance, using polymer A with a Tg of 30°C or higher is preferable. From this perspective, a Tg of polymer A above 40°C is more preferable, above 50°C is even better, above 60°C is particularly desirable, and above 70°C is optimal.

Alkali-soluble resins can be used alone or in combination of two or more. The proportion of alkali-soluble resins to the total mass of the photosensitive layer is preferably 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 development time, it is preferable to set the proportion of alkali-soluble resins to the total mass of the photosensitive layer to 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, it is preferable to set the proportion of alkali-soluble resins to the total mass of the photosensitive layer to 10% by mass or more.

The photosensitive layer may contain resins other than alkali-soluble resins. As for resins other than alkali-soluble resins, any resin that has a solubility of less than 0.1g in 100g of a 1% sodium carbonate aqueous solution at a liquid temperature of 22°C is acceptable. Examples include acrylic resins, styrene-acrylic acid copolymers (wherein the styrene content is less than 40% by mass), polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimine, polyallylamine, and polyalkylene glycol.

(Polymerizable Compound) When the photosensitive layer is a negative photosensitive layer, it is preferable that the negative photosensitive layer contains a polymerizable compound having polymerizable groups. In this disclosure, "polymerizable compound" refers to a compound that polymerizes under the action of a polymerization initiator described later, and specifically refers to a compound different from an alkaline-soluble resin. It is preferable that the molecular weight of the polymerizable compound is 1,500 or less. It is preferable that the molecular weight of the polymerizable compound is 150 or more.

The type of polymerizable group is not limited as long as it participates in the polymerization reaction. Examples of polymerizable groups include vinyl, acrylonitrile, methacrylonitrile, styrene, and cis-butenedieliimino groups, which have vinyl unsaturated groups. Examples of polymerizable groups include epoxy and oxobutyl groups, which have cationic polymerizable groups. Groups with vinyl unsaturated groups are preferred as polymerizable groups, with acrylonitrile or methacrylonitrile being even more preferred.

Polymerizable compounds containing two or more polymerizable groups are preferred. Polymerizable compounds containing two or more polymerizable groups and polymerizable compounds containing three or more polymerizable groups are even more preferred.

From the perspective of superior photosensitivity of negative photosensitive layers, compounds having one or more ethylene unsaturated groups (i.e., ethylene unsaturated compounds) are preferred as polymeric compounds, and compounds having two or more ethylene unsaturated groups per molecule (i.e., polyfunctional ethylene unsaturated compounds) are even more preferred. Furthermore, from the perspective of superior resolution and peelability, it is preferred that the number of ethylene unsaturated groups per molecule of the ethylene unsaturated compound is six or less, more preferably three or less, and even more preferably two or less.

From the perspective of achieving a superior balance between photosensitivity, resolution, and peelability of the negative photosensitive layer, it is preferable that the photosensitive layer contains compounds having two or three ethylene unsaturated groups per molecule (i.e., difunctional or trifunctional ethylene unsaturated compounds), and even more preferable that it contains compounds having two ethylene unsaturated groups per molecule (i.e., difunctional ethylene unsaturated compounds). From the perspective of excellent peelability, it is preferable that the content of difunctional ethylene unsaturated compounds relative to the total mass of the polymerizable compound is 20% by mass or more relative to the total mass of the negative photosensitive layer, more than 40% by mass is more preferable, and 55% by mass or more is even more preferable. The upper limit is not particularly limited and can be 100% by mass. That is, the polymerizable compounds can all be difunctional vinyl unsaturated compounds. Furthermore, as vinyl unsaturated compounds, (meth)acrylate compounds having (meth)acrylic groups as polymerizable groups are preferred.

The photosensitive layer preferably contains an ethylene-unsaturated compound B1 having an aromatic ring and two ethylene-unsaturated groups. The ethylene-unsaturated compound B1 is a difunctional ethylene-unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned ethylene-unsaturated compounds.

In the photosensitive layer, from the viewpoint of superior resolution, it is preferable for the mass ratio of the content of ethylene unsaturated compound B1 to the content of ethylene unsaturated compounds to be 40% by mass or more, better for 50% by mass or more, further better for 55% by mass or more, and exceptionally better for 60% by mass or more. There is no particular upper limit, but from the viewpoint of peelability, it is preferable for 99% by mass or less, better for 95% by mass or less, further better for 90% by mass or less, and exceptionally better for 85% by mass or less.

The aromatic rings possessed by the ethylene-unsaturated compound B1 can include, for example, aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocyclic rings such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; as well as their condensed rings. Aromatic hydrocarbon rings are preferred, and benzene rings are even more preferred. Furthermore, the aforementioned aromatic rings may have substituents. The ethylene-unsaturated compound B1 may have only one aromatic ring or may have two or more aromatic rings.

From the perspective of improving resolution by suppressing the swelling of the photosensitive layer caused by the developer, it is preferable that the vinyl unsaturated compound B1 has a bisphenol structure. Examples of bisphenol structures include 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.

As an ethylene-unsaturated compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acrylyl) bonded to both ends of the bisphenol structure. The two polymerizable groups at both ends of the bisphenol structure can be directly bonded or bonded via one or more alkoxy groups. As alkoxy groups added to both ends of the bisphenol structure, ethoxy or propyleneoxy is preferred, with ethoxy being more preferred. The number of alkoxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 is more preferred. Regarding the ethylene-unsaturated compound B1 having a bisphenol structure, it is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

As an ethylene-unsaturated compound B1, a difunctional ethylene-unsaturated compound with a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is even more preferred. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.). 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)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.).

As an ethylene-unsaturated compound B1, from the viewpoints of linewidth variation over time, linewidth variation at development temperature, and sensitivity, compounds containing the following formula (Bis) are preferred.

[Chemical Formula 1]

In formula ₍ Bis), _R1 and _R2 independently represent a hydrogen atom or a methyl group, 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; the repeating units of -(AO)- and -(BO)- can be arranged randomly or in blocks. Furthermore, in the case of blocks, either -(AO)- or -(BO)- can be on the bisphenol structure side. In a given state, it is preferable for _n1 + _n2 + _n3 + _n4 to be integers between 2 and 20, even better if they are integers between 2 and 16, and further better if they are integers between 4 and 12. Also, it is preferable for _n2 + _n4 to be integers between 0 and 10, even better if they are integers between 0 and 4, further better if they are integers between 0 and 2, and 0 is the best.

Ethylene unsaturated compound B1 can be used alone or in combination with two or more. From the viewpoint of superior resolution, it is preferable that the content of ethylene unsaturated compound B1 in the photosensitive layer is 10% by mass or more relative to the total mass of the photosensitive layer, and even better that it is 20% by mass or more. There is no particular upper limit, but from the viewpoint of transferability and edge melting (the phenomenon of components in the photosensitive layer seeping out from the ends of the transfer material), it is preferable that it is 70% by mass or less, and even better that it is 60% by mass or less.

The photosensitive layer may contain ethylene unsaturated compounds other than the ethylene unsaturated compound B1 mentioned above. The ethylene unsaturated compounds other than ethylene unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, compounds having one ethylene unsaturated group in one molecule (monofunctional ethylene unsaturated compounds), difunctional ethylene unsaturated compounds without an aromatic ring, and trifunctional or more ethylene unsaturated compounds can be cited.

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

Examples of difunctional ethylene-unsaturated compounds that do not have an aromatic ring include alkyl glycol di(meth)acrylate, polyalkyl glycol di(meth)acrylate, amine ester di(meth)acrylate, and trihydroxymethylpropane diacrylate.

Examples of alkyl glycol di(meth)acrylates include 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.

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

Examples of amine dimethacrylates include propylene oxide-modified amine dimethacrylates and ethylene oxide and propylene oxide-modified amine dimethacrylates. Commercially available amine dimethacrylates include 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.).

Examples of trifunctional or higher ethylene-unsaturated compounds include dinepentylenetetrol (tri/tetra/penta/hexa)methacrylate, neopentylenetetrol (tri/tetra)methacrylate, trihydroxymethylpropane tri(methacrylate), ditrihydroxymethylpropane tetra(methacrylate), trihydroxymethylethane tri(methacrylate), isocyanurate tri(methacrylate), glycerol tri(methacrylate), and their epoxide-modified forms. The term "(tri/tetra/penta/hexa)methacrylate" encompasses tri(methacrylate), tetra(methacrylate), penta(methacrylate), and hexa(methacrylate), while "(tri/tetra)methacrylate" encompasses both tri(methacrylate) and tetra(methacrylate). In one embodiment, it is preferable that the photosensitive layer contains the aforementioned ethylene unsaturated compound B1 and a trifunctional or higher ethylene unsaturated compound, and even more preferably, it contains the aforementioned ethylene unsaturated compound B1 and two or more trifunctional or higher ethylene unsaturated compounds. In this case, the mass ratio of ethylene unsaturated compound B1 to trifunctional or higher ethylene unsaturated compounds is preferably 1:1 to 5:1 (total mass of ethylene unsaturated compound B1):(total mass of trifunctional or higher ethylene unsaturated compounds) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. Furthermore, in one embodiment, it is preferable that the photosensitive layer contains the aforementioned ethylene unsaturated compound B1 and two or more trifunctional ethylene unsaturated compounds.

Examples of epoxide-modified compounds that are trifunctional or higher-functionalized ethylene 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.), and ethoxylated glycerol triacrylates (such as those manufactured by Shin-Nakamura Chemical Co., Ltd.). A-GLY-9E, etc. manufactured by Co., Ltd., ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO.,LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO.,LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO.,LTD.).

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

From the viewpoints of resolution and linearity, it is preferable that the ratio of the content of vinyl unsaturated compounds (Mm) in the photosensitive layer to the content of alkali-soluble resin (Mb), i.e., the value of Mm/Mb, is 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more but less than 0.9. Furthermore, from the viewpoints of curability and resolution, it is preferable that the vinyl unsaturated compounds in the photosensitive layer include (meth)acrylic acid compounds, and even more preferably (meth)acrylate compounds. Moreover, from the viewpoints of curability, resolution, and linearity, it is preferable that the vinyl unsaturated compounds in the photosensitive layer include (meth)acrylic acid compounds, and that the content of acrylic acid compounds relative to the total mass of the aforementioned (meth)acrylic acid compounds contained in the photosensitive layer is 60% by mass or less.

The molecular weight (weight average molecular weight (Mw) when distributed) of the ethylene unsaturated compound containing ethylene unsaturated compound B1 is preferably 200–3,000, more preferably 280–2,200, and even more preferably 300–2,200.

The polymerizable compound is preferably selected from at least one of the group consisting of ethoxylated acrylate compounds and ethoxylated methacrylate compounds, with ethoxylated methacrylate compounds being more preferred. Examples of ethoxylated methacrylate compounds include 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-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodecylethoxytetrapropoxy)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-(methacryloxydiethoxy)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.).

The polymeric compound can be used alone or in combination with two or more. The content of the polymeric compound in the photosensitive layer relative to the total mass of the photosensitive layer is preferably 10% to 70% by mass, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass.

The ratio of the mass of the polymeric compound contained in the photosensitive layer to the mass of the polymeric compound contained in the photosensitive layer is preferably 50% or less, more preferably 40%, and even more preferably 35%. If the ratio of the mass of the polymeric compound to the mass of the polymeric compound decreases, the hardness of the photosensitive layer increases. If the hardness of the photosensitive layer increases, for example, the strength of the photosensitive layer increases. Furthermore, the smoothness of the photosensitive layer surface improves. The ratio of the mass of the polymeric compound contained in the photosensitive layer to the mass of the polymeric compound contained in the photosensitive layer is preferably 10% or more, more preferably 20% or more, and even more preferably 25%. If the ratio of the mass of the polymeric compound to the mass of the polymeric compound increases, the dissolution rate of the developing solution increases, and the straightness of the line pattern improves.

(Polymerization Initiator) When the photosensitive layer is a negative photosensitive layer, it is preferable that the negative photosensitive layer contains a polymerization initiator. The polymerization initiator can be selected according to the form of polymerization reaction; for example, thermal polymerization initiators and photopolymerization initiators can be cited. Furthermore, free radical polymerization initiators and cationic polymerization initiators can be cited as examples.

It is preferable that the negative photosensitive layer contains a photopolymerization initiator. A photopolymerization initiator is a compound that undergoes polymerization upon exposure to active light sources such as ultraviolet, visible, and X-rays. There are no particular limitations on the photopolymerization initiator; any known photopolymerization initiator can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators, with photoradical polymerization initiators being preferred.

Examples of photoradical polymerization initiators include photopolymerization initiators with oxime ester structures, photopolymerization initiators with α-aminoalkylphenyl ketone structures, photopolymerization initiators with α-hydroxyalkylphenyl ketone structures, photopolymerization initiators with acetylsine oxide structures, and photopolymerization initiators with N-phenylglycine structures.

Furthermore, from the viewpoints of photosensitivity, visibility of the exposed portion, and resolution of the unexposed portion, it is preferable that the negative photosensitive layer includes at least one selected from the group consisting of 2,4,5-triarylimidazolium dimers and their derivatives as a photoradical polymerization initiator. Additionally, the two 2,4,5-triarylimidazolium structures in the 2,4,5-triarylimidazolium dimer and its derivatives may be identical or different. As derivatives of 2,4,5-triarylimidazolium dimers, examples include 2-(orthochlorophenyl)-4,5-diphenylimidazolium dimer, 2-(orthochlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(orthofluorophenyl)-4,5-diphenylimidazolium dimer, 2-(orthomethoxyphenyl)-4,5-diphenylimidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer.

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.

Examples of photoradical polymerization initiators include 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 B.V.), and 2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-1,2’-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins). Omnirad 907, manufactured by IGM Resins B.V., 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropyl)benzyl]phenyl}-2-methylpropane-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.) Omnirad 184 (manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.), and oxime ester-based photopolymerization initiators (trade name: Lunar 6, DKSH Japan). K.K. manufactures), 2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer) (trade name: B-CIM, manufactured by Hampford Company) and 2-(orthochlorophenyl)-4,5-diphenylimidazolium dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoxyxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials). (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.).

Photoionic polymerization initiators (photoacid generators) are compounds that produce acids upon exposure to active light. As photoionic polymerization initiators, compounds that produce acids upon exposure to active light with wavelengths above 300 nm, preferably between 300 nm and 450 nm, are preferred, but their chemical structure is not limited. Furthermore, photoionic polymerization initiators that do not directly sensitize to active light with wavelengths above 300 nm, as long as they are compounds that produce acids upon exposure to active light with wavelengths above 300 nm by being used in conjunction with a sensitizer, can also be used in combination with the sensitizer for optimal results. As a photocatalytic polymerization initiator, it is preferable to produce an acid photocatalytic polymerization initiator with a pKa of 4 or lower, even better to produce an acid photocatalytic polymerization initiator with a pKa of 3 or lower, and especially preferable to produce an acid photocatalytic polymerization initiator with a pKa of 2 or lower. There is no specific requirement for the lower limit of pKa, but for example, a value above -10.0 is preferred.

Examples of ionic and nonionic photopolymerization initiators include those for photopolymerization. Examples of ionic photopolymerization initiators include onium salts such as diarylamium salts and triarylstromium salts, as well as quaternary ammonium salts. As ionic photopolymerization initiators, those described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 may be used.

Examples of nonionic photoionic polymerization initiators include trichloromethyl-s-triazine compounds, diazomethane compounds, amide sulfonate compounds, and oxime sulfonate compounds. For trichloromethyl-s-triazine compounds, diazomethane compounds, and amide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 can be used. Furthermore, for oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be used.

The photosensitive layer may contain only one type of photopolymerization initiator, or it may contain two or more types. The content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but it is preferable to be 0.1% by mass or more relative to the total mass of the photosensitive layer, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. There is no particular upper limit, but it is preferable to be 10% by mass or less relative to the total mass of the photosensitive layer, and even more preferably 5% by mass or less.

(Pigment) From the perspective of visibility of both exposed and unexposed areas, visibility of the developed pattern, and resolution, it is better for the photosensitive layer to contain pigment. It is even better to contain pigments with a maximum absorption wavelength of 450nm or higher in the wavelength range of 400nm–780nm during color development, and whose maximum absorption wavelength changes with acids, alkalis, or free radicals (also referred to as "pigment N"). While the detailed mechanism is not yet fully understood, the presence of pigment N improves adhesion to adjacent layers (e.g., temporary supports and intermediate layers), resulting in superior resolution.

In this disclosure, the phrase "the maximum absorption wavelength of a pigment changes due to acids, alkalis, or free radicals" can refer to any of the following states: a pigment in a chromogenic state that decolorizes due to acids, alkalis, or free radicals; a pigment in a decolorized state that develops color due to acids, alkalis, or free radicals; or a pigment in a chromogenic state that changes to another hue. Specifically, pigment N can be a compound that changes from a decolorized state to a chromogenic state upon exposure, or a compound that changes from a chromogenic state to a decolorized state upon exposure. In this case, the pigment can be one whose color development or decolorization occurs due to the generation of acids, alkalis, or free radicals within the photosensitive layer upon exposure. Alternatively, the pigment can be one whose color development or decolorization occurs due to changes in the state (e.g., pH) within the photosensitive layer caused by acids, alkalis, or free radicals. Furthermore, the pigment can also be one whose color development or decolorization occurs directly upon exposure to acids, alkalis, or free radicals without prior exposure.

From the perspective of visibility and resolution of both exposed and unexposed areas, it is preferable that pigment N is a pigment whose absorption wavelength changes with acid or free radicals, and even more preferable that is a pigment whose absorption wavelength changes with free radicals. From the perspective of visibility and resolution of both exposed and unexposed areas, it is preferable that the photosensitive layer contains both a pigment (pigment N) whose absorption wavelength changes with free radicals and a photoradical polymerization initiator. Furthermore, from the perspective of visibility of both exposed and unexposed areas, it is preferable that pigment N is a pigment that develops color through acid, alkali, or free radicals.

As an example of the color-developing mechanism of pigment N in this disclosure, one can cite the following: a free radical reactive pigment, an acid reactive pigment, or an alkali reactive pigment (e.g., a colorless pigment) develops color from the free radicals, acids, or alkalis generated by the photoradical polymerization initiator, photocation polymerization initiator (photoacid generator), or photoalkali generator after exposure to the photosensitive layer.

From the perspective of visibility of both the exposed and unexposed areas, it is preferable that the maximum absorption wavelength of pigment N in the wavelength range of 400nm–780nm is 550nm or higher, 550nm–700nm is even better, and 550nm–650nm is even better. Furthermore, pigment N may have only one maximum absorption wavelength in the wavelength range of 400nm–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–780nm for color development, the maximum absorption wavelength with the highest absorbance among these two or more maximum absorption wavelengths should be 450nm or higher.

The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) in the range of 400nm to 780nm using a UV3100 spectrophotometer (manufactured by Shimadzu Corporation) in an atmospheric environment and detecting the wavelength at which the light intensity becomes minimal (maximum absorption wavelength).

As pigments that develop or decolorize upon exposure, examples include colorless compounds. As pigments that decolorize upon exposure, examples include colorless compounds, diarylmethane pigments, acetylene pigments, sigmazone pigments, iminonaphthoquinone pigments, azomethine pigments, and anthraquinone pigments. From the viewpoint of visibility of both exposed and unexposed areas, colorless compounds are preferable as pigment N.

Colorless compounds include, for example, those with a triarylmethane skeleton (triarylmethane pigments), those with a spiropipran skeleton (spiropipran pigments), those with a fluorescent yellow parent skeleton (fluorescent yellow parent pigments), those with a diarylmethane skeleton (diarylmethane pigments), those with a rhodamine lactone skeleton (rhodamine lactone pigments), those with an indolephthalide skeleton (indolephthalide pigments), and those with a colorless auramine skeleton (colorless auramine pigments). Among these, triarylmethane pigments or fluorescent yellow parent pigments are preferred, and colorless compounds with a triphenylmethane skeleton (triphenylmethane pigments) or fluorescent yellow parent pigments are even more preferred.

From the perspective of visibility of both exposed and unexposed areas, it is preferable for a colorless compound to possess 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 from a photoradical polymerization initiator or with acids generated from a photoionic polymerization initiator, thereby either decolorizing the colorless compound by changing it to a closed-ring state or making it color-developing by changing it to an open-ring state. As a colorless compound, a compound having a lactone ring, sulfinolone ring, or sulfonolone ring, and the lactone ring, sulfinolone ring, or sulfonolone ring showing color through ring-opening by free radicals or acids, is preferred; a compound having a lactone ring and the lactone ring showing color through ring-opening by free radicals or acids is even more preferred.

As a pigment N, examples include the following dyes and colorless compounds. Among pigments N, specific examples of dyes 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-naphthyl 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.), and Oil Blue #603 (orient Chemical Industries). Oil Red #312 (manufactured by Orient Chemical Industries Co., Ltd.), 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.), Spilon Red BEH Special (Hodogaya Chemical Co., Ltd.) (Manufactured by Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, aureamine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-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.

Among pigments N, specific examples of colorless compounds include p,p',p”-hexamethyltriaminetriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoxide colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow parent material, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl)fluorescent yellow parent material, 3,6-dimethoxyfluorescent yellow parent material, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorescent yellow parent material, and 3-(N-cyclohexyl-N-methylamino)-6-methyl -7-aniline fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-aniline fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-amino fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow parent material, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorescent yellow parent material, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorescent yellow parent material, 3- (N,N-Diethylamino)-7-benzylamino fluorescent yellow parent compounds, 3-(N,N-Diethylamino)-7,8-benzofluorine, 3-(N,N-Dibutylamino)-6-methyl-7-aniline fluorescent yellow parent compounds, 3-(N,N-Dibutylamino)-6-methyl-7-aniline fluorescent yellow parent compounds, 3-piperidinyl-6-methyl-7-aniline fluorescent yellow parent compounds, 3-pyrrolidinyl-6-methyl-7-aniline fluorescent yellow parent compounds, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalolide (phthali de), 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalolide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalolide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalolide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalolide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]-yamagata-3-one.

From the perspectives of visibility of both exposed and unexposed areas, as well as the visibility and resolution of the developed pattern, pigment N that absorbs wavelengths at extremely high wavelengths and changes color due to free radicals is preferred, and pigments that develop color through free radicals are even better. As pigment N, colorless crystalline violet, crystalline violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate are preferred.

Pigment N can be used alone or in combination with other pigments. From the perspective of visibility of both exposed and unexposed areas, as well as the visibility and resolution of the developed pattern, a pigment N content of 0.1% by mass or more relative to the total mass of the photosensitive layer is preferred, 0.1% to 10% by mass is more preferred, 0.1% to 5% by mass is even more preferred, and 0.1% to 1% by mass is particularly preferred. Furthermore, from the perspective of visibility of both exposed and unexposed areas, as well as the visibility and resolution of the developed pattern, a pigment N content of 0.1% by mass or more relative to the total mass of the photosensitive layer is preferred, 0.1% to 10% by mass is more preferred, 0.1% to 5% by mass is even more preferred, and 0.1% to 1% by mass is particularly preferred.

The content of pigment N refers to the amount of pigment required to bring all pigment N contained in the photosensitive layer to a colored state. The following explanation uses a pigment that develops color via free radicals as an example to illustrate the quantitative method for determining the content of pigment N. Two solutions were prepared, each containing 0.001 g or 0.01 g of pigment dissolved in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (trade name: Irgacure OXE01, manufactured by BASF) was added to each solution, and the solutions were irradiated with 365 nm light to generate free radicals, thus bringing all pigments to a colored state. Then, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and calibration curves were constructed. Next, except that 3g of the photosensitive layer was dissolved in methyl ethyl ketone instead of the pigment, the absorbance of the solution that caused the pigment to fully develop was measured using the same method as described above. Based on the absorbance of the obtained solution containing the photosensitive layer, the content of pigment contained in the photosensitive layer was calculated according to the calibration curve.

(Thermocrosslinking compounds) From the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film, it is preferable for the photosensitive layer to contain a thermocrosslinking compound. Furthermore, in this disclosure, the thermocrosslinking compounds having vinyl unsaturated groups described later are not treated as vinyl unsaturated compounds, but are treated as thermocrosslinking compounds. Examples of thermocrosslinking compounds include hydroxymethyl compounds and capped isocyanate compounds. Among these, capped isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film. End-capped isocyanate compounds react with hydroxyl and carboxyl groups. Therefore, when alkaline soluble resins and/or vinyl unsaturated compounds, for example, have at least one of hydroxyl and carboxyl groups, the hydrophilicity of the resulting film decreases, thereby enhancing the function of the film formed by curing the photosensitive layer as a protective film. Furthermore, end-capped isocyanate compounds refer to compounds having a structure in which "isocyanate groups of isocyanate are protected (masked) by an end-capping agent."

The dissociation temperature of the terminal isocyanate compound is not particularly limited, but 100°C to 160°C is preferred, and 130°C to 150°C is even better. The dissociation temperature of the terminal isocyanate refers to "the temperature of the endothermic peak accompanying the deprotection reaction of the terminal isocyanate when analyzed and determined using a differential scanning calorimeter by DSC (Differential Scanning Calorimetry)." For example, a differential scanning calorimeter manufactured by Seiko Instruments Inc. (model: DSC6200) is preferred. However, the differential scanning calorimeter is not limited to this.

Examples of end-capping agents with a dissociation temperature of 100°C to 160°C include active methylene compounds (malonate diesters (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., compounds having a structure represented by -C (=N-OH)- in the molecule). Among these, for example, from the viewpoint of maintaining stability, end-capping agents with a dissociation temperature of 100°C to 160°C containing oxime compounds are preferred.

For example, from the viewpoint of improving film brittleness and enhancing adhesion to the substrate, it is preferable for the capping isocyanate compound to have an isocyanurate structure. A capping isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanuric acid esterification of hexamethylene diisocyanate to protect it. Among capping isocyanate compounds having an isocyanurate structure, from the viewpoint that it is easier to set the dissociation temperature within a better range and easier to reduce developing residue compared to compounds without an oxime structure, compounds with an oxime structure in which an oxime compound is used as a capping agent are preferred.

Terminal isocyanate compounds can have polymerizable groups. There are no particular limitations on the polymerizable group; known polymerizable groups can be used, with free radical polymerizable groups being preferred. Examples of polymerizable groups include vinyl unsaturated groups such as (meth)acryloxy, (meth)acrylamine, and styrene, as well as epoxy groups such as glycidyl groups. Among these, vinyl unsaturated groups are preferred, (meth)acryloxy is more preferred, and acryloxy is even more preferred.

Commercially available products can be used as terminal-capped isocyanate compounds. Examples of commercially available terminal-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 K.K.), and the terminal-capped Duranat series (e.g., Duranat (registered trademark) TPA-B80E, Duranat (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Furthermore, compounds with the following structure can also be used as terminal-capped isocyanate compounds.

[Chemical Formula 2]

A single thermal crosslinking compound can be used alone, or two or more can be used. When the photosensitive layer contains a thermal crosslinking compound, the content of the thermal crosslinking compound relative to the total mass of the photosensitive layer is preferably 1% to 50% by mass, and 5% to 30% by mass is even better.

(Other Components) The photosensitive layer may contain components other than the alkaline-soluble resins, polymerizable compounds, polymerization initiators, pigments, and thermally crosslinking compounds mentioned above. Examples of other components include free radical polymerization inhibitors, surfactants, sensitizers, and various additives. These other components may be used individually or in combination.

<Free Radical Polymerization Inhibitor> The photosensitive layer may contain a free radical polymerization inhibitor. Examples of free radical polymerization inhibitors include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenanthrene, phenanthrene, or 4-methoxyphenol are preferred. Other free radical polymerization inhibitors include naphthylamine, copper(I), aluminum nitrosophenylhydroxyamine, and diphenylnitrosamine. To avoid impairing the sensitivity of the photosensitive layer, aluminum nitrosophenylhydroxyamine is preferred as the free radical polymerization inhibitor.

Free radical polymerization inhibitors can be used alone or in combination. When the photosensitive layer contains a free radical polymerization inhibitor, the content of the free radical polymerization inhibitor relative to the total mass of the photosensitive layer is preferably 0.001% to 5.0% by mass, more preferably 0.01% to 3.0% by mass, and even more preferably 0.02% to 2.0% by mass. Furthermore, the content of the free radical polymerization inhibitor relative to the total mass of the polymerizable compound is preferably 0.005% to 5.0% by mass, more preferably 0.01% to 3.0% by mass, and even more preferably 0.01% to 1.0% by mass.

-Surfactant- It is preferable that the photosensitive layer contains a surfactant. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Application Publication No. 2009-237362. Furthermore, nonionic surfactants, fluorinated surfactants, or silicone surfactants are preferred.

Commercially available fluorinated surfactants include, for example, MEGAFACE (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, and F- 568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS578-2, 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) Fluorinated surfactants include Ftergent (trade name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by Neos Company Limited), and U-120E (Uni-chem Co., Ltd.). Furthermore, fluorinated surfactants can also better utilize acrylic compounds, which have a molecular structure containing functional groups with fluorine atoms. When heated, these functional groups are cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the MEGAFACE (trade name) DS series manufactured by DIC Corporation (Kako Kogyo Nichijou (February 22, 2016), Nikkei Business Daily (February 23, 2016)), such as MEGAFACE (trade name) DS-21.

Furthermore, polymers containing fluorinated ethylene ether compounds with fluorinated alkyl or fluorinated alkyl ether groups and hydrophilic ethylene ether compounds are preferred as fluorinated surfactants. End-capped polymers can also be used as fluorinated surfactants. Fluorinated polymers containing fluorinated atoms, comprising (meth)acrylate compounds having fluorinated atoms and (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propyleneoxy), are also preferred as fluorinated surfactants. Fluorinated polymers having vinyl unsaturated groups in the side chains can also be used as fluorinated surfactants. Examples include MEGAFACE (trade name) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). As fluorinated surfactants, compounds with linear perfluoroalkyl groups having 7 or more carbon atoms can also be used. However, from the perspective of improving environmental adaptability, it is preferable to use perfluorooctanoic acid (PFOA) or perfluorooctanoic acid (PFOS) as alternatives to fluorinated surfactants.

Examples of nonionic surfactants include glycerol, trihydroxymethylpropane, trihydroxymethylethane, and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, dehydrated 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, and HYDROPALAT WE 3323 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-1105, D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends. Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (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 (manufactured by Dow Corning Toray Silicone). (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (manufactured by BYK...). (Manufactured by Chemie Corporation, etc.)

The photosensitive layer may contain only one type of surfactant or two or more types. The surfactant content relative to the total mass of the photosensitive layer is preferably 0.001% to 10% by mass, and even more preferably 0.01% to 3% by mass.

-Sensitizer- The photosensitive layer may contain a sensitizer. There are no particular limitations on the sensitizer; known sensitizers, dyes, and pigments can be used. Examples of sensitizers include, for instance, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridinium compounds, acetazole compounds, benzo[a]acetazole compounds, thiazole compounds, benzo[a]thiazole compounds, triazole compounds (e.g., 1,2,4-triazole), zirconia compounds, triazine compounds, thiophene compounds, naphthalenedimethylimine compounds, triarylamine compounds, and aminoacridine compounds.

Sensitizers can be used alone or in combination. When a photosensitive layer contains a sensitizer, the amount of sensitizer can be selected appropriately according to the purpose. However, from the perspective of improving the sensitivity to light sources and increasing the curing speed by balancing the polymerization rate and chain transfer, a content of 0.01% to 5% of the total mass of the photosensitive layer is preferred, and 0.05% to 1% is even better.

-Additives- In addition to the components mentioned above, the photosensitive layer may contain known additives as needed. Examples of additives include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (such as isoniazid amides), purine bases (such as adenine), and solvents. The photosensitive layer may contain one or more additives.

Examples of benzotriazoles include 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.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethyl carboxybenzotriazole. Commercially available products such as CBT-1 (JOHOKU CHEMICAL CO.,LTD., trade name) are also examples of carboxybenzotriazoles.

The combined content of benzotriazoles and carboxybenzotriazoles relative to the total mass of the photosensitive layer is preferably 0.01% to 3% by mass, and more preferably 0.05% to 1% by mass. From the viewpoint of preserving the stability of the photosensitive 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 fading, it is preferable to set the above content to 3% by mass or less.

The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of plasticizers and heterocyclic compounds include compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018/179640.

Photosensitive layers may contain solvents. When a photosensitive layer is formed from a photosensitive resin composition containing solvent, sometimes solvent residue remains in the photosensitive layer.

Furthermore, the photosensitive layer may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, developing agents, conductive fibers, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors. The additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated herein by reference.

(Impurities, etc.) The photosensitive layer may contain a certain amount of impurities. 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, halogen ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferred.

The impurity content in the photosensitive layer is preferably below 80 ppm by mass, even better if it is below 10 ppm, and further preferably below 2 ppm by mass. The impurity content can be set to above 1 ppb by mass, or it can be set to above 0.1 ppm by mass.

As a method to keep impurities within the aforementioned range, examples include selecting raw materials with low impurity content, preventing impurity contamination during the fabrication of the photosensitive layer, and cleaning to remove impurities. By using these methods, the amount of impurities can be kept within the aforementioned range.

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

It is preferable that the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is low. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and further preferably 4 ppm or less. The lower limit relative to the total mass of the photosensitive layer can be set to 10 ppb or more, or 100 ppb or more. The content of these compounds can be suppressed using the same method as for impurities in the aforementioned metals. Furthermore, they can be quantified using known methods.

From the perspective of improving reliability and lamination, the water content in the photosensitive layer is preferably 0.01% to 1.0% by mass, and even better is 0.05% to 0.5% by mass.

(Residual monomers) The photosensitive layer sometimes contains residual monomers corresponding to the constituent units of the aforementioned alkali-soluble resin. From the viewpoint of patternability and reliability, it is preferable that the content of residual monomers relative to the total mass of the alkali-soluble resin is 5,000 ppm or less, more preferably 2,000 ppm or less, and even more preferably 500 ppm or less. The lower limit is not particularly limited, but 1 ppm or more is preferable, and 10 ppm or more is even more preferable. From the perspective of patternability and reliability, it is preferable that the residual monomers of each constituent unit of the alkali-soluble resin relative to the total mass of the photosensitive layer be below 3,000 ppm, more preferably below 600 ppm, and even more preferably below 100 ppm. The lower limit is not particularly limited, but above 0.1 ppm is preferable, and above 1 ppm is even better.

When synthesizing alkali-soluble resins via polymer reactions, it is preferable that the residual monomer content be within the aforementioned range. For example, when synthesizing alkali-soluble resins by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable that the glycidyl acrylate content be within the aforementioned range. The amount of residual monomers can be determined using known methods such as liquid chromatography and gas chromatography.

[Physical Properties, etc.] From the viewpoint of development and resolution, a photosensitive layer thickness of 20 μm or less is preferred, 10 μm or less is even better, 8 μm or less is further better, 5 μm or less is particularly good, and 1 μm or more but less than 5 μm is optimal. The thickness of the photosensitive layer is calculated using the method described for calculating the thickness of the temporary support.

Furthermore, from the perspective of superior adhesion, a transmittance of 10% or higher for light with a wavelength of 365nm in the photosensitive layer is preferable, 30% or higher is even better, and 50% or higher is even better. There is no particular upper limit, but 99.9% or lower is preferred.

[Forming Method] The method for forming the photosensitive layer is not particularly limited as long as it is capable of forming a layer containing the above-mentioned components. For example, a method for forming the photosensitive layer can be described by the following steps: preparing a photosensitive resin composition containing an alkali-soluble resin, an ethylene-unsaturated compound, a photopolymerization initiator, and a solvent; coating the photosensitive resin composition onto the surface of a temporary support or similar structure; and drying the coating of the photosensitive resin composition. From the viewpoint of controlling the roughness Ra of the first surface of the photosensitive layer, it is preferable that the photosensitive layer is formed by coating the surface of a temporary support with the photosensitive resin composition. As a drying method for a coating of photosensitive resin composition, heating drying and depressurization drying are preferred. Furthermore, in this disclosure, "drying" refers to the removal of at least a portion of the solvent contained in the composition. Examples of drying methods include natural drying, heating drying, and depressurization drying. These methods can be used individually or in combination. As a drying temperature, 80°C or higher is preferred, and 90°C or higher is more preferred. Furthermore, as an upper limit, 130°C or lower is preferred, and 120°C or lower is more preferred. Drying can also be performed by continuously changing the temperature. As a drying time, 20 seconds or more is preferred, 40 seconds or more is more preferred, and 60 seconds or more is further preferred. Furthermore, as for its upper limit, it is not specifically limited, but 600 seconds or less is better, and 300 seconds or less is even better.

Photosensitive resin compositions used in the formation of the photosensitive layer may include, for example, compositions containing an alkaline-soluble resin, an ethylene-unsaturated compound, a photopolymerization initiator, any of the above components, and a solvent. It is preferable that the photosensitive resin composition contains a solvent to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive layer.

As a solvent contained in the photosensitive resin composition, there are no particular limitations as long as it can dissolve or disperse the alkaline soluble resin, the vinyl unsaturated compound, the photopolymerization initiator, and any of the above components; any known solvent can be used. Examples of solvents include alkyl glycol ether solvents, alkyl glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these. The photosensitive resin composition preferably contains at least one solvent selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents. More preferably, it contains a mixed solvent consisting of at least one solvent selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents and at least one solvent selected from the group consisting of ketone solvents and cyclic ether solvents. It is further preferred that it contains at least one solvent selected from the group consisting of at least one solvent selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

Examples of alkyl glycol ether solvents include, for example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Examples of alkyl glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. Solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may also be used, the contents of which are incorporated herein by reference.

Photosensitive resin compositions may contain only one solvent or two or more solvents. When applying a photosensitive resin composition, the solvent content relative to 100 parts by weight of the total solids in the photosensitive resin composition is preferably 50 parts by weight to 1,900 parts by weight, and more preferably 100 parts by weight to 900 parts by weight.

The preparation method of the photosensitive resin composition is not particularly limited. For example, a method can be given by pre-preparing a solution in which each component is dissolved in the above-mentioned solvent, and then mixing the resulting solutions in a predetermined ratio to prepare the photosensitive resin composition. It is preferable to filter the photosensitive resin composition using a filter with a pore size of 0.2 μm to 30 μm before forming the photosensitive layer.

The application method of the photosensitive resin composition is not particularly limited, and any known method can be used. Examples of application methods include slit application, spin coating, curtain coating, and inkjet coating. Furthermore, the photosensitive layer can be formed by applying the photosensitive resin composition onto the protective film described later and then drying it.

The protective film, in one embodiment of the transfer material disclosed herein, is preferably the outermost layer on the side opposite to the temporary support. Furthermore, it is preferable that the protective film contacts both the photosensitive layer and the side opposite to the contact surface with the temporary support.

Materials used to construct protective films include resin films and paper; from the perspective of strength and flexibility, resin films are preferred. Examples of resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred.

The thickness (layer thickness) of the protective film is not particularly limited, but 1 μm to 100 μm is preferred, 5 μm to 50 μm is more preferred, 5 μm to 40 μm is even more preferred, and 15 μm to 30 μm is particularly preferred. Furthermore, from the viewpoint of superior resolution, it is preferred that the arithmetic mean roughness Ra value of the surface of the protective film in contact with the photosensitive layer (hereinafter also referred to as the "surface of the protective film") be 0.3 μm or less, 0.1 μm or less is more preferred, and 0.05 μm or less is even more preferred. This is because if the Ra value of the protective film surface is within the above range, the uniformity of the thickness of the photosensitive layer and the formed resin pattern is improved. The lower limit of the Ra value of the protective film surface is not particularly limited, but values above 0.001 μm are preferred.

The Ra value of the protective film surface was measured using the following method. The surface profile of the optical film was obtained by measuring the surface of the protective film under the following conditions using a 3D optical profilometer (New View 7300, manufactured by Zygo). The Microscope Application of MetroPro ver 8.3.2 was used as the measurement/analysis software. Next, a Surface Map was displayed using the aforementioned analysis software, and histogram data was obtained from the Surface Map. The arithmetic mean roughness was calculated based on the obtained histogram data, thereby obtaining the Ra value of the protective film surface. When the protective film was adhered to the transfer material, it was peeled off from the transfer material, and the Ra value of the peeled-off surface was measured.

Furthermore, transfer materials can be manufactured by laminating a protective film onto a photosensitive layer, etc. The method of laminating the protective film onto the photosensitive layer, etc., is not particularly limited, and known methods can be cited. Known laminators such as vacuum laminators and automatic cutting laminators can be cited as devices for laminating the protective film onto the photosensitive layer. It is preferable to use a laminator equipped with any heatable rollers, such as rubber rollers, and capable of both pressurization and heating.

Refractive Index Adjustment Layer One embodiment of the transfer material disclosed herein may include a refractive index adjustment layer (i.e., a contrast enhancement layer). The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018/179640. Other layers 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.

From the perspective of resolution and adhesion to the substrate, it is preferable that the total thickness of all layers in the transfer material, excluding the temporary support and the protective film, is less than 20 μm, even better than 10 μm, further better than 8 μm, and especially better than 2 μm and less than 8 μm.

"Relationship between Temporary Support, Photosensitive Layer and Protective Film" In the transfer material of one embodiment disclosed herein, it is preferable that the hardened film formed by hardening the photosensitive layer has an elongation at break of 15% or more at 120°C, the arithmetic mean roughness Ra of the photosensitive layer side surface of the temporary support is 50 nm or less, and the arithmetic mean roughness Ra of the photosensitive layer side surface of the protective film is 150 nm or less.

Furthermore, the transfer material disclosed herein preferably satisfies the following formula (R1): X×Y < 1,500: Formula (R1) Wherein, in the above formula (R1), X represents the elongation at break (%) of the hardened film formed by curing the photosensitive layer at 120°C, and Y represents the arithmetic mean roughness Ra (nm) of the surface of the photosensitive layer side of the temporary support. X×Y being 750 or less is more preferred.

Compared to the elongation at break of a hardened film formed by curing the photosensitive layer at 23°C, it is preferable to have an elongation at break of more than twice that at 120°C. The elongation at break is determined by using a hardened film and conducting a tensile test. The hardened film is formed by curing a 20μm thick photosensitive layer by exposure to an ultra-high pressure mercury lamp at 120mJ/ ^cm² , followed by further exposure to a high pressure mercury lamp at 400mJ/ ^cm² , and then heating at 145°C for 30 minutes.

Furthermore, it is preferable that the transfer material disclosed herein satisfies the following formula (R2). A. Y≤Z: Formula (R2) Wherein, in the above formula (R2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the photosensitive layer side of the temporary support, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface of the photosensitive layer side of the protective film.

The manufacturing method of the transfer material disclosed herein is not particularly limited, and known manufacturing methods, such as known methods for forming each layer, can be used. Hereinafter, the manufacturing method of the transfer material disclosed herein will be described with reference to FIG1. However, the transfer material disclosed herein is not limited to having the structure shown in FIG1.

As a method for manufacturing the transfer material 100, an example method may include the following steps: after coating the surface of the temporary support 10 with a photosensitive resin composition comprising an alkali-soluble resin and an ethylene-unsaturated compound, the photosensitive resin composition is dried to form a photosensitive layer 20. In the above manufacturing method, it is preferable to use a photosensitive resin composition comprising an alkali-soluble resin, an ethylene-unsaturated compound, and at least one selected from the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents.

The protective film 30 is pressed onto the photosensitive layer 20 of the laminate manufactured by the above-described manufacturing method, thereby producing the transfer material 100. As a method for manufacturing the transfer material used in this disclosure, it is preferable to manufacture the transfer material 100 having the temporary support 10, the photosensitive layer 20, and the protective film 30 by including a step of disposing the protective film 30 in contact with the surface of the photosensitive layer 20 opposite to the side where the temporary support 10 is disposed. After the transfer material 100 is manufactured by the above-described manufacturing method, a roll-shaped transfer material can be produced and stored by rolling the transfer material 100. The roll-shaped transfer material can be directly supplied in this form to the roll-to-roll bonding step described later.

The transfer material of one embodiment disclosed herein is preferably used in various applications requiring precision microfabrication based on photolithography. After patterning the photosensitive layer, it can be etched as a film or electroformed using electroplating as the main process. Furthermore, the hardened film obtained by 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 transfer material of one embodiment disclosed herein is preferably used in various wiring formation applications in semiconductor packaging, printed circuit boards, and sensor substrates, as well as in touch panels, electromagnetic wave shielding materials, conductive films such as thin-film heaters, liquid crystal sealing materials, and the formation of structures in the fields of micromechanics or microelectronics.

Furthermore, the transfer material of one embodiment disclosed herein can also preferably be exemplified as a colored resin layer in which the photosensitive layer contains pigment. In addition to the above-mentioned applications, the colored resin layer is suitable for, for example, forming colored pixels or black matrices in color filters used in liquid crystal display devices (LCDs) and solid-state imaging elements (e.g., CCDs and CMOS). In recent years, electronic devices sometimes have cover glass with a black frame-shaped light-shielding layer formed on the back periphery of a transparent glass substrate or the like to protect the liquid crystal display window. A colored resin layer can be used to form this light-shielding layer. The state of the colored resin layer, excluding the pigment, is the same as described above.

As for the pigments used in the coloring resin layer, they can be selected appropriately according to the desired hue, and can be chosen from black pigments, white pigments, and colored pigments other than black and white. Among them, when forming a black pattern, black pigment is the better choice.

As a black pigment, any known black pigment (organic or inorganic pigment, etc.) can be appropriately selected, provided it does not impair the effects described herein. From the viewpoint of optical concentration, carbon black, titanium oxide, titanium carbide, iron oxide, and graphite are preferred black pigments, with carbon black being particularly advantageous. From the viewpoint of surface resistance, carbon black with at least a portion of its surface coated with resin is preferred.

From the perspective of dispersion stability, the particle size of black pigment is preferably 0.001 μm to 0.1 μm, and even more preferably 0.01 μm to 0.08 μm, based on the number average particle size. Here, particle size refers to the diameter of a circle with the same area as the pigment particle when calculating the area of the pigment particle from an electron microscope photograph. The number average particle size is the average value obtained by averaging the above particle size for any 100 particles.

Regarding white pigments other than black pigments, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Publication No. 2005-007765 may be used. Specifically, among white pigments, titanium oxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, with titanium oxide or zinc oxide being more preferred, and titanium oxide being even more preferred. As inorganic pigments, rutile or anatase-type titanium oxide is even more preferred, and rutile-type titanium oxide is particularly preferred. Furthermore, the surface of titanium oxide can be treated with silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide, or organic materials, or two or more of these treatments can be applied. This suppresses the catalytic activity of titanium oxide and improves its heat resistance and fading properties. From the viewpoint of reducing the thickness of the heated photosensitive layer, at least one of aluminum oxide treatment and zirconium dioxide treatment is preferred for the surface treatment of titanium oxide, with both aluminum oxide treatment and zirconium dioxide treatment being particularly preferred.

Furthermore, when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is preferable for the photosensitive layer to further include colored pigments other than black and white pigments. When colored pigments are included, from the viewpoint of better dispersibility, a particle size of 0.1 μm or less is preferable, and 0.08 μm or less is even better. As color pigments, examples include Victoria Blue BO (Color Index 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolight Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hostaperm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), and Pastel Pink. Pink) B Supura (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolight Fast Black B (C.I. Pigment Black 1), and Carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, and C.I. Pigment Violet 23, etc. Among them, C.I. Pigment Red 177 is better.

When the photosensitive layer contains pigments, the pigment content relative to the total mass of the photosensitive layer is preferably more than 3% and less than 40% by mass, even better is more than 3% and less than 35% by mass, further better is more than 5% and less than 35% by mass, and best is more than 10% and less than 35% by mass.

When the photosensitive layer contains pigments other than black pigment (white pigment and colored pigment), it is better for the content of pigments other than black pigment to be less than 30% by mass, 1% to 20% by mass is better, and 3% to 15% by mass is even better.

Furthermore, when the photosensitive layer contains black pigment and is formed of a photosensitive resin composition, it is preferable that the black pigment (preferably carbon black) be introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion can be prepared by adding a mixture of pre-mixed black pigment and a pigment dispersant to an organic solvent (or vehicle) 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 vehicle refers to the medium that disperses the pigment during the preparation of the pigment dispersion; it is liquid and includes a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

There are no particular limitations on what a dispersant can be; examples include well-known dispersants such as kneaders, roller mills, attritors, super mills, dissolvers, homogenizers, and sand mills. Additionally, mechanical grinding can be used to achieve micronization through friction. For more information on dispersants and micronization, please refer to the "Pigment Dictionary" (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

<Manufacturing Method of a Laminate> A method for manufacturing a laminate according to an embodiment disclosed herein includes the following steps in sequence: bonding a transfer material comprising a temporary support and a photosensitive layer in contact with the temporary support to a substrate; sequentially disposing the photosensitive layer and the temporary support on the substrate (hereinafter, sometimes referred to as the "bonding step"); and peeling the temporary support from the photosensitive layer. The process involves peeling off a body (hereinafter sometimes referred to as the "peeling step"); and applying exposure and development processing to the photosensitive layer exposed by peeling off the temporary support body to form a pattern (hereinafter sometimes referred to as the "pattern forming step"). The surface roughness Ra of the photosensitive layer exposed by peeling off the temporary support body is 2 nm or more. In the manufacturing method of the laminate in one embodiment of the present disclosure, the transfer material described in the "transfer material" section above is preferably used as the transfer material. Furthermore, it is preferable that at least a portion of the pattern obtained in the pattern forming step includes a line and a spatial pattern. It is preferable that the combined width of at least one set of lines and spaces in the line and spatial pattern is 20 μm or less.

In the bonding step, a transfer material including a temporary support and a photosensitive layer in contact with the temporary support is bonded to the substrate. The photosensitive layer and the temporary support are sequentially disposed on the substrate. When a conductive layer is provided on the surface of the substrate, it is preferable to bond the transfer material to the conductive layer of the substrate. Bonding the transfer material to the substrate preferably involves pressing the transfer material to the substrate. Because the adhesion between the transfer material and the substrate is improved, the patterned photosensitive layer after exposure and development can be better used as an etching resist during the etching of the conductive layer. Furthermore, when the transfer material has a protective film, the protective film can be removed before bonding.

The method for bonding the transfer material to the substrate is not particularly limited, and known transfer and lamination methods can be used. It is preferable to bond the transfer material to the substrate by stacking the transfer material and the substrate and applying pressure and heat using a mechanism such as rollers. Known laminators such as laminators, vacuum laminators, and automated cutting laminators that can further improve productivity can be used for lamination. The lamination temperature is not particularly limited, but for example, 70°C to 130°C is preferred.

A method for manufacturing a laminate, including a bonding step, is preferably performed using a roller-to-roll method. The roller-to-roll method will be explained below. The roller-to-roll method refers to the following: using a substrate capable of being wound and unwound as the substrate, the method includes a step of unwound the substrate or a structure containing the substrate (also called the "unwound step") before any step included in the method for manufacturing the laminate, and a step of winding the substrate or a structure containing the substrate (also called the "winding step") after any step, 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 conveyed. The winding method in the winding step and the winding method in the winding step are not particularly restricted, as long as known methods are used in the manufacturing method applicable to the roller-to-roll method.

As a substrate, any known substrate can be used, but a substrate with a conductive layer is preferred, and a conductive layer on the surface of the substrate is even more preferred. The substrate may have any layer other than a conductive layer, as needed. Examples of substrates include resin substrates, glass substrates, and semiconductor substrates. A preferred embodiment of the substrate is, for example, paragraph 0140 of International Publication No. 2018/155193, the contents of which are incorporated herein by reference. As a material for the resin substrate, cycloolefin polymers and polyimide are preferred. A thickness of 5 μm to 200 μm is preferred, and 10 μm to 100 μm is even more preferred.

As a conductive layer, examples include those used in general circuit wiring or touch panel wiring. Furthermore, from the viewpoint of conductivity and fine-line formation, a conductive layer preferably selected from at least one of the group consisting of metal layers, conductive metal oxide layers, graphene layers, carbon nanotube layers, and conductive polymer layers, with metal layers being more preferred, and copper or silver layers being even more preferred. The substrate may have only one conductive layer or may have two or more conductive layers. When there are two or more conductive layers, conductive layers of different materials are preferred.

Materials used as conductive layers include metals and conductive metal oxides. Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and _SiO₂ . Furthermore, in this disclosure, "conductivity" refers to a volume resistivity of less than 1 × ^10⁶ Ωcm. Preferably, the volume resistivity of the conductive metal oxide is less than 1 × ^10⁴ Ωcm.

When a resin pattern is manufactured using a substrate having a plurality of conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide. As a conductive layer, it is preferable to have an electrode pattern or wiring equivalent to the peripheral lead of a sensor in a visual recognition unit used in an electrostatic capacitive touch panel. A preferred example of a conductive layer is, for instance, paragraph 0141 of International Publication No. 2018/155193, the contents of which are incorporated herein by reference.

As a substrate with a conductive layer, a substrate having at least one of a transparent electrode and a circuitry is preferred. The substrate described above is preferably used as a substrate for a touch panel. The transparent electrode is preferably configured to function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), as well as metal wires such as a metal mesh and metal nanowires. Examples of metal wires include silver and copper wires. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

Metals are preferred as materials for circuit routing. Examples of metals suitable 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 metal elements. Copper, molybdenum, aluminum, or titanium are preferred materials for circuit routing, with copper being particularly preferred.

For the purpose of protecting electrodes (i.e., at least one of the electrodes for the touch panel and the wiring for the touch panel), it is preferable to provide the electrode protective film for the touch panel formed using the transfer material disclosed herein by directly or through other layers covering the electrodes.

The peeling procedure involves peeling the temporary support from the photosensitive layer. The method for peeling the temporary support is not particularly limited. In peeling the temporary support, a mechanism identical to the cover film peeling mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Publication No. 2010-072589 can be used.

The surface roughness Ra of the photosensitive layer exposed by peeling off the temporary support from the photosensitive layer, i.e., the first surface of the photosensitive layer, is 2 nm or more. If the roughness Ra of the first surface of the photosensitive layer is 2 nm or more, the smoothness of the photosensitive layer surface is improved. A preferred range of the roughness Ra of the first surface of the photosensitive layer is described in the "Photosensitive Layer" section above.

It is preferable that the static friction coefficient of the surface of the photosensitive layer exposed by peeling off the temporary support from the photosensitive layer, i.e., the first surface of the photosensitive layer, is less than 2.0. If the static friction coefficient of the first surface of the photosensitive layer is 1.0 or less, the smoothness of the photosensitive layer surface is improved. The preferred range of the static friction coefficient of the first surface of the photosensitive layer is described in the "Photosensitive Layer" section above.

It is preferable that the coefficient of kinetic friction of the surface of the photosensitive layer exposed by peeling it from the temporary support, i.e., the first surface of the photosensitive layer, is less than 1.5. If the coefficient of kinetic friction of the first surface of the photosensitive layer is less than 1.5, the smoothness of the photosensitive layer surface is improved. The preferred range of the coefficient of kinetic friction of the first surface of the photosensitive layer is described in the "Photosensitive Layer" section above.

The pattern formation process involves applying exposure and development processing to the photosensitive layer exposed by the peeling off of the temporary support to create the pattern. Development processing is usually performed after exposure processing.

[Exposure Processing] Exposure processing preferably includes patterned exposure of the photosensitive layer. "Patterned exposure" refers to exposure in a patterned form, that is, exposure with exposed and unexposed areas. The positional relationship between the exposed and unexposed areas in patterned exposure is not particularly restricted and can be adjusted appropriately. The photosensitive layer can be exposed from the side opposite to the side where the substrate is located, or it can be exposed from the side where the substrate is located.

The detailed configuration and specific size of the pattern in the pattern exposure are not particularly limited. 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 removed wiring, at least a portion of the pattern (preferably the electrode pattern of the touch panel and/or the portion where the wiring is removed) preferably includes fine lines with a width of 20 μm or less, and more preferably includes fine lines with a width of 10 μm or less.

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

As for exposure levels, 5 mJ/ ^cm² to 200 mJ/ ^cm² is preferred, and 10 mJ/ ^cm² to 100 mJ/ ^cm² is even better.

As a preferred example of the light source, exposure amount and exposure method used in the exposure, for example, the description in paragraphs 0146 to 0147 of International Publication No. 2018/155193 can be cited, which is incorporated into this specification.

Regarding exposure methods, in contact exposure, the appropriate exposure method can be selected and used. In non-contact exposure, appropriate methods can be selected and used, such as proximity exposure, projection exposure using a lens system or mirror system, or direct exposure using an exposure laser. In projection exposure using a lens system or mirror system, an exposure machine with an appropriate lens aperture number (NA) can be used according to the required resolution and depth of focus. In direct exposure, the photosensitive layer can be directly drawn on, or the photosensitive layer can be reduced and projected through a lens. Furthermore, exposure can be performed not only in the atmosphere, but also under reduced pressure or vacuum, and can be carried out by placing liquids such as water between the light source and the photosensitive layer. When using a photomask to expose the photosensitive layer, the photosensitive layer can be exposed by contact with the photomask, or the photomask can be brought close to the photosensitive layer without contact between the photosensitive layer and the photomask. It is preferable to expose the photosensitive layer by contact with the photomask.

[Developing Process] The development of the exposed photosensitive layer can be performed using a developing solution. For example, known developing solutions such as those described in Japanese Patent Application Publication No. 5-72724 can be used. A developing solution containing an alkaline aqueous solution of a compound with a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L is preferred. The developing solution may contain a water-soluble organic solvent and/or a surfactant. Examples of alkaline compounds that can be contained in alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). As a developing solution, the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferred. As a preferred developing method, the developing method described in paragraph 0195 of International Publication No. 2015/093271 is also preferred.

As a development method, there are no particular limitations; it can be any of the following: immersion development, shower development, shower and spin development, or dip development. Shower development refers to a development process in which developing solution is sprayed onto the exposed photosensitive layer to remove exposed or unexposed areas. After development, it is preferable to spray cleaning agent while simultaneously wiping with a brush to remove developing residue. The temperature of the developing solution is not particularly limited, but 20°C to 40°C is preferred.

"Peeling of the Protective Film" When the transfer material includes a protective film, it is preferable that the manufacturing method of the laminate includes the step of peeling the protective film from the transfer material. The method of peeling off the protective film is not limited and well-known methods may be used.

The method for manufacturing a laminate according to one embodiment disclosed herein may include a step of exposing a pattern obtained by a pattern forming step (post-exposure step) and/or a step of heating the pattern obtained by a pattern forming step (post-baking step). When the method for manufacturing a laminate includes both a post-exposure step and a post-baking step, it is preferable to perform post-baking after post-exposure. The exposure amount for post-exposure is preferably 100 mJ/ ^cm² to 5,000 mJ/ ^cm² , and more preferably 200 mJ/ ^cm² to 3,000 mJ/ ^cm² . The post-baking temperature is preferably 80°C to 250°C, and more preferably 90°C to 160°C. The best baking time is 1 minute to 180 minutes, and even better is 10 minutes to 60 minutes.

Other Steps The method for manufacturing a laminate of one embodiment disclosed herein may include any steps other than those described above. For example, steps described in the method for manufacturing circuit wiring or the method for manufacturing a touch panel may be cited, but are not limited to such steps.

Applications: The laminate manufactured by the method for manufacturing a laminate according to an embodiment of the present invention is applicable to various devices. As a device having the laminate, examples include input devices, with touch panels being preferred, and electrostatic capacitive touch panels being even more preferred. Furthermore, the input device is applicable to display devices such as organic electroluminescent displays and liquid crystal displays. When the laminate is applied to a touch panel, it is preferable to use the formed pattern as a protective film for the electrodes or wiring of the touch panel. That is, it is preferable to use the transfer material disclosed herein for forming the protective film for the electrodes of the touch panel or the wiring of the touch panel.

<Manufacturing Method of Circuit Wiring> A method for manufacturing circuit wiring according to an embodiment disclosed herein includes the following steps in sequence: bonding a transfer material comprising a temporary support and a photosensitive layer in contact with the temporary support to a substrate; sequentially disposing the photosensitive layer and the temporary support on the substrate (i.e., the "bonding step"); peeling the temporary support from the photosensitive layer (i.e., the "peeling step"); and applying the photosensitive layer to the substrate. The photosensitive layer exposed by peeling off the temporary support is subjected to exposure and development processing to form a pattern (i.e., the "pattern formation step"); and the substrate in the area where the pattern is not disposed is etched (hereinafter, sometimes referred to as the "etching step"). The surface roughness Ra of the photosensitive layer exposed by peeling off the temporary support is 2 nm or more. Hereinafter, each step included in the method for manufacturing circuit wiring will be described, but unless specifically mentioned, the description of each step included in the method for manufacturing laminates also applies to each step included in the method for manufacturing circuit wiring.

The etching process involves etching the substrate in areas where no pattern is present. Specifically, the etching process uses a pattern formed from a photosensitive layer as an etching resist. Known methods can be applied, such as those described in paragraphs 0209-0210 of Japanese Patent Application Publication No. 2017-120435, paragraphs 0048-0054 of Japanese Patent Application Publication No. 2010-152155, wet etching by immersion in an etching solution, and dry etching methods such as plasma etching.

The etching solution used in wet etching can be either acidic or alkaline, depending on the object being etched. Examples of acidic etching solutions include aqueous solutions of acidic components alone, such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, as well as mixed aqueous solutions of acidic components with salts selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component can also be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions of the alkaline component alone, such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as mixed aqueous solutions of the alkaline component with salts (e.g., potassium permanganate). Alkaline components can also be components composed of multiple alkaline components.

The method for manufacturing a circuit wiring according to one embodiment disclosed herein preferably includes a step of removing residual patterns (hereinafter, sometimes referred to as the "removal step"). It is preferable that the removal step is performed after the etching step. The method for removing residual patterns is not particularly limited; examples include chemical removal, and removal using a removal solution is preferred. As a method for removing residual patterns, an example is immersing a substrate with residual patterns in a stirred removal solution at a preferred temperature of 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute to 30 minutes.

Examples of removal solutions include those prepared by dissolving inorganic or organic alkali components in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture thereof. Examples of inorganic alkali components include sodium hydroxide and potassium hydroxide. Examples of organic alkali components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salts. Furthermore, removal solutions can be used and removal can be achieved by known methods such as spraying, rinsing, and rotary immersion.

Other Steps The method for manufacturing a circuit wiring according to one embodiment disclosed herein may include any steps other than those described above. For example, the following steps can be cited, but are not limited to these steps. Furthermore, as exposure steps, development steps, and other steps applicable to the method for manufacturing circuit wiring, the steps described in paragraphs 0035 to 0051 of Japanese Patent Application Publication No. 2006-23696 can be cited. In addition, other steps may include, for example, the step of reducing visible light reflectivity described in paragraph 0172 of International Publication No. 2019/022089, and the step of forming a new conductive layer on the insulating film described in paragraph 0173 of International Publication No. 2019/022089, but are not limited to these steps.

[Steps to Reduce Visible Light Reflectivity] A method for manufacturing a circuit wiring according to an embodiment of this disclosure may include a step of performing a process to reduce the visible light reflectivity of some or all of the plurality of conductive layers having a substrate. As a process for reducing visible light reflectivity, oxidation treatment can be cited. When the substrate has a conductive layer containing copper, the copper is oxidized to become copper oxide, and the conductive layer is blackened, thereby reducing the visible light reflectivity of the conductive layer. The treatment for reducing visible light reflectance is 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, and the contents described in these publications are incorporated in this specification.

[Steps for forming an insulating film and forming a new conductive layer on the surface of the insulating film] A method for manufacturing a circuit wiring according to one embodiment of this disclosure preferably includes the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through the above steps, a second electrode pattern that is insulated from the first electrode pattern can be formed. The steps for forming the insulating film are not particularly limited, and known methods for forming permanent films can be cited. Furthermore, an insulating photosensitive material can also be used to form an insulating film with the desired pattern by photolithography. The steps for forming a new conductive layer on an insulating film are not particularly limited. For example, a photosensitive material with conductive properties can be used to form a new conductive layer with the desired pattern by photolithography.

The disclosed embodiment of the circuit wiring manufacturing method uses a substrate having a plurality of conductive layers on each of its two surfaces, and it is preferable to form the circuit sequentially or simultaneously on the conductive layers formed on the two surfaces of the substrate. With this configuration, it is possible to form a 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 surfaces of the substrate in a roll-to-roll manner.

Applications of Circuit Wiring The circuit wiring manufactured using the method disclosed herein can be applied to various devices. Examples of devices incorporating the circuit wiring manufactured by the above method include input devices, preferably touch panels, and even more preferably electrostatic capacitive touch panels. Furthermore, the above-mentioned input devices can be applied to display devices such as organic EL displays and liquid crystal displays.

(Manufacturing Method of Touch Panel) A method for manufacturing a touch panel according to an embodiment disclosed herein includes the following steps in sequence: bonding a transfer material comprising a temporary support and a photosensitive layer in contact with the temporary support to a substrate; sequentially disposing the photosensitive layer and the temporary support on the substrate (i.e., the "bonding step"); peeling the temporary support from the photosensitive layer (i.e., the "peeling step"); and so on. The photosensitive layer exposed by peeling off the temporary support is subjected to exposure processing and development processing to form a pattern (i.e., "pattern formation step"); and the substrate in the area where the pattern is not disposed is etched (i.e., "etching step"). The surface roughness Ra of the photosensitive layer exposed by peeling off the temporary support is 2 nm or more.

Regarding the specific embodiments of each step in the method for manufacturing a touch panel and the order in which they are performed, the preferred embodiments are the same as those described in the sections on "Method for Manufacturing a Laminate" and "Method for Manufacturing Circuit Wiring" above. For methods other than forming the wiring for a touch panel using the methods described above, please refer to known methods for manufacturing touch panels. Furthermore, the method for manufacturing a touch panel may include any steps other than those described above (other steps).

An example of the pattern of the mask used in the manufacture of a touch panel is shown in Figures 2 and 3. In pattern A of Figure 2 and pattern B of Figure 3, GR is the non-image area (light-shielding area), EX is the image area (exposure area), and DL is a virtual alignment frame. In the manufacturing method of the touch panel, for example, a negative photosensitive layer can be exposed by a mask having pattern A shown in Figure 2, thereby manufacturing a touch panel having circuit wiring corresponding to pattern A corresponding to EX. Specifically, it can be manufactured using the method described in Figure 1 of International Publication No. 2016/190405. In one example of the manufactured touch panel, the central part of the exposure section EX (the patterned part formed by the four corners) is the part with transparent electrodes (electrodes for the touch panel), and the peripheral part of the exposure section EX (the fine line part) is the part with peripheral lead-out wiring.

By employing the above-described method for manufacturing a touch panel, a touch panel having at least the wiring required for the touch panel can be manufactured. It is preferable that the touch panel has a transparent substrate, electrodes, and an insulating layer or protective layer. Known methods for detection in the touch panel include resistive film methods, electrostatic capacitance methods, ultrasonic methods, electromagnetic induction methods, and optical methods. Among these, the electrostatic capacitance method is preferred.

As for touch panel types, examples include in-cell type (e.g., those shown in Figures 5, 6, 7, and 8 of Japanese Patent Application Publication No. 2012-517051), on-cell type (e.g., those shown in Figure 19 of Japanese Patent Application Publication No. 2013-168125 and Figures 1 and 5 of Japanese Patent Application Publication No. 2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (e.g., those shown in Figure 2 of Japanese Patent Application Publication No. 2013-54727), and various out-cell types. Types (such as GG, G1/G2, GFF, GF2, GF1, and G1F) and other components (e.g., those shown in Figure 6 of Japanese Patent Application Publication No. 2013-164871). As a touch panel, for example, those described in paragraph 0229 of Japanese Patent Application Publication No. 2017-120435 can be cited. [Example]

The following examples further illustrate the embodiments of this disclosure. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified as long as they do not depart from the intent of the embodiments of this disclosure. Therefore, the scope of the embodiments of this disclosure is not limited to the specific examples shown below. Furthermore, unless otherwise specified, "parts" and "%" are mass standards. Also, in the following examples, the weight-average molecular weight of the resin is the weight-average molecular weight calculated using polystyrene based on gel osmosis chromatography (GPC). Furthermore, the theoretical acid value is used.

<Temporary Support> Temporary supports are provided as shown in the table below.

[Table 1] Temporary support body S-1 S-2 S-3 S-4 S-5 PET layer thickness 16μm 16μm 16μm 25μm 25μm Other resin layers without 10μm polyethylene 10μm polyethylene without without Roughness Ra of the first surface 1nm 50nm 130nm 360nm 620nm

(Temporary Support S-1) The temporary support S-1 is LUMIRROR 16QS62 manufactured by Toray Industries, Inc.

(Temporary Support S-2) Polyethylene was melt-extruded and laminated onto a 16 μm thick polyethylene terephthalate (PET) film with a polyethylene thickness of 10 μm. During lamination, a matting roller with a surface roughness Ra of 0.1 μm was pressed onto the polyethylene layer. Through the above steps, a PET film with matting polyethylene was produced as the temporary support S-2. The roughness Ra of the first surface of the temporary support S-2 recorded in Table 1 is a value measured on the surface of the polyethylene layer.

(Temporary Support S-3) Temporary support S-3 was obtained by following the same manufacturing method as temporary support S-2, except that the surface roughness Ra of the matting roller was changed to 0.2 μm. The roughness Ra of the first surface of temporary support S-3 recorded in Table 1 is a value measured on the surface of the polyethylene layer.

(Temporary Support S-4) Temporary support S-4 is a sand mat processed film type S manufactured by KAISEI INDUSTRY CO.,LTD.

(Temporary Support S-5) Temporary support S-5 is a sandblasted matte film of type A manufactured by KAISEI INDUSTRY CO.,LTD.

<Preparation of Photosensitive Resin Composition> A photosensitive resin composition was prepared by mixing the ingredients shown in the table below.

[Table 2] Photosensitive resin components P-1 P-2 P-3 P-4 P-5 P-6 Polymer (Polymer A) A-1 (solid content concentration 30% by mass) 166.67 166.67 - - - - A-2 (solid content concentration 30% by mass) - - 183.34 200.00 183.34 183.34 Ethylene-unsaturated compounds (polymeric compounds) B-1 36.20 36.20 16.29 14.66 16.29 16.29 B-2 5.00 5.00 4.50 4.05 4.50 4.50 B-3 - - 16.29 14.66 16.29 16.29 Photopolymerization initiator B-CIM 7.00 7.00 7.00 7.00 7.00 7.00 Sensitive agent SB-PI 701 0.50 0.50 0.50 0.50 0.50 0.50 pigment LCV 0.40 0.40 0.40 0.40 0.40 0.40 Chain transfer agent N-Phenylglycine 0.20 0.20 0.20 0.20 0.20 0.20 Rust inhibitor CBT-1 0.10 0.10 0.10 0.10 0.10 0.10 Polymerization inhibitors TDP-G 0.30 0.30 0.30 0.30 0.30 0.30 antioxidants phenidone 0.01 0.01 0.01 0.01 0.01 0.01 surfactants MEGAFACE F-552 0.29 0.29 0.29 0.29 0.29 0.29 particle MEK-ST-40 (solid content concentration 40% by mass) - 62.50 - - 27.80 62.50 solvent Methyl ethyl ketone 399.99 399.99 399.99 399.99 399.99 399.99 PGMEA 133.33 133.33 133.33 133.33 133.33 133.33 Total (parts by weight) 749.99 812.49 762.54 775.50 790.34 825.04

(Polymer) • A-1: A composition comprising 30% by mass of polymer A-1, produced by the method described below. • A-2: A composition comprising 30% by mass of polymer A-2, produced by the method described below.

[A-1] A composition comprising 30% by mass of polymer A-1 was obtained by the following method. In the following method, the following abbreviations represent the following compounds respectively. St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation) MAA: Methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) V-601: Dimethyl 2,2’-azobis(isobutyrate) (manufactured by FUJIFILM Wako Pure Chemical Corporation, polymerization initiator) PGMEA: Propylene glycol monomethyl ether acetate

PGMEA (116.5 parts by mass) was added to a three-necked flask and heated to 90°C under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked flask at 90°C ± 2°C, a mixture of St (52.0 parts by mass), MMA (19.0 parts by mass), MAA (29.0 parts by mass), V-601 (4.0 parts by mass), and PGMEA (116.5 parts by mass) was added dropwise to the three-necked flask over a period of 2 hours. After the addition was completed, the mixture was stirred for 2 hours while maintaining the liquid temperature at 90°C ± 2°C, thereby obtaining a composition containing 30% by mass of polymer A-1. The properties of polymer A-1 are shown in the table below.

[A-2] Except that the amount of V-601 added was changed to 12.0 parts by mass, a composition containing 30% by mass of polymer A-2 was obtained by following the synthesis method of polymer A-1. The properties of polymer A-2 are shown in the following table.

[Table 3] polymer A-1 A-2 acid value 189mgKOH/g 189mgKOH/g molecular weight 60000 20000 Glass transition temperature Tg 131℃ 131℃

(Ethylene-unsaturated compounds) • B-1: NK Ester BPE-500 (2,2-bis(4-(methacryloxypentethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.) • B-2: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO.,LTD.) • B-3: Sartomer SR-454 (epoxytrimethylolpropane triacrylate, manufactured by Arkema S.A.)

(Photopolymerization Initiator) · B-CIM (Photoradical Polymerization Initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer, manufactured by Hampford)

(Sensitizer) ·SB-PI 701 (4,4’-bis(diethylamino)benzophenone, sold by Sanyo Trading Co., Ltd.)

(Pigment) ·LCV (Colorless Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd., a pigment that develops color through free radicals)

(Chain transfer agent) · N-Phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Rust Inhibitor) ·CBT-1 (Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.)

(Polymerization inhibitor) ·TDP-G (Phenylephrine, manufactured by Kawaguchi Chemical Industry Company, Limited)

(Antioxidant) Phenylidene (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Surfactant) · MEGAFACE F-552 (Fluoro-based surfactant, manufactured by DIC Corporation)

(Particles) ·MEK-ST-40 (Methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Corporation)

(Soluble) · Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.) · PGMEA (propylene glycol monomethyl ether acetate, manufactured by SHOWA DENKO K.K.)

<Example 1> (Preparation of transfer material) A photosensitive resin composition P-3 is coated onto the polyethylene layer of the temporary support S-2 with a dry film thickness of 3.0 μm, and dried in an oven at 100°C for 2 minutes. A polypropylene film (TORAYFAN#30-2500H, 26 μm thickness, manufactured by Toray Industries, Inc.) is then laminated as a protective film to produce the transfer material.

(Fabrication of PET substrate with copper layer) A copper layer with a thickness of 200nm is fabricated on a 100μm thick polyethylene terephthalate (PET) film by sputtering, thereby creating a PET substrate with copper layer.

(Resin Pattern Creation) After peeling off the protective film, the transfer material is laminated onto the copper-coated PET substrate under lamination conditions of 0.6 MPa linear pressure and 0.5 m/min linear speed (lamination speed). The temporary support is then removed. While adjusting the exposure position (alignment), the exposed photosensitive layer is brought into contact with a glass mask containing a line and spatial pattern with a linewidth of 3μm to 20μm (Duty ratio = 1:1). The photosensitive layer is then exposed to ultra-high pressure mercury lamps through the mask, left to stand for 30 minutes, and then developed to form the resin pattern. Development was performed using a 1.0% sodium carbonate aqueous solution at 28°C for 40 seconds by spraying. Through the above steps, a laminate containing the resin pattern was obtained.

(Creation of the circuit wiring pattern) The laminate containing the resin pattern was etched at 23°C for 30 seconds using copper etching solution (Cu-02, manufactured by KANTO CHEMICAL CO.,INC.), and the resist was stripped using a 4% sodium hydroxide solution to create the circuit wiring pattern. The circuit wiring pattern obtained in Example 1 was observed under a microscope, and the result showed no stripping or missing parts, indicating a complete pattern.

<Examples 2-9 and Comparative Examples 1-2> Except for changing the type of temporary support and the type of photosensitive resin composition according to Table 4, the transfer material, the copper-coated PET substrate, the resin pattern and the circuit wiring pattern are produced by following the method of Example 1.

<Static and Dynamic Friction Coefficients> After peeling off the protective film, the transfer material is laminated onto the copper-coated PET substrate under lamination conditions of 0.6 MPa linear pressure and 0.5 m/min linear speed (lamination speed). Through the lamination of the transfer material on the copper-coated PET substrate, a photosensitive layer and a temporary support are sequentially disposed on the copper layer of the copper-coated PET substrate. The temporary support is then peeled off, exposing the photosensitive layer to contact a 5 mm thick transparent sodium glass (200 x 200 mm). The static and dynamic coefficients of friction were determined using a Tensilon universal testing machine (RTF1210, manufactured by A&D Company, Limited) and a plastic friction coefficient measuring fixture (J-PZ2-50N, manufactured by A&D Company, Limited) according to the test method for the coefficient of friction of plastic films and sheets (JIS K7125:1999). The test conditions are shown below, and the test results are presented in Table 4. Load: 200g; Contact area: 63mm × 63mm; Test speed: 100mm/min.

<Smoothness (Static Friction)> Smoothness was evaluated according to the following criteria based on the coefficient of static friction. The evaluation results are shown in Table 4. 5: Less than 0.4; 4: 0.4 or higher but less than 0.6; 3: 0.6 or higher but less than 1.0; 2: 1.0 or higher but less than 2.0; 1: 2.0 or higher or unmeasurable.

<Smoothness (Kinetic Friction)> Smoothness was evaluated according to the coefficient of kinetic friction based on the following criteria. The evaluation results are shown in Table 4. 5: Less than 0.3 4: 0.3 or higher but less than 0.45 3: 0.45 or higher but less than 0.75 2: 0.75 or higher but less than 1.5 1: 1.5 or higher or unmeasurable

<Linearity> After peeling off the protective film, the transfer material is laminated onto a copper-coated PET substrate under lamination conditions of 0.6 MPa linear pressure and 0.5 m/min linear speed (lamination speed). The temporary support is then removed, allowing the photosensitive layer of the transfer material to contact a glass mask with a 10 μm linewidth and spatial pattern (duty ratio = 1:1). The 10 μm linewidth after development is used as the exposure dose, and the photosensitive layer is exposed to light including gamma rays (436 nm), hamma rays (405 nm), and iamma rays (365 nm) through the mask using an ultra-high pressure mercury lamp. After standing for 30 minutes, development was performed. During development, a 40-second spray development using a 1.0% sodium carbonate aqueous solution at 28°C was used to create the resin pattern. The laminate containing the resin pattern was etched at 23°C for 30 seconds using copper etching solution (Cu-02, manufactured by KANTO CHEMICAL CO.,INC.), followed by resist stripping using a 4% sodium hydroxide solution to create the wiring pattern. The linewidth of the wiring pattern was measured at 100 points, and the LWR (i.e., the standard deviation of the linewidth) was calculated. Based on the LWR, the straightness of the wiring was evaluated according to the following criteria. The evaluation results are shown in Table 4. The larger the value of criteria 1-5 shown below, the better the straightness of the wiring pattern. 5: Less than 150nm; 4: 150nm or more but less than 200nm; 3: 200nm or more but less than 300nm; 2: 300nm or more but less than 500nm; 1: 500nm or more.

[Table 4] Temporary support body Photosensitive layer Smoothness (static friction) Smoothness (dynamic friction) linearity Kind Roughness Ra of the first surface Kind Roughness Ra of the first surface The coefficient of static friction of the first surface Coefficient of kinetic friction on the first surface Implementation Example 1 S-2 50nm P-3 50nm 1.54 1.14 2 2 5 Implementation Example 2 S-3 130nm P-3 130nm 0.85 0.52 3 3 4 Implementation Example 3 S-4 360nm P-3 360nm 0.80 0.65 3 3 3 Implementation Example 4 S-5 620nm P-3 620nm 0.81 0.62 3 3 2 Implementation Example 5 S-3 130nm P-1 130nm 1.23 1.10 2 2 3 Implementation Example 6 S-3 130nm P-2 130nm 0.84 0.63 3 3 3 Implementation Example 7 S-3 130nm P-4 130nm 0.69 0.44 3 4 4 Implementation Example 8 S-3 130nm P-5 130nm 0.59 0.42 4 4 3 Implementation Example 9 S-3 130nm P-6 130nm 0.55 0.40 4 4 3 Comparative example 1 S-1 1nm P-1 1nm 5.0 and above (cannot be measured) Unable to measure 1 1 5 Comparative example 2 S-1 1nm P-6 1nm 5.0 and above (cannot be measured) Unable to measure 1 1 4

Table 4 shows that the smoothness (static friction) of Examples 1-9 is superior to that of Comparative Examples 1-2. Table 4 also shows that the smoothness (dynamic friction) of Examples 1-9 is superior to that of Comparative Examples 1-2.

10: Temporary support; 20: Photosensitive layer; 30: Protective film; 100: Transfer material; GR: Light-blocking part (non-image part); EX: Exposure part (image part); DL: Alignment frame

Figure 1 is a schematic diagram showing an example of the composition of a transfer material in one embodiment. Figure 2 is a schematic top view of pattern A. Figure 3 is a schematic top view of pattern B.

10: Temporary support; 20: Photosensitive layer; 30: Protective film; 100: Transfer material.

Claims (16)

A transfer material includes a temporary support and a photosensitive layer in contact with the temporary support. The surface roughness Ra of the photosensitive layer exposed when it is peeled off from the temporary support is 2 nm or more and 1,000 nm or less. The static friction coefficient of the surface of the photosensitive layer exposed when it is peeled off from the temporary support is 1.0 or less. The transfer material as described in claim 1, wherein the surface roughness Ra of the surface of the temporary support exposed when the photosensitive layer is peeled off from the temporary support is 2 nm or more. The transfer material as described in claim 1 or claim 2, wherein the surface roughness Ra of the surface of the temporary support exposed when the photosensitive layer is peeled off from the temporary support is less than 1,000 nm. The transfer material as described in claim 1, wherein the static friction coefficient of the surface of the aforementioned photosensitive layer exposed when the aforementioned photosensitive layer is peeled off from the aforementioned temporary support is 0.6 or less. The transfer material as described in claim 1, wherein the coefficient of dynamic friction of the surface of the aforementioned photosensitive layer exposed when the aforementioned photosensitive layer is peeled off from the aforementioned temporary support is 1.0 or less. The transfer material as described in claim 1 or claim 2, wherein the aforementioned photosensitive layer comprises a polymer compound having a weight average molecular weight of 10,000 or more, and the glass transition temperature of the aforementioned polymer compound is 50°C or more. The transfer material as described in claim 6, wherein the aforementioned photosensitive layer contains a polymeric compound having a molecular weight of 1,500 or less, and the mass ratio of the aforementioned polymeric compound contained in the aforementioned photosensitive layer to the mass ratio of the aforementioned polymeric compound contained in the aforementioned photosensitive layer is 50% or less. The transfer material as described in claim 7, wherein the aforementioned polymeric compound comprises a polymeric compound having two or more polymeric groups. The transfer material as described in claim 7, wherein the aforementioned polymeric compound includes polymeric compounds having two or more polymeric groups and polymeric compounds having three or more polymeric groups. The transfer material as described in claim 7, wherein the aforementioned polymeric compound is an ethoxylated methacrylate compound. The transfer material as described in claim 1 or claim 2, wherein the aforementioned photosensitive layer comprises a surfactant. The transfer material as described in claim 1 or claim 2, wherein the thickness of the aforementioned photosensitive layer is less than 5 μm. A method for manufacturing a laminate includes the following steps in sequence: bonding a transfer material comprising a temporary support and a photosensitive layer in contact with the temporary support to a substrate, thereby sequentially disposing the photosensitive layer and the temporary support on the substrate; peeling off the temporary support from the photosensitive layer; and performing exposure and development processing on the photosensitive layer exposed by the peeling off of the temporary support to form a pattern, wherein the surface roughness Ra of the photosensitive layer exposed by peeling off the temporary support is 2 nm or more and 1,000 nm or less. When the photosensitive layer is peeled off from the temporary support, the static friction coefficient of the surface of the exposed photosensitive layer is 1.0 or less. The method for manufacturing a laminate as described in claim 13, wherein the aforementioned exposure processing includes the following steps: exposing the aforementioned photosensitive layer to a photomask. The method for manufacturing the laminate as described in claim 13, wherein the static friction coefficient of the surface of the aforementioned photosensitive layer exposed when the aforementioned photosensitive layer is peeled off from the aforementioned temporary support is 0.6 or less. The method for manufacturing the laminate as described in claim 13, wherein the coefficient of dynamic friction of the surface of the aforementioned photosensitive layer exposed when the aforementioned photosensitive layer is peeled off from the aforementioned temporary support is 1.0 or less.