TW202413096A - Photosensitive transfer material, and method for manufacturing thereof, method for manufacturing resin pattern, and method for manufacturing circuit wiring - Google Patents

Abstract

A photosensitive transfer material and a method for manufacturing the same, as well as a method for manufacturing a resin pattern using the photosensitive transfer material and a method for manufacturing circuit wiring, wherein the photosensitive transfer material has a transfer layer and a pseudo-support in sequence on a covering film, the transfer layer has a photosensitive layer and a particle layer containing particles in sequence, the surface of the particle layer on the pseudo-support side has a convex structure containing the particles, the average layer thickness of a portion of the particle layer where the convex structure does not exist is less than the arithmetic average particle size of the particles contained in the particle layer, or the transfer layer has a photosensitive layer, an intermediate layer and a particle layer containing particles in sequence, the surface of the particle layer on the pseudo-support side has a convex structure containing the particles.

Description

Photosensitive transfer material and method for producing the same, method for producing resin pattern, and method for producing circuit wiring

The present invention relates to a photosensitive transfer material and a manufacturing method thereof, a manufacturing method of a resin pattern, and a manufacturing method of a circuit wiring.

In a display device (organic electroluminescent (EL) display device and liquid crystal display device, etc.) having a touch panel such as an electrostatic capacitive input device, a conductive layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition part, a peripheral wiring part, and wiring of a lead wiring part is provided inside the touch panel. Generally, when forming a patterned layer, since the number of steps for obtaining the desired pattern shape is small, a method of developing after exposing a layer of a photosensitive layer forming composition provided on an arbitrary substrate using a photosensitive transfer material is widely used.

In addition, as a conventional photosensitive transfer material, those described in Japanese Patent Publication No. 2019-128445 or International Publication No. 2019/146380 are known. Japanese Patent Publication No. 2019-128445 describes a photosensitive transfer material having a photosensitive layer, an adhesive layer and a pseudo-support in order on a cover film, the photosensitive layer containing particles, the photosensitive layer and the adhesive layer are in contact, the photosensitive layer and the adhesive layer can be peeled off, and the surface of the photosensitive layer after the photosensitive layer and the adhesive layer are peeled off has concavities and convexities formed by the particles.

International Publication No. 2019/146380 describes a photosensitive transfer material having a photosensitive layer, an intermediate layer, an adhesive layer and a pseudo-support in sequence on a covering film, wherein the intermediate layer contains particles, the intermediate layer is in contact with the adhesive layer, the intermediate layer and the adhesive layer can be peeled off, and the surface of the intermediate layer after the intermediate layer and the adhesive layer are peeled off has bumps and depressions formed by the particles.

One embodiment of the present invention aims to provide a photosensitive transfer material with excellent smoothness and a method for manufacturing the same. In addition, another embodiment of the present invention aims to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material and a method for manufacturing circuit wiring.

Means for solving the above-mentioned problems include the following aspects. ＜1＞ A photosensitive transfer material, which has a transfer layer and a pseudo-support in sequence on a covering film, the transfer layer having a photosensitive layer and a particle layer containing particles in sequence, the particle layer being in contact with the pseudo-support, the particle layer and the pseudo-support being capable of being peeled off, the surface of the particle layer on the pseudo-support side having a convex structure containing the particles, and the average layer thickness of a portion of the particle layer where the convex structure does not exist is less than the arithmetic average particle size of the particles contained in the particle layer. <2> A photosensitive transfer material, which has a transfer layer and a pseudo support on a cover film in sequence, wherein the transfer layer has a photosensitive layer, an intermediate layer and a particle layer containing particles in sequence, the particle layer is in contact with the pseudo support, the particle layer and the pseudo support can be peeled off, and the surface of the particle layer on the pseudo support side has a convex structure containing the particles. <3> The photosensitive transfer material as described in <1> or <2>, wherein the pseudo support has an adhesive layer on the surface in contact with the particle layer. <4> The photosensitive transfer material as described in <3>, wherein the adhesive layer contains a polyester resin. <5> The photosensitive transfer material as described in any one of <1> to <4>, wherein the photosensitive layer is a negative photosensitive layer. <6> The photosensitive transfer material as described in any one of <1> to <5>, wherein the oxygen permeability of the transfer layer is 25,000cc/ ^m2 ·day·atm or less. <7> The photosensitive transfer material as described in <2>, wherein the intermediate layer comprises polyvinyl alcohol. <8> The photosensitive transfer material as described in any one of <1> to <7>, wherein the particle layer comprises an alkali-soluble resin. <9> The photosensitive transfer material as described in any one of <1> to <8>, wherein the arithmetic average particle size of the particles is 10nm to 200nm. <10> A photosensitive transfer material as described in any one of <1> to <9>, wherein the average layer thickness of the portion of the particle layer where the convex structure does not exist is 10nm to 200nm. <11> A method for manufacturing a photosensitive transfer material, comprising the following steps: a step of providing a photosensitive layer-forming composition on a cover film to form a photosensitive layer; a step of providing a particle layer-forming composition on the photosensitive layer to form a particle layer having a convex structure containing particles on its surface; and a step of attaching a pseudo-support to the surface of one side of the particle layer having the convex structure in a manner that the pseudo-support is in contact with the particle layer, wherein the average layer thickness of the portion of the particle layer where the convex structure does not exist is less than the arithmetic average particle size of the particles contained in the particle layer. <12> A method for manufacturing a photosensitive transfer material, comprising the following steps: a step of providing a photosensitive layer-forming composition on a covering film to form a photosensitive layer; a step of providing an intermediate layer-forming composition on the photosensitive layer to form an intermediate layer; a step of providing a particle layer-forming composition on the intermediate layer to form a particle layer; and a step of bonding a pseudo-support to the particle layer in contact with the particle layer. <13> A method for manufacturing a resin pattern, which comprises the following steps in sequence: a step of peeling off the above-mentioned covering film in the photosensitive transfer material described in any one of items <1> to <10>; a step of bringing the outermost layer on the side of the photosensitive layer in the photosensitive transfer material from which the above-mentioned covering film has been peeled into contact with and bonding with a support having a conductive layer; a step of peeling off the above-mentioned pseudo-support from the above-mentioned particle layer; a step of bringing an exposure mask into contact with the above-mentioned particle layer and exposing the above-mentioned photosensitive layer to a pattern through the above-mentioned exposure mask; and a step of developing the above-mentioned photosensitive layer to form a resin pattern. <14> A method for manufacturing a circuit wiring, which comprises the following steps in order: a step of peeling off the cover film in the photosensitive transfer material described in any one of <1> to <10>; a step of bringing the outermost layer of the photosensitive layer side of the photosensitive transfer material from which the cover film has been peeled off into contact with a support having a conductive layer and bonding them together; The invention relates to a step of: peeling off the pseudo-support from the particle layer; bringing an exposure mask into contact with the particle layer and exposing the photosensitive layer in a pattern through the exposure mask; developing the photosensitive layer to form a resin pattern; and etching the conductive layer using the formed resin pattern as a mask. <15> A method for manufacturing a circuit wiring, which comprises the following steps in order: a step of peeling off the above-mentioned covering film in the photosensitive transfer material described in any one of <1> to <10>; a step of bringing the outermost layer of the photosensitive layer side of the above-mentioned photosensitive transfer material from which the above-mentioned covering film has been peeled into contact with and bonding with a supporting body having a conductive layer; a step of peeling off the above-mentioned pseudo-support from the above-mentioned particle layer; The invention further comprises the steps of: bringing an exposure mask into contact with the particle layer and exposing the photosensitive layer in a pattern through the exposure mask; developing the photosensitive layer to form a resin pattern; electroplating the conductive layer using the formed resin pattern as a mask; peeling off the formed resin pattern; and etching the conductive layer. [Effects of the invention]

According to one embodiment of the present invention, a photosensitive transfer material with excellent smoothness and a method for manufacturing the same can be provided. In addition, according to another embodiment of the present invention, a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material and a method for manufacturing circuit wiring can be provided.

The contents of the present disclosure are described below. In addition, the description is made with reference to the attached drawings, but symbols are sometimes omitted. In addition, in this specification, the numerical range represented by "~" refers to the range that includes the numerical values recorded before and after "~" as the lower limit and upper limit. In addition, in this specification, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, "(meth)acrylate" means both or either acrylate and methacrylate, and "(meth)acryloyl" means both or either acryl and methacryloyl. Furthermore, in this specification, regarding the amount of each component in the composition, unless otherwise specified, when there are multiple substances equivalent to each component in the composition, it refers to the total amount of the multiple substances present in the composition. In this specification, the term "step" includes not only independent steps, but also steps that can achieve the intended purpose of the step even if they cannot be clearly distinguished from other steps. In the marking of the base (atomic group) in this specification, the marking of substituted and unsubstituted is not recorded, and it also includes those without substitution and those with substitution. For example, "alkyl" includes not only alkyl without substitution (unsubstituted alkyl) but also alkyl with substitution (substituted alkyl). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle radiation such as electron beam and ion beam. In addition, as the light used for exposure, the bright line spectrum of mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam and other active light (active energy radiation) can generally be cited. In addition, the chemical structure in this specification is sometimes recorded as a simplified structure in which hydrogen atoms are omitted. In this disclosure, the meaning of "mass %" is the same as "weight %", and the meaning of "mass parts" is the same as "weight parts". In addition, in this disclosure, a combination of two or more preferred aspects is a more preferred aspect. In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure, unless otherwise specified, are molecular weights converted by using a gel permeation chromatography (GPC) analysis device using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION), using a solvent THF (tetrahydrofuran) and a differential refractometer, and using polystyrene as a standard substance. In this specification, "total solid content" refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, as mentioned above, the "solid content" is the component after removing the solvent, for example, it can be solid or liquid at 25°C.

(Photosensitive transfer material) The first embodiment of the photosensitive transfer material disclosed herein has a transfer layer and a pseudo-support on a cover film in sequence, the transfer layer has a photosensitive layer and a particle layer containing particles in sequence, the particle layer is in contact with the pseudo-support, the particle layer and the pseudo-support can be peeled off, the surface of the particle layer on the pseudo-support side has a convex structure containing the particles, and the average layer thickness of the portion of the particle layer where the convex structure does not exist is less than the arithmetic average particle size of the particles contained in the particle layer. The second embodiment of the photosensitive transfer material disclosed herein has a transfer layer and a pseudo-support on a cover film in sequence, the transfer layer has a photosensitive layer, an intermediate layer and a particle layer containing particles in sequence, the particle layer is in contact with the pseudo-support, the particle layer and the pseudo-support can be peeled off, and the surface of the particle layer on the pseudo-support side has a convex structure containing the particles.

In addition, in this specification, when it is not particularly specified and is abbreviated as "the photosensitive transfer material of the present disclosure", both the first embodiment and the second embodiment are described. In addition, when it is not particularly specified and is abbreviated as "cover film", the cover film of both or either of the first embodiment and the second embodiment is described.

Dry film resist (DFR) is widely used because it can easily form resist patterns on various substrates by using thermal lamination. In addition, due to the trend of high integration of semiconductors and invisible fine wiring in recent years, the use of DFR in pattern formation below 5μm requires high resolution. On the other hand, the pseudo support (PET substrate, etc.) used for dry film resist has some cases where foreign matter is removed by filtering, and some cases where foreign matter that is difficult to remove is mixed in. When exposing the photoresist through a dummy support, in order to eliminate exposure obstacles (shadows caused by foreign matter) caused by such foreign matter, it is effective to adopt a method of transferring to the photoresist exposure step after peeling off the dummy support, that is, the dummy support peeling exposure method. In addition, when exposing through a mask, the smaller the gap (exposure GAP) between the photoresist and the mask is, the clearer the optical image becomes. Therefore, after peeling off the dummy support that causes the expansion of the exposure GAP, it is effective to expose in a way that the mask contacts the surface after the dummy support is peeled off (also called mask contact exposure) for high resolution. However, when the mask contact exposure is performed after the dummy support is peeled off, the outermost layer (e.g., photosensitive layer or intermediate layer) exposed after the dummy support is peeled off will be directly printed with the surface shape of the flat dummy support, thus becoming a flat shape. As a result, the smoothness of the flat mask in contact is poor, which may cause blocking in extreme cases, sometimes hindering the alignment of the exposure machine or hindering the exhaust during vacuum sealing, causing uneven exposure gaps within the surface and deviations in line width. In addition, when the material is transported in a roll-to-roll manner, the outermost layer of the photoresist adheres to the roller, sometimes causing poor transport. Therefore, the inventors of the present invention have made painstaking research to solve this problem, and found that by setting the above-mentioned first embodiment or the above-mentioned second embodiment, the smoothness of the photoresist outermost layer and the mask surface is excellent. In the above-mentioned first embodiment, by the average layer thickness of the part of the particle layer where there is no convex structure is smaller than the arithmetic average particle size of the particles contained in the particle layer, the convex structure of the required height is formed by the above-mentioned particles, and the smoothness of the photoresist outermost layer and the mask surface is improved. In addition, in the above-mentioned second embodiment, by having both the intermediate layer and the particle layer, the details are unclear, but the convex structure based on the particles is well formed, and the smoothness is improved. By setting the intermediate layer, it is easy to maintain smoothness and oxygen barrier properties. Thereby, the sensitivity and the clarity of the pattern are improved, especially when the photosensitive layer is negative. In this disclosure, smoothness is sometimes used to mean the smoothness of the photoresist top layer and the surface of the mask, in addition to the smoothness of the photoresist top layer and the surface of the roller.

The photosensitive transfer material disclosed herein may have other layers between the pseudo-support and the photosensitive layer or intermediate layer, between the intermediate layer and the photosensitive layer, between the photosensitive layer and the particle layer, between the particle layer and the covering film, etc. From the perspective of further exerting the effects of the disclosure, the photosensitive transfer material disclosed herein is preferably a roll-shaped photosensitive transfer material.

From the viewpoint of defect suppression, sensitivity and resolution in the obtained photoresist pattern, the oxygen permeability of the transfer layer in the photosensitive transfer material disclosed herein is preferably 25,000cc/(m ² ·day·atm) or less, more preferably 1,000cc/(m ² ·day·atm) or less, further preferably 100cc/(m ² ·day·atm) or less, and particularly preferably 50cc/(m ² ·day·atm) or less. Within the above range, the polymerization inhibition of the photosensitive layer caused by oxygen is suppressed, the durability after curing is excellent, and the exposure unevenness can be suppressed, the shape stability and resolution are excellent, and when forming wiring such as circuit wiring, a conductor pattern in which short circuit (short circuit failure) and disconnection (open circuit failure) are suppressed can be obtained. In addition, the unit of oxygen permeability can be converted into SI unit by the conversion formula 1fm/(s·Pa)=8.752cc/(m ² ·day·atm).

The method for measuring the oxygen permeability of the transfer layer in the present disclosure is as follows. Under the lamination conditions of roller temperature of 100°C, linear pressure of 1.0 MPa, and linear speed of 4.0 m/min, the photosensitive transfer material is laminated on a triacetate cellulose (TAC) substrate (40 μm thickness) from the photosensitive resin layer side, and the pseudo support is peeled off, thereby preparing a measurement sample with the transfer layer transferred on the TAC substrate. The measurement sample is attached to the electrode part of the measuring device (oxygen concentration meter MODEL3600 manufactured by Hach Ultra Analytics) through polysilicone grease, and the measurement environment is adjusted to 23°C 50% RH. The oxygen permeability coefficient is estimated based on the amount of oxygen reaching the electrode in a stable state.

There is no particular limitation on the method for adjusting the oxygen permeability of the transfer layer within the above range, and the following methods can be cited: a method in which, in addition to the above photosensitive resin layer, an intermediate layer or the like is provided as an oxygen barrier layer; a method in which an inorganic compound is added to the intermediate layer; a method in which an inorganic layered compound is added to the intermediate layer; a method in which the intermediate layer includes a water-soluble compound with low oxygen permeability, preferably a water-soluble resin, etc.

The following is an example of the photosensitive transfer material disclosed in the present invention, but the present invention is not limited thereto. (1) "pseudo-support body/particle layer/photosensitive layer/covering film" (2) "pseudo-support body/particle layer/intermediate layer/photosensitive layer/covering film" (3) "pseudo-support body/particle layer/thermoplastic resin layer/intermediate layer/photosensitive layer/covering film" In addition, in each of the above structures, the photosensitive layer is preferably a negative photosensitive layer. In addition, the photosensitive layer is also preferably a colored resin layer. The photosensitive transfer material disclosed in the present invention is preferably used as a photosensitive transfer material for etching resist. When used as a photosensitive transfer material for etching photoresist, the composition of the photosensitive transfer material is preferably any one of the above (1) to (3).

In the photosensitive transfer material, when the photosensitive layer further has other layers on the side opposite to the pseudo-support side, the total thickness of the other layers arranged on the side opposite to the pseudo-support side of the photosensitive layer is preferably 0.1% to 30%, and more preferably 0.1% to 20% relative to the thickness of the photosensitive layer.

Hereinafter, a specific example of an implementation mode is given to explain the photosensitive transfer material disclosed in the present invention.

Hereinafter, an example is given to explain the photosensitive transfer material. The photosensitive transfer material 20 shown in FIG. 1 has a pseudo-support 11, a transfer layer 12 including a particle layer 18, a thermoplastic resin layer 13, an intermediate layer 15 and a photosensitive layer 17, and a cover film 19 in order. The particle layer 18 has a convex structure 18a, and the convex structure 18a contains particles (not shown). In addition, the photosensitive transfer material 20 shown in FIG. 1 is a form in which the particle layer 18, the thermoplastic resin layer 13 and the intermediate layer 15 are arranged, but the thermoplastic resin layer 13 and the intermediate layer 15 are arbitrary layers and may not be arranged. In addition, as the layers included in the above transfer layer, a photosensitive layer, an intermediate layer, a particle layer, and a thermoplastic resin layer can be cited. In addition, it is assumed that the pseudo support and the covering film are not included in the above transfer layer. Below, the various elements constituting the photosensitive transfer material are explained.

[Particle layer] The photosensitive transfer material disclosed herein has a particle layer containing particles, the particle layer is in contact with the pseudo support, the particle layer and the pseudo support can be peeled off, and the surface of the particle layer on the pseudo support side has a convex structure containing the particles. The peeling off of the particle layer and the pseudo support can be confirmed by observing the surface of the substrate side exposed after peeling off the covering film of the photosensitive transfer material and thermally laminating it on the substrate, and further peeling off the pseudo support using a scanning electron microscope (SEM). The particle layer contains particles. A convex structure refers to a structure with a locally large layer thickness. It is preferred that the convex structure protrudes toward the pseudo-support body side. For a convex structure, by taking out the photosensitive transfer material in the form of a slice (thin slice) with a film thickness of about 100nm by the focused ion beam (FIB) processing method, and observing the cross section using a transmission electron microscope (TEM), it can be confirmed that the structure has a locally large layer thickness relative to the surrounding area. For a convex structure, by using SEM to observe the surface of the substrate side exposed after peeling off the covering film of the photosensitive transfer material and laminating it on the substrate, and further peeling off the pseudo-support body, it can be confirmed that the structure is locally protruding relative to the surrounding area.

In the first embodiment of the photosensitive transfer material disclosed herein, the average layer thickness of the portion of the particle layer where the convex structure does not exist is smaller than the arithmetic average particle size of the particles contained in the particle layer. In addition, in the second embodiment of the photosensitive transfer material disclosed herein, from the viewpoints of smoothness, line width uniformity of the obtained resin pattern (hereinafter, also referred to as "line width uniformity"), and linearity of the obtained resin pattern and etching pattern (hereinafter, also referred to as "linearity"), the average layer thickness of the portion of the particle layer where the convex structure does not exist is preferably smaller than the arithmetic average particle size of the particles contained in the particle layer. Furthermore, in the first embodiment of the photosensitive transfer material disclosed herein, from the viewpoints of smoothness, line width uniformity and linearity, the value of the ratio R/L of the arithmetic average particle size R of the particles contained in the particle layer to the average layer thickness L of the portion of the particle layer where the convex structure does not exist is preferably greater than 1 and less than 5, more preferably greater than 1.1 and less than 4, and particularly preferably greater than 1.2 and less than 3. Furthermore, in the second embodiment of the photosensitive transfer material disclosed herein, from the viewpoints of smoothness, line width uniformity and linearity, the value of the ratio R/L of the arithmetic average particle size R of the particles contained in the particle layer to the average layer thickness L of the portion of the particle layer where the convex structure does not exist is preferably greater than 0.5 and less than 5, more preferably greater than 1 and less than 4, and particularly preferably greater than 1 and less than 3.

The average layer thickness of the portion of the particle layer where the convex structure does not exist is measured by observing the cross section of the photosensitive transfer material in a direction perpendicular to the main surface using a scanning electron microscope (SEM) and measuring the thickness of the portion of the particle layer where the convex structure does not exist at more than 10 points based on the observed image obtained and calculating the arithmetic average thereof.

From the viewpoints of smoothness, line width uniformity and linearity, the average layer thickness of the portion of the particle layer where the convex structure does not exist is preferably 5nm to 250nm, more preferably 10nm to 200nm, more preferably 10nm to 100nm, and particularly preferably 15nm to 70nm.

The particles may be spherical, flat, or fibrous, and may be inorganic or organic. From the perspective of smoothness, the particles are preferably inorganic.

As the inorganic particles, known inorganic particles can be used. Examples of the material of the inorganic particles include BN, Al ₂ O ₃ , AlN, TiO ₂ , SiO ₂ , barium titanate, strontium titanate, aluminum hydroxide, calcium carbonate, and materials containing two or more of these. Among them, as the inorganic particles, metal oxide particles are preferred from the viewpoints of smoothness, line width uniformity, and linearity, silicon dioxide particles or titanium dioxide particles are more preferred, and silicon dioxide particles are particularly preferred.

As organic particles, known organic particles can be used. As materials of organic particles, for example, polyethylene, polystyrene, urea-formaldehyde filler, polyester, cellulose, acrylic resin, fluororesin, hardened epoxy resin, cross-linked benzoguanamine resin, cross-linked acrylic resin, liquid crystal polymer, and materials containing two or more of these can be cited. In addition, organic particles can be fibrous such as nanofibers, or hollow resin particles. Among them, as organic particles, cross-linked resin particles are preferred from the viewpoints of smoothness, line width uniformity, and linearity, and cross-linked acrylic resin particles are more preferred.

From the viewpoint of smoothness, line width uniformity and linearity, the arithmetic average particle size of the above-mentioned particles contained in the above-mentioned particle layer is preferably 5nm to 300nm, more preferably 10nm to 200nm, further preferably 20nm to 150nm, and particularly preferably 20nm to 65nm.

The arithmetic mean particle size of the particles disclosed herein is measured by the following method. The photosensitive transfer material is taken out in the form of a slice (thin slice) with a thickness of 100 nm by focused ion beam (FIB) processing, and the cross section is observed using a transmission electron microscope (TEM). The length diameter of any 100 observed particles is measured, and the arithmetic mean thereof is used as the arithmetic mean particle size.

The particle layer further preferably includes a resin. In the first embodiment of the photosensitive transfer material disclosed herein, the resin preferably includes a water-soluble resin from the viewpoint of layer formation and convex structure formation. In the second embodiment of the photosensitive transfer material disclosed herein, the resin preferably includes an alkali-soluble resin or a water-soluble resin from the viewpoint of layer formation and convex structure formation, and more preferably includes an alkali-soluble resin. Furthermore, in the second embodiment of the photosensitive transfer material disclosed herein, when the intermediate layer is in direct contact with the particle layer, the particle layer preferably includes an alkali-soluble resin. On the other hand, in the second embodiment of the photosensitive transfer material disclosed herein, when the thermoplastic resin layer described later is in direct contact with the above-mentioned particle layer, it is preferred that the above-mentioned particle layer contains a water-soluble resin.

As the water-soluble resin in the particle layer, the water-soluble resin in the intermediate layer described later can be preferably cited. In addition, as the alkali-soluble resin in the particle layer, the alkali-soluble resin in the photosensitive layer described later can be preferably cited.

The particle layer may contain one type of particle alone or more than two types. From the viewpoint of smoothness, line width uniformity and linearity, the content of particles in the particle layer is preferably 5% to 80% by mass relative to the total mass of the particle layer, more preferably 10% to 70% by mass, further preferably 15% to 65% by mass, and particularly preferably 20% to 60% by mass.

The particle layer may contain only one type of resin or more than two types. From the viewpoint of smoothness, line width uniformity and linearity, the content of the resin in the particle layer is preferably 20% to 95% by mass relative to the total mass of the particle layer, more preferably 30% to 90% by mass, further preferably 35% to 85% by mass, and particularly preferably 40% to 80% by mass.

The particle layer may contain other known components such as a surfactant. As surfactants, for example, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be cited, and nonionic surfactants are preferred. In addition, as surfactants, from the perspective of layer formation and convex structure formation, fluorine-based surfactants or silicone-based surfactants are preferred, and fluorine-based surfactants are more preferred. As preferred specific examples of surfactants, the surfactants described in the photosensitive layer described later can be cited.

[Pseudo-support] The photosensitive transfer material disclosed herein has a pseudo-support. The pseudo-support is a peelable support that supports the photosensitive layer or a laminate containing the photosensitive layer. The pseudo-support preferably has a concave structure corresponding to the convex structure of the particle layer. The pseudo-support and the particle layer can be peeled off, so the peeling force between the pseudo-support and the particle layer is preferably 0.5N/25mm or less. In addition, in order to prevent the pseudo-support and the particle layer from peeling off at the interface in the state of the photosensitive transfer material, the peeling force between the pseudo-support and the particle layer is preferably 0.001N/25mm or more. The above peeling force is measured by the method described below.

From the perspective of being able to expose the photosensitive layer through the pseudo support when the photosensitive layer is pattern-exposed, it is preferred that the pseudo support has light transmittance. In addition, in this specification, "light transmittance" means that the transmittance of the wavelength used in the pattern exposure is 50% or more. From the perspective of improving the exposure sensitivity of the photosensitive layer, the transmittance of the wavelength (preferably 365nm) used in the pattern exposure of the pseudo support is preferably 60% or more, and more preferably 70% or more. In addition, the transmittance of the layer possessed by the photosensitive transfer material is the ratio of the intensity of the outgoing light that passes through the layer to the intensity of the incident light when the light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

As materials constituting the pseudo-support, for example, glass substrates, resin films and paper can be cited. From the perspective of strength, flexibility and light transmittance, resin films are preferred. As resin films, polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films and polycarbonate films can be cited. Among them, PET films are preferred, and biaxially stretched PET films are more preferred.

The thickness (layer thickness) of the dummy support is not particularly limited. From the perspective of the strength of the support, the flexibility required in bonding with the circuit wiring forming substrate, and the light transmittance required during the initial exposure, it can be selected according to the material. The thickness of the dummy support is preferably in the range of 5μm to 100μm. From the perspective of ease of operation and versatility, the range of 10μm to 50μm is more preferred, the range of 10μm to 20μm is further preferred, and the range of 10μm to 16μm is particularly preferred. In addition, from the perspective of defect suppression, resolution, and linearity of the resin pattern, the thickness of the dummy support is preferably 50μm or less, more preferably 25μm or less, and particularly preferably 20μm or less.

Furthermore, it is preferred that the film used as the pseudo support has no deformation such as wrinkles, scratches, or defects. From the viewpoint of pattern formation during exposure of the pattern through the pseudo support and the transparency of the pseudo support, it is preferred that the number of particles, foreign matter, defects, precipitates, etc. contained in the pseudo support is small. The number of particles, foreign matter, or defects with a diameter of 1 μm or more is preferably 50 pieces/ ¹⁰ mm2 or less, more preferably 10 pieces/ ¹⁰ mm2 or less, further preferably 3 pieces/10 ^mm2 or less, and particularly preferably 0 pieces/ ¹⁰ mm2 or less.

From the perspective of defect suppression and resolution of the resin pattern and transparency of the pseudo support, the smaller the haze of the pseudo support, the better. Specifically, the haze value of the pseudo support is preferably 2% or less, 1.5% or less is more preferred, less than 1.0% is further preferred, and 0.5% or less is particularly preferred. The haze value in this disclosure is measured using a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.) in accordance with JIS K 7105:1981.

From the viewpoint of providing operability, a layer containing microparticles (lubricant layer) can be provided on the surface of the pseudo-support. The lubricant layer can be provided on one side of the pseudo-support or on both sides. The diameter of the particles contained in the lubricant layer can be set to 0.05 μm to 0.8 μm, for example. Furthermore, the thickness of the lubricant layer can be set to 0.05 μm to 1.0 μm, for example.

From the perspective of transportability, defect suppression of the resin pattern, and analytical properties, the arithmetic average roughness Ra of the surface on the side opposite to the photosensitive layer in the dummy support is preferably equal to or greater than the arithmetic average roughness Ra of the surface on the photosensitive layer in the dummy support. From the perspective of transportability, defect suppression of the resin pattern, and analytical properties, the arithmetic average roughness Ra of the surface on the side opposite to the photosensitive layer in the dummy support is preferably 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, and particularly preferably 10 nm or less. From the perspective of the releasability of the pseudo support, the defect suppression of the resin pattern, and the analytical properties, the arithmetic average roughness Ra of the surface on the photosensitive layer side of the pseudo support is preferably 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, and particularly preferably 10 nm or less. In addition, from the perspective of the transportability, the defect suppression of the photoresist pattern, and the analytical properties, the difference between the arithmetic average roughness Ra of the surface on the photosensitive layer side of the pseudo support and the arithmetic average roughness Ra of the surface on the photosensitive layer side of the pseudo support is preferably 0 nm to 10 nm, and more preferably 0 nm to 5 nm. That is, it is preferred that the arithmetic average roughness Ra of the surface on the side opposite to the photosensitive layer side in the pseudo-support is equal to or greater than the arithmetic average roughness Ra of the surface on the photosensitive layer side.

The arithmetic mean roughness Ra of the surface of the pseudo support or the covering film in this disclosure is measured by the following method. The surface of the pseudo support or the covering film is measured under the following conditions using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation) to obtain the surface profile of the film. As the measurement/analysis software, the Microscope Application of MetroPro ver8.3.2 is used. Then, the Surface Map screen is displayed using the above analysis software, and the histogram data is obtained in the Surface Map screen. The arithmetic mean roughness is calculated based on the obtained histogram data to obtain the Ra value of the surface of the pseudo support or the covering film. When the dummy support or covering film is attached to the photosensitive layer, etc., the dummy support or covering film is peeled off from the photosensitive layer and the Ra value of the surface on the peeled side is measured.

From the perspective of suppressing the peeling of the pseudo-support caused by the connection between the upper and lower stacked laminates when the rolled-up laminate is transported again by a roll-to-roll method, the peeling force of the pseudo-support, specifically, the peeling force between the pseudo-support and the photosensitive layer or the thermoplastic resin layer, is preferably 0.5 mN/mm or more, and more preferably 0.5 mN/mm to 2.0 mN/mm.

The peeling force of the pseudo support in the present disclosure is measured as follows. A copper layer with a thickness of 200 nm is formed on a polyethylene terephthalate (PET) film with a thickness of 100 μm by sputtering, thereby preparing a PET substrate with a copper layer. The cover film is peeled off from the prepared photosensitive transfer material and laminated on the above-mentioned PET substrate with a copper layer under lamination conditions of a lamination roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (lamination speed) of 1.0 m/min. Next, after attaching tape (PRINTACK manufactured by Nitto Denko Corporation) to the surface of the dummy support, the laminate having at least the dummy support and the photosensitive layer on the PET substrate with the copper layer was cut into 70 mm × 10 mm to prepare a sample. The PET substrate side of the above sample was fixed on the test stand. Using a tensile compression tester (manufactured by IMADA SEISAKUSHO CO., LTD., SV-55), the tape was stretched at 5.5 mm/s in a 180-degree direction to peel off between the photosensitive layer or thermoplastic resin layer and the dummy support, and the force required for peeling (peeling force) and the adhesion force were measured.

Preferred embodiments of the pseudo-support body are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Publication No. 2016-27363, paragraphs 0041 to 0057 of International Publication No. 2012/081680, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese Patent Publication No. 2019-101405, and the contents of these publications are incorporated into this specification.

[Adhesive layer] From the viewpoints of smoothness, releasability, and convex structure formation, it is preferable that the pseudo-support has an adhesive layer on the surface in contact with the particle layer. The material of the adhesive layer is not particularly limited and can be appropriately selected according to the purpose. For example, a layer containing a known adhesive or bonding agent can be cited.

Examples of adhesives include acrylic adhesives, urethane adhesives, rubber adhesives, silicone adhesives, and the like. Also, examples of adhesives include acrylic adhesives, ultraviolet (UV) curing adhesives, silicone adhesives, and the like described in "Evaluation of properties of release paper, release film, and adhesive tape and its control technology", Information Agency, 2004, Chapter 2. In addition, acrylic adhesives refer to adhesives containing polymers of (meth) acrylic acid monomers ((meth) acrylic acid polymers). When an adhesive is included, an adhesive imparting agent may be further included. As adhesives, for example, urethane resin adhesives, polyester resin adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, silicone adhesives, etc. can be cited. Among them, from the perspectives of smoothness, releasability, and convex structure formation, it is preferred that the adhesive layer contains a polyester resin.

The method for forming the adhesive layer is not particularly limited, and the following methods can be cited: a method of laminating a pseudo support having an adhesive layer in a manner that the adhesive layer is in contact with the intermediate layer; a method of laminating an adhesive layer in a manner that the adhesive layer is in contact with the intermediate layer alone; a method of applying a composition containing the above-mentioned adhesive or adhesive on the intermediate layer, etc. As a pseudo support having an adhesive layer, commercially available ones can be used, for example, E-MASK AW303D, E-MASK RP207 (both manufactured by Nitto Denko Corporation), PANAPROTECT HP25, PANAPROTECT MK38S (both manufactured by PANAC CO., LTD.), etc. can be cited.

As for the thickness of the adhesive layer, 5μm to 100μm is preferred from the viewpoint of both adhesion and operability. The thickness of the adhesive layer is preferably 0.01μm or more and 50μm or less, more preferably 0.1μm or more and 20μm or less, and particularly preferably 0.2μm or more and 10μm or less. When the thickness of the adhesive layer is 0.01μm or more, it is possible to prevent the particles from being buried in the photosensitive layer during lamination, and sometimes it is easy to show good smoothness when the mask contacts. In addition, when it is 50μm or less, sometimes the releasability of the pseudo-support and the particle layer becomes good.

[Photosensitive layer] The photosensitive transfer material used in the present disclosure has a photosensitive layer. The photosensitive layer may be a positive photosensitive layer or a negative photosensitive layer, but a negative photosensitive layer is preferred. The negative photosensitive layer preferably comprises an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. Based on the total mass of the above-mentioned photosensitive layer, the negative photosensitive layer preferably comprises an alkali-soluble resin: 10 mass% to 90 mass%; an ethylenically unsaturated compound: 5 mass% to 70 mass%; and a photopolymerization initiator: 0.01 mass% to 20 mass%. The positive photosensitive layer is not limited, and a known positive photosensitive layer can be used. The positive photosensitive layer preferably contains an acid-degradable resin, i.e., a polymer having a constituent unit with an acid group protected by an acid-degradable group, and a photoacid generator. In addition, the positive photosensitive layer preferably contains a resin having a constituent unit with a phenolic hydroxyl group and a quinone diazide compound. In addition, the positive photosensitive layer is more preferably a chemically amplified positive photosensitive layer containing a polymer having a constituent unit with an acid group protected by an acid-degradable group and a photoacid generator. Below, each component is explained in order. In addition, when abbreviated as "photosensitive layer", it refers to both the positive photosensitive layer and the negative photosensitive layer.

"Polymerizable compound" It is preferred that the negative photosensitive layer contains a polymerizable compound. In addition, in this specification, "polymerizable compound" refers to a compound that is polymerized by the action of a photopolymerization initiator described later, which is different from the "alkali-soluble resin" described later.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group that participates in the polymerization reaction. For example, groups having ethylenically unsaturated groups such as vinyl, acryl, methacryl, styrene, and butylene diimide groups; and groups having cationic polymerizable groups such as epoxide and cyclobutylene groups can be cited. As the polymerizable group, a group having ethylenically unsaturated groups is preferred, and an acryl or methacryl group is more preferred. In addition, as the polymerizable compound, it is preferred to contain an ethylenically unsaturated compound, and it is more preferred to contain a (meth)acrylate compound.

From the perspective of resolution and pattern formation, it is preferred that the negative photosensitive layer contain a polymerizable compound having two or more functions (multifunctional polymerizable compound), and it is more preferred that it contain a polymerizable compound having three or more functions. Here, a polymerizable compound having two or more functions refers to a compound having two or more polymerizable groups in one molecule. In addition, from the perspective of excellent resolution and peeling properties, it is preferred that the number of polymerizable groups in one molecule of the polymerizable compound is 6 or less.

From the viewpoint of a better balance between the photosensitivity, resolution and release properties of the photosensitive layer, it is preferred that the negative photosensitive layer contain a difunctional or trifunctional ethylenically unsaturated compound, and it is more preferred that the negative photosensitive layer contain a difunctional ethylenically unsaturated compound. From the viewpoint of excellent release properties, the content of the difunctional or trifunctional ethylenically unsaturated compound in the negative photosensitive layer is preferably 60% by mass or more relative to the total content of the ethylenically unsaturated compound, more preferably more than 70% by mass, and even more preferably more than 90% by mass. The upper limit is not particularly limited and may be 100% by mass. That is, the ethylenically unsaturated compounds contained in the negative photosensitive layer may all be difunctional ethylenically unsaturated compounds.

From the viewpoint of resolution and pattern formation, it is preferable that the negative photosensitive layer contains a polymerizable compound having a polyalkylene oxide structure, and it is more preferable that the negative photosensitive layer contains a polymerizable compound having a polyethylene oxide structure. As the polymerizable compound having a polyalkylene oxide structure, polyalkylene glycol di(meth)acrylate described later can be preferably cited.

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

In the negative photosensitive layer, from the viewpoint of better resolution, the mass ratio of the content of the ethylenically unsaturated compound B1 relative to the total content of the ethylenically unsaturated compound is preferably 40 mass % or more, more preferably 50 mass % or more, further preferably 55 mass % or more, and particularly preferably 60 mass % or more. The upper limit is not particularly limited, but from the viewpoint of releasability, 99 mass % or less is preferably, 95 mass % or less is more preferably, 90 mass % or less is further preferably, and 85 mass % or less is particularly preferably.

As the aromatic ring possessed by the ethylenically unsaturated compound B1, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof can be cited, and aromatic hydrocarbon rings are preferred, and benzene ring is more preferred. In addition, the above aromatic rings may have substituents. The ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

From the viewpoint of improving resolution by suppressing swelling of the negative photosensitive layer caused by the developer, it is preferable that the ethylenically unsaturated compound B1 has a bisphenol structure. As the bisphenol structure, for example, there can be cited a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), and the bisphenol A structure is preferable.

As the ethylenically unsaturated compound B1 having a bisphenol structure, for example, there can be cited a compound having a bisphenol structure and two ethylenically unsaturated groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. The two ends of the bisphenol structure may be bonded directly to the two ethylenically unsaturated groups, or may be bonded via one or more alkoxy groups. As the alkoxy groups added to both ends of the bisphenol structure, ethoxy groups or propoxy groups are preferred, and ethoxy groups are more preferred. The number of alkoxy groups added to the bisphenol structure is not particularly limited, but preferably 4 to 16 per molecule, and more preferably 6 to 14. The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, and the contents described in the publication are incorporated into this specification.

As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is 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-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydodeethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxypentadecethoxy)phenyl)propane (BPE-1300, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, Shin-Nakamura Chemical Co., Ltd.).

As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

[Chemical formula 1]

In formula (Bis), _R1 and _R2 each independently represent a hydrogen atom or a methyl group, A is _C2H4 , B is _C3H6 , _n1 and _n3 each independently represent an integer of 1 to 39, and _n1 + n3 _each represent an integer of 2 to 40, _n2 and _n4 each independently represent an integer of 0 to 29, and _n2 + n4 _{each represent} an integer of 0 to 30, and the arrangement of _the repeating units of -(AO)- and -(BO)- may be random or in blocks. In the case of blocks, any one of -(AO)- and -(BO)- may be on the bisphenol structure side. In one embodiment, _n1 + _n2 + _n3 + _n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0.

The ethylenically unsaturated compound B1 may be used alone or in combination of two or more. From the viewpoint of better analytical properties, the content of the ethylenically unsaturated compound B1 in the negative photosensitive layer is preferably 10% by mass or more, and more preferably 20% by mass or more relative to the total mass of the negative photosensitive layer. The upper limit is not particularly limited, but from the viewpoint of transferability and suppression of edge melting, 70% by mass or less is preferably, and 60% by mass or less is more preferably. The above-mentioned edge melting refers to the phenomenon that the components in the negative photosensitive layer seep out from the end of the photosensitive transfer material.

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

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

Examples of bifunctional ethylenically unsaturated compounds without an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, amine di(meth)acrylate, and trihydroxymethylpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol 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 di(meth)acrylates include propylene oxide-modified amine di(meth)acrylate and ethylene oxide and propylene oxide-modified amine di(meth)acrylate. Examples of commercially available products 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 ethylenically unsaturated compounds include dipentatriol (tri/tetra/penta/hexa) (meth)acrylate, pentatriol (tri/tetra) (meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ditrihydroxymethylpropane tetra(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, and oxirane modified products thereof. Here, "(tri/tetra/penta/hexa) (meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri/tetra) (meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the negative photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the trifunctional or higher ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compounds) = 1:1 to 5:1, preferably 1.2:1 to 4:1, and more preferably 1.5:1 to 3:1. In one embodiment, the negative photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified products of trifunctional or higher ethylenic unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glyceryl triacrylate (Shin-Nakamura Chemical 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.).

As ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1, ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

From the viewpoint of resolution and linearity, the value of the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound to the content Mb of the alkali-soluble resin in the negative photosensitive layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. In addition, from the viewpoint of curability and resolution, it is preferred that the ethylenically unsaturated compound in the negative photosensitive layer includes a (meth) acrylic compound. Furthermore, from the viewpoint of curability, resolution and linearity, it is preferred that the ethylenically unsaturated compound in the negative photosensitive layer includes a (meth) acrylic compound, and the content of the acrylic compound is 60% by mass or less relative to the total mass of the (meth) acrylic compound contained in the negative photosensitive layer.

The molecular weight (when having a distribution, weight average molecular weight (Mw)) of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

The ethylenically unsaturated compound may be used alone or in combination of two or more. The content of the ethylenically unsaturated compound in the negative 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 relative to the total mass of the negative photosensitive layer.

《Photopolymerization initiator》 It is preferable that the negative photosensitive layer contains a photopolymerization initiator. The photopolymerization initiator is a compound that initiates polymerization of ethylenically unsaturated compounds when exposed to active light such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photoradical polymerization initiator and a photocationic ion polymerization initiator can be cited. Among them, from the viewpoint of resolution and pattern formation, it is preferable that the photosensitive layer is a photoradical polymerization initiator.

As the photoradical polymerization initiator, for example, a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a biimidazole compound can be cited.

As the photoradical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783 can be used.

Examples of the photoradical polymerization initiator include dimethylaminobenzoic acid ethyl ester (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.).

Examples of commercially available photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime) (trade name: IRGACURE OXE02, manufactured by BASF), IRGACURE OXE03 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-indole)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-isopropylpropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-isopropylphenyl)butanone-1-one (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan K.K.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: B-CIM, manufactured by Hampford) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

Photocatalytic ion polymerization initiators (photoacid generators) are compounds that generate acid when exposed to active light. As photocatalytic ion polymerization initiators, compounds that generate acid by responding to active light with a wavelength of 300nm or more, preferably 300nm to 450nm, are preferred, but their chemical structures are not limited. In addition, photocatalytic ion polymerization initiators that do not directly respond to active light with a wavelength of 300nm or more can also be used in combination with a sensitizer as long as they are compounds that respond to active light with a wavelength of 300nm or more and generate acid by using a sensitizer. As a photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is particularly preferred. There is no particular lower limit for pKa, for example, -10.0 or more is preferred.

As the photocatalytic polymerization initiator, there can be mentioned ionic photocatalytic polymerization initiators and nonionic photocatalytic polymerization initiators. As the ionic photocatalytic polymerization initiator, for example, onium salt compounds such as diaryl iodonium salts and triaryl stibnium salts and quaternary ammonium salts can be mentioned. As the ionic photocatalytic polymerization initiator, the ionic photocatalytic polymerization initiators described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 can be used.

As nonionic photocatalytic polymerization initiators, for example, trichloromethyl-s-trioxanes, diazomethane compounds, acylimide sulfonate compounds, and oxime sulfonate compounds can be cited. As trichloromethyl-s-trioxanes, diazomethane compounds, and acylimide sulfonate compounds, the compounds described in paragraphs 0083 to 0088 of Japanese Patent Publication No. 2011-221494 can be used. In addition, as oxime sulfonate compounds, the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be used.

The negative photosensitive layer may contain one photopolymerization initiator alone or two or more. The content of the photopolymerization initiator in the negative photosensitive layer is not particularly limited, but preferably 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. The upper limit is not particularly limited, but preferably 10% by mass or less relative to the total mass of the negative photosensitive layer, and more preferably 5% by mass or less.

《Alkali-soluble resin》 The negative photosensitive layer preferably contains an alkali-soluble resin. In addition, in this specification, "alkali-soluble" means that the solubility in 100g of a 1 mass% aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1g or more. There is no particular limitation on the alkali-soluble resin, and for example, a known alkali-soluble resin used for etching photoresist can be preferably cited. In addition, the alkali-soluble resin is preferably a binder polymer. As the alkali-soluble resin, an alkali-soluble resin having an acid group is preferably used. Among them, as the alkali-soluble resin, the polymer A described later is preferably used.

-Polymer A- As the alkali-soluble resin, it is preferable to include polymer A. From the viewpoint of better resolution by suppressing the swelling of the photosensitive layer caused by the developer, the acid value of polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and further preferably less than 190 mgKOH/g. The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better development, 60 mgKOH/g or more is preferred, 120 mgKOH/g or more is more preferred, 150 mgKOH/g or more is further preferred, and 170 mgKOH/g or more is particularly preferred.

In addition, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1g of the sample. In this manual, the unit is recorded as mgKOH/g. The acid value can be calculated, for example, based on the average content of the acid group in the compound. The acid value of polymer A can be adjusted using the type of constituent units constituting 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, it is preferred that the weight average molecular weight is 500,000 or less. It is more preferred that the weight average molecular weight is 100,000 or less, further preferred that it is 60,000 or less, and particularly preferred that it is 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge melting and cutting properties, it is preferred that the weight average molecular weight is 5,000 or more. It is more preferred that the weight average molecular weight is 10,000 or more, further preferred that it is 20,000 or more, and particularly preferred that it is 30,000 or more. Edge melting refers to the ease with which the photosensitive layer overflows from the end surface of the roll when the photosensitive transfer material is rolled into a roll. Cutting property refers to the ease with which cutting chips fly when the unexposed film is cut with a cutter. If the cutting chips adhere to the upper surface of the photosensitive layer, etc., they will be transferred to the mask in the subsequent exposure step, etc., and become a defective product. The dispersion degree of polymer A is preferably 1.0 to 6.0, 1.0 to 5.0 is more preferably, 1.0 to 4.0 is further preferably, and 1.0 to 3.0 is further preferably. In this disclosure, the molecular weight is a value measured using gel permeation analysis. In addition, the dispersion degree is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing the deterioration of line width or resolution when the focus position deviates during exposure, it is preferable that the negative photosensitive layer contains a monomer component having an aromatic hydrocarbon group as polymer A. In addition, as such an aromatic hydrocarbon group, for example, a substituted or unsubstituted phenyl group or a substituted or unsubstituted aralkyl group can be cited. The content of the monomer component having an aromatic hydrocarbon group in polymer A is preferably 20% by mass or more, 30% by mass or more is more preferably, 40% by mass or more is further preferably, 45% by mass or more is particularly preferably, and 50% by mass or more is the best, based on the total mass of all monomer components. As an upper limit, it is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. In addition, when the negative photosensitive layer contains multiple polymers A, the content of the monomer component having an aromatic hydrocarbon group is calculated as a weight average value.

As the above-mentioned monomer having an aromatic hydrocarbon group, for example, monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methyl styrene, vinyl toluene, tertiary butoxy styrene, acetyloxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.) can be cited. Among them, monomers having an aralkyl group or styrene are preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content of the styrene monomer component is preferably 20% to 50% by mass based on the total mass of all monomer components, more preferably 25% to 45% by mass, further preferably 30% to 40% by mass, and particularly preferably 30% to 35% by mass.

As the aralkyl group, there can be mentioned a substituted or unsubstituted phenylalkyl group (excluding benzyl group), a substituted or unsubstituted benzyl group, and the like, and a substituted or unsubstituted benzyl group is preferred.

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

As the monomer having a benzyl group, there can be cited (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate, benzyl (meth)acrylate chloride, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, etc. Among them, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon in polymer A is benzyl (meth)acrylate, the content of the benzyl (meth)acrylate monomer component is preferably 50 mass% to 95 mass%, more preferably 60 mass% to 90 mass%, further preferably 70 mass% to 90 mass%, and particularly preferably 75 mass% to 90 mass%, based on the total mass of all monomer components.

The polymer A containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one first monomer described later and/or at least one second monomer described later.

The polymer A containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one first monomer described below, and is more preferably obtained by copolymerizing at least one first monomer and at least one second monomer described below.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, etc. Among them, (meth)acrylic acid is preferred. The content of the first monomer in polymer A is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, and even more preferably 15% to 30% by mass based on the total mass of all monomer components.

The copolymerization ratio of the first monomer is preferably 10 mass % to 50 mass % based on the total mass of all monomer components. From the viewpoint of showing good developing properties and controlling edge melting properties, it is preferred that the copolymerization ratio is 10 mass % or more, 15 mass % or more is more preferred, and 20 mass % or more is further preferred. From the viewpoint of high resolution and shape of the bottom hem of the photoresist pattern, and further from the viewpoint of the chemical resistance of the photoresist pattern, it is preferred that the copolymerization ratio is 50 mass % or less, and from these viewpoints, 35 mass % or less is more preferred, 30 mass % or less is further preferred, and 27 mass % or less is particularly preferred.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate n-propyl, (meth)acrylate isopropyl, (meth)acrylate n-butyl, (meth)acrylate isobutyl, (meth)acrylate tertiary butyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate 2-hydroxypropyl, (meth)acrylate cyclohexyl, (meth)acrylate 2-ethylhexyl, (meth)acrylate and other (meth)acrylate esters; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred. The content of the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass based on the total mass of all monomer components.

From the viewpoint of suppressing the deterioration of line width or resolution when the focus position deviates during exposure, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, etc. are preferable. In one embodiment, polymer A is preferably a polymer containing 25% to 40% by mass of a monomer component having an aromatic hydrocarbon, 20% to 35% by mass of a first monomer component, and 30% to 45% by mass of a second monomer component. In another embodiment, a polymer containing 70% to 90% by mass of a monomer component having an aromatic hydrocarbon and 10% to 25% by mass of a first monomer component is preferable.

Polymer A may have any of a straight chain structure, a branched structure, and an alicyclic structure in the side chain. By using a monomer containing a base having a branched structure in the side chain or a monomer containing a base having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer A. The base having an alicyclic structure may be monocyclic or polycyclic. Specific examples of monomers containing a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, tertiary pentyl (meth)acrylate, isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and tertiary octyl (meth)acrylate. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tertiary butyl (meth)acrylate is preferred, and isopropyl (meth)acrylate or tertiary butyl (meth)acrylate is more preferred. Examples of the monomer containing a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group, a monomer having a polycyclic aliphatic hydrocarbon group, and a (meth)acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. As more specific examples, for example, (bicyclo[2.2.1]heptyl-2-(meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like can be cited. methyl (meth)acrylate, 1-mentholyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like. Among the (meth)acrylates, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-mentholyl (meth)acrylate or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate or tricyclodecane (meth)acrylate is particularly preferred.

Polymer A may be used alone or in combination of two or more. When two or more polymers are used in combination, it is preferred to use two polymers A containing monomer components having aromatic hydrocarbon groups in combination or to use a polymer A containing monomer components having aromatic hydrocarbon groups and a polymer A not containing monomer components having aromatic hydrocarbon groups in combination. In the latter case, the proportion of polymer A containing monomer components having aromatic hydrocarbon groups used relative to the total amount of polymer A is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

The synthesis of polymer A is preferably carried out by adding an appropriate amount of a free radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution prepared by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc., and heating and stirring. Sometimes, a part of the mixture is added dropwise to the reaction solution while the synthesis is carried out. After the reaction is completed, a solvent is sometimes further added to adjust the concentration to the desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization can be used.

The glass transition temperature Tg of polymer A is preferably above 30°C and below 135°C. By using polymer A having a Tg of below 135°C in the photosensitive layer, it is possible to suppress the deterioration of line width coarseness or resolution when the focus position deviates during exposure. From this point of view, it is more preferable that the Tg of polymer A is below 130°C, further preferably below 120°C, and particularly preferably below 110°C. Furthermore, from the viewpoint of improving edge melting resistance, it is preferable to use polymer A having a Tg of above 30°C. From this point of view, it is more preferable that the Tg of polymer A is above 40°C, further preferably above 50°C, particularly preferably above 60°C, and best above 70°C.

The negative photosensitive layer may contain a resin other than an alkali-soluble resin. As the resin other than an alkali-soluble resin, there may be mentioned acrylic resin, styrene-acrylic acid copolymer (wherein the styrene content is 40% by mass or more), polyurethane resin, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycol.

Alkali-soluble resins may be used alone or in combination of two or more. The ratio of the alkali-soluble resin to the total mass of the negative photosensitive layer is preferably in the range of 10 mass% to 90 mass%, more preferably 30 mass% to 70 mass%, and further preferably 40 mass% to 60 mass%. From the viewpoint of controlling the development time, it is preferred that the ratio of the alkali-soluble resin to the negative photosensitive layer is 90 mass% or less. On the other hand, from the viewpoint of improving the edge melting resistance, it is preferred that the ratio of the alkali-soluble resin to the negative photosensitive layer is 10 mass% or more.

《Compounds with unshared electron pairs》 From the viewpoint of adhesion to the conductive layer, it is preferred that the photosensitive layer contains a compound with unshared electron pairs. As compounds with unshared electron pairs, from the viewpoint of adhesion to the conductive layer, compounds having at least nitrogen atoms, oxygen atoms or sulfur atoms are preferred, heterocyclic compounds, thiol compounds or disulfide compounds are more preferred, heterocyclic compounds are further preferred, and nitrogen-containing heterocyclic compounds are particularly preferred. Furthermore, from the viewpoint of coordination and dimensional stability of the conductive pattern after energization, the nitrogen-containing heterocyclic compound preferably has a heterocyclic ring having two or more nitrogen atoms, more preferably has a heterocyclic ring having three or more nitrogen atoms, and particularly preferably has a heterocyclic ring having three or four nitrogen atoms.

The heterocyclic compound may be a monocyclic or polycyclic heterocyclic compound. As heteroatoms in the heterocyclic compound, nitrogen atoms, oxygen atoms, and sulfur atoms can be cited. It is preferred that the heterocyclic compound has at least one atom selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and it is more preferred that the heterocyclic compound has a nitrogen atom.

As the heterocyclic compound, for example, a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a trioxane compound, a thiodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound or a pyrimidine compound can be preferably mentioned. Among the above, from the viewpoint of close adhesion with the conductive layer a, the heterocyclic compound is preferably at least one compound selected from the group including triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, trioxane compounds, thiazole compounds, benzimidazole compounds and benzothiazole compounds, more preferably at least one compound selected from the group including triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzothiazole compounds, further preferably at least one compound selected from the group including triazole compounds and tetrazole compounds, and triazole compounds are particularly preferred.

Preferred specific examples of the heterocyclic compound are shown below. As the triazole compound and the benzotriazole compound, the following compounds can be exemplified.

[Chemical formula 2]

[Chemical formula 3]

As the tetrazole compound, the following compounds can be exemplified.

[Chemical formula 4]

[Chemical formula 5]

As the thiadiazole compound, the following compounds can be exemplified.

[Chemical formula 6]

As the tribasic compound, the following compounds can be exemplified.

[Chemical formula 7]

As the peridotanninine compound, the following compounds can be exemplified.

[Chemical formula 8]

As the thiazole compound, the following compounds can be exemplified.

[Chemical formula 9]

As the benzothiazole compound, the following compounds can be exemplified.

[Chemical formula 10]

As the benzimidazole compound, the following compounds can be exemplified.

[Chemical formula 11]

[Chemical formula 12]

As the benzoxazole compound, the following compounds can be exemplified.

[Chemical formula 13]

As the sulfur-containing compound, thiol compounds and disulfide compounds can be preferably cited. As the thiol compound, aliphatic thiol compounds can be preferably cited. As the aliphatic thiol compound, monofunctional aliphatic thiol compounds or polyfunctional aliphatic thiol compounds (that is, aliphatic thiol compounds with two or more functionalities) can be preferably used. Examples of the polyfunctional aliphatic thiol compound include trihydroxymethylpropane tris(3-butylbutyrate), 1,4-bis(3-butylbutyryloxy)butane, pentaerythritol tetra(3-butylbutyrate), 1,3,5-tris(3-butylbutyryloxyethyl)-1,3,5-tris(3-butylbutyryloxyethyl)-2,4,6(1H,3H,5H)-trione, trihydroxymethylethane tris(3-butylbutyrate), tris[(3-butylpropionyloxy)ethyl]isocyanurate, trihydroxymethylpropane Tris(3-butyl propionate), pentaerythritol tetra(3-butyl propionate), tetraethylene glycol bis(3-butyl propionate), dipentaerythritol hexa(3-butyl propionate), ethylene glycol bis(thiopropionate), 1,4-bis(3-butylbutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dibutylsuccinic acid and di(butylethyl) ether. Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-butylpropionic acid, methyl-3-butylpropionate, 2-ethylhexyl-3-butylpropionate, n-octyl-3-butylpropionate, methoxybutyl-3-butylpropionate, and stearyl-3-butylpropionate.

Examples of the disulfide compounds include 2-(4'-benzothiazolyl disulfide)benzothiazole, 2,2'-benzothiazolyl disulfide, bis(2-benzoamidophenyl) disulfide, 1,1-thiobis(2-naphthol), bis(2,4,5-trichlorophenyl) disulfide, 4,4'-dithiobenzothiazolyl disulfide, tetraethylthiuram disulfide, dibenzyl disulfide, bis(2,4-dinitrophenyl) disulfide, 4,4'-diaminodiphenyl disulfide, diallyl disulfide, di-tert-butyl disulfide, bis(6-hydroxy-2-naphthyl) disulfide, dicyclohexyl disulfide, o-isobutylthiamine disulfide, and diphenyl disulfide.

Furthermore, from the viewpoint of adhesion with the conductive layer, the molecular weight of the compound having an unshared electron pair is preferably less than 1,000, more preferably 50 to 500, further preferably 50 to 200, and particularly preferably 50 to 150.

The photosensitive layer may contain one compound having an unshared electron pair alone, or may contain two or more compounds. From the viewpoint of adhesion with the conductive layer, the content of the compound having an unshared electron pair is preferably 0.01 mass% to 20 mass% relative to the total mass of the photosensitive layer, more preferably 0.1 mass% to 10 mass%, further preferably 0.3 mass% to 8 mass%, and particularly preferably 0.5 mass% to 5 mass%.

《Pigment》 From the perspective of visibility of the exposed and non-exposed parts, visibility of the pattern after development, and resolution, it is better for the photosensitive layer to contain a pigment, and it is more preferable to contain a pigment whose maximum absorption wavelength is 450nm or more in the wavelength range of 400nm to 780nm during color development and whose maximum absorption wavelength changes by acid, alkali, or free radicals (also referred to as "pigment N" for short). If the photosensitive layer contains pigment N, the detailed mechanism is not clear, but the adhesion between the adjacent layers (e.g., pseudo-support and substrate) and the photosensitive layer is improved, and the resolution is better.

In this specification, "the maximum absorption wavelength of a pigment changes due to acid, alkali or free radicals" may refer to any of the following: a pigment in a coloring state decolorizes due to acid, alkali or free radicals, a pigment in a decolorizing state develops color due to acid, alkali or free radicals, and a pigment in a coloring state changes to a coloring state of another hue. Specifically, the pigment N may be a compound that changes from a decolorizing state to a coloring state due to exposure, or may be a compound that changes from a coloring state to a decoloring state due to exposure. In this case, the dye may be a dye that generates acid, alkali or free radicals in the photosensitive layer by exposure and changes the state of coloring or decoloring by the action of these dyes, or a dye that changes the state (e.g., pH) in the photosensitive layer by acid, alkali or free radicals. In addition, the dye may be a dye that changes the state of coloring or decoloring by being directly stimulated by acid, alkali or free radicals without exposure.

Among them, from the viewpoint of visibility and resolution of the exposed and non-exposed parts, it is preferable that the dye N is a dye whose maximum absorption wavelength changes by acid or free radicals, and it is more preferable that the dye whose maximum absorption wavelength changes by free radicals. From the viewpoint of visibility and resolution of the exposed and non-exposed parts, it is preferable that the photosensitive layer contains both a dye whose maximum absorption wavelength changes by free radicals as the dye N and a photoradical polymerization initiator. Furthermore, from the viewpoint of visibility of the exposed and non-exposed parts, it is preferable that the dye N is a dye that develops color by acid, alkali or free radicals.

As an example of the coloring mechanism of the dye N in the present disclosure, a radical-reactive dye, an acid-reactive dye or an alkali-reactive dye (for example, a colorless dye) can be cited in which a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photoalkali generator is added to a photosensitive layer and then exposed to light, and then the free radicals, acid or base generated by the photoradical polymerization initiator, the photocationic polymerization initiator or the photoalkali generator develop color.

From the viewpoint of visibility of the exposed and non-exposed parts, the maximum absorption wavelength of the dye N during color development in the wavelength range of 400 nm to 780 nm is preferably 550 nm or more, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

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

As a dye that develops or fades by exposure, for example, a colorless compound can be cited. As a dye that fades by exposure, for example, a colorless compound, a diarylmethane-based dye, a thiocyanate-based dye, a galaxy-based dye, an imino-naphthoquinone-based dye, an azomethine-based dye, and an anthraquinone-based dye can be cited. As the dye N, a colorless compound is preferred from the viewpoint of visibility of the exposed portion and the non-exposed portion.

As colorless compounds, for example, colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorescent yellow matrix skeleton (fluorescent yellow matrix pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactamide skeleton (rhodamine lactamide pigments), colorless compounds having an indolylphthalide skeleton (indolylphthalide pigments), and colorless compounds having a colorless golden amine skeleton (colorless golden amine pigments) can be cited. Among them, triarylmethane pigments or fluorescent yellow matrix pigments are preferred, and colorless compounds having a triphenylmethane skeleton (triphenylmethane pigments) or fluorescent yellow matrix pigments are more preferred.

From the viewpoint of visibility of the exposed part and the non-exposed part, the colorless compound preferably has a lactone ring, a sultine ring or a sultone ring. In this way, the lactone ring, the sultine ring or the sultone ring of the colorless compound can react with the radical generated by the photo-radical polymerization initiator or the acid generated by the photo-cationic polymerization initiator to change the colorless compound into a closed ring state and decolorize it, or change the colorless compound into an open ring state and develop color. As the colorless compound, a compound having a lactone ring, a sulphenone ring or a sultone ring which develops color by free radical or acid ring opening is preferred, and a compound having a lactone ring which develops color by free radical or acid ring opening is more preferred.

As pigment N, for example, the following dyes and colorless compounds can be cited. Specific examples of dyes in the pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurpurine 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue-naphthalenesulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Industries, Ltd.), and so on. Co., Ltd.), Oil Pink #312 (Orient Chemical Industries Co., Ltd.), Oil Red 5B (Orient Chemical Industries Co., Ltd.), Oil Scarlet #308 (Orient Chemical Industries Co., Ltd.), Oil Red OG (Orient Chemical Industries Co., Ltd.), Oil Red RR (Orient Chemical Industries Co., Ltd.), Oil Green #502 (Orient Chemical Industries Co., Ltd.), Spilon Red BEH Special (Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonate rhodamine 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 the pigments N, specific examples of colorless compounds include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by BASF), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow matrix, 2-anilino-3-methyl-6-(N-ethyl-p-toluinyl) fluorescent yellow matrix, 3,6-dimethoxy fluorescent yellow matrix, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino) fluorescent yellow matrix, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7 -aniline fluorescent yellow matrix, 3-(N,N-diethylamino)-6-methyl-7-aniline fluorescent yellow matrix, 3-(N,N-diethylamino)-6-methyl-7-sulphoamino fluorescent yellow matrix, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow matrix, 3-(N,N-diethylamino)-6-methyl-7-amino fluorescent yellow matrix, 3-(N,N-diethylamino)-6-methoxy-7-amino fluorescent yellow matrix, 3-(N,N-diethylamino)-7-(4-chloroaniline) fluorescent yellow matrix, 3-(N,N-diethylamino)-7-chlorofluorescent yellow matrix, -(N,N-diethylamino)-7-benzylamino fluorescent yellow matrix, 3-(N,N-diethylamino)-7,8-benzofluorescent yellow matrix, 3-(N,N-dibutylamino)-6-methyl-7-anilino fluorescent yellow matrix, 3-(N,N-dibutylamino)-6-methyl-7-sulphoamino fluorescent yellow matrix, 3-piperidinyl-6-methyl-7-anilino fluorescent yellow matrix, 3-pyrrolidinyl-6-methyl-7-anilino fluorescent yellow matrix, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalolide, 3,3-Bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-Bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]-o-yamatocin-3-one.

From the perspective of visibility of the exposed and non-exposed parts, and visibility and resolution of the pattern after development, it is preferred that the pigment N is a pigment whose maximum absorption wavelength changes due to free radicals, and it is more preferred that the pigment develops color due to free radicals. As the pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue-naphthalenesulfonate is preferred.

The pigment may be used alone or in combination of two or more. From the viewpoint of visibility of the exposed and non-exposed parts, and the visibility and resolution of the pattern after development, the content of the pigment is preferably 0.1% by mass or more relative to the total mass of the photosensitive layer, 0.1% by mass to 10% by mass is more preferred, 0.1% by mass to 5% by mass is further preferred, and 0.1% by mass to 1% by mass is particularly preferred. Furthermore, from the viewpoint of visibility of the exposed and non-exposed parts, and the visibility and resolution of the pattern after development, the content of the pigment N is preferably 0.1% by mass or more relative to the total mass of the photosensitive layer, 0.1% by mass to 10% by mass is more preferred, 0.1% by mass to 5% by mass is further preferred, and 0.1% by mass to 1% by mass is particularly preferred.

The content of pigment N refers to the content of pigment when all pigment N contained in the photosensitive layer is in a colored state. The following is an example of a pigment that develops color by free radicals to explain the quantitative method of the content of pigment N. Two solutions were prepared by dissolving 0.001g or 0.01g of pigment in 100mL of methyl ethyl ketone. Photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) was added to each of the obtained solutions, and irradiated with 365nm light to generate free radicals, so that all pigments are in a colored state. Then, in an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve was prepared. Next, 3 g of the photosensitive layer was dissolved in methyl ethyl ketone instead of the pigment, and the absorbance of the solution in which the pigment was fully colored was measured using the same method as above. Based on the absorbance of the solution containing the photosensitive layer obtained, the content of the pigment contained in the photosensitive layer was calculated according to the calibration curve.

《Thermal crosslinking compound》 From the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film, it is preferable that the photosensitive layer contains a thermal crosslinking compound. In addition, in this specification, the thermal crosslinking compound having an ethylenic unsaturated group described later is not treated as a polymerizable compound, but as a thermal crosslinking compound. As thermal crosslinking compounds, hydroxymethyl compounds and blocked isocyanate compounds can be cited. Among them, blocked isocyanate compounds are preferable from the viewpoint of the strength of the obtained cured film and the adhesion of the obtained uncured film. Blocked isocyanate compounds react with hydroxyl groups and carboxyl groups, so when, for example, a resin and/or polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film decreases, thereby increasing the function of the film formed by curing the photosensitive layer as a protective film. In addition, a blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent."

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, and more preferably 130°C to 150°C. The dissociation temperature of the blocked isocyanate refers to "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter." As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

As the end-capping agent with a dissociation temperature of 100°C to 160°C, there can be cited active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc., compounds having a structure represented by -C (=N-OH)- in the molecule). Among them, as the end-capping agent with a dissociation temperature of 100°C to 160°C, for example, from the viewpoint of storage stability, it is preferable to include oxime compounds.

For example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer body, the blocked isocyanate compound preferably has an isocyanurate structure. The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanuricating hexamethylene diisocyanate to protect it. Among the blocked isocyanurate compounds having an isocyanurate structure, the compound having an oxime structure using an oxime compound as a blocking agent is preferred from the viewpoint that the dissociation temperature is easily set within a preferred range compared to the compound without an oxime structure and the development residue is easily reduced.

The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a free radical polymerizable group is preferred. As the polymerizable group, ethylenically unsaturated groups such as (meth)acryloxy, (meth)acrylamide, and styrene groups, and groups having epoxy groups such as glyoxypropyl groups can be cited. Among them, as the polymerizable group, ethylenically unsaturated groups are preferred, (meth)acryloxy groups are more preferred, and acryloxy groups are further preferred.

As the blocked isocyanate compound, a commercial product can be used. Examples of commercial products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by SHOWA DENKO K.K.), and blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). In addition, as the blocked isocyanate compound, a compound having the following structure can also be used.

[Chemical formula 14]

The thermally crosslinkable compound may be used alone or in combination of two or more. When the photosensitive layer contains the thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% to 50% by mass, and more preferably 5% to 30% by mass, relative to the total mass of the photosensitive layer.

《Polymer having a constituent unit having an acid group protected by an acid-degradable group》 The positive photosensitive layer preferably contains a polymer (hereinafter sometimes referred to as "polymer X") having a constituent unit having an acid group protected by an acid-degradable group (hereinafter sometimes referred to as "constituent unit A"). The positive photosensitive layer may contain a single polymer X or two or more polymers X.

In polymer X, the acid groups protected by the acid-decomposable groups are converted into acid groups through a deprotection reaction by the action of a catalytic amount of an acidic substance (e.g., an acid) generated by exposure. By generating acid groups in polymer X, the solubility of the positive photosensitive layer in the developer solution increases.

The polymer X is preferably an addition polymerization type polymer, and more preferably a polymer having a constituent unit derived from (meth)acrylic acid or its ester.

- Constituent unit having an acid group protected by an acid-degradable group- It is preferable that the polymer X has a constituent unit having an acid group protected by an acid-degradable group (constituent unit A). When the polymer X has constituent unit A, the sensitivity of the positive photosensitive layer can be improved.

The acid group is not limited, and a known acid group can be used. The acid group is preferably a carboxyl group or a phenolic hydroxyl group.

As the acid-decomposable group, for example, a group that is relatively easy to decompose by acid and a group that is relatively difficult to decompose by acid can be cited. As the group that is relatively easy to decompose by acid, for example, an acetal type protecting group (for example, 1-alkoxyalkyl, tetrahydropyranyl and tetrahydrofuranyl) can be cited. As the group that is relatively difficult to decompose by acid, for example, a tertiary alkyl (for example, tertiary butyl) and a tertiary alkoxycarbonyl (for example, tertiary butoxycarbonyl) can be cited. Among the above, it is preferred that the acid-decomposable group is an acetal type protecting group.

From the viewpoint of suppressing the variation in line width of the resin pattern, the molecular weight of the acid-decomposable group is preferably 300 or less.

From the viewpoint of sensitivity and resolution, the constituent unit A is preferably a constituent unit represented by the following formula A1, a constituent unit represented by the following formula A2, or a constituent unit represented by the following formula A3, and a constituent unit represented by the following formula A3 is more preferred. The constituent unit represented by the following formula A3 is a constituent unit having a carboxyl group protected by an acetal-type acid-decomposable group.

[Chemical formula 15]

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, R ¹³ represents an alkyl group or an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, X ¹ represents a single bond or a divalent linking group, R ¹⁵ represents a substituent, and n represents an integer of 0 to 4.

In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, R ²³ represents an alkyl group or an aryl group, R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, R ²⁴ each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.

In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an aryl group.

In formula A3, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. In formula A3, when R ³¹ or R ³² is an aryl group, a phenyl group is preferred. In formula A3, R ³¹ and R ³² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which is preferred. In formula A3, R ³³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms, which is preferred. In formula A3, the alkyl and aryl groups represented by R ³¹ to R ³³ may have a substituent. In formula A3, R ³¹ or R ³² is preferably linked to R ³³ to form a cyclic ether. The number of ring members of the cyclic ether is preferably 5 or 6, and more preferably 5. In formula A3, X ⁰ is preferably a single bond. The arylene group may have a substituent. In Formula A3, from the viewpoint of being able to further lower the glass transition temperature (Tg) of the polymer X, it is preferred that R ³⁴ is a hydrogen atom.

The content of the constituent unit in which R ³⁴ in formula A3 is a hydrogen atom is preferably 20 mass % or more relative to the total mass of the constituent units A contained in the polymer X. The content of the constituent unit in which R ³⁴ in formula A3 is a hydrogen atom in the constituent unit A can be confirmed by using the intensity ratio of the peak intensity calculated by a conventional method based on ¹³ C-nuclear magnetic resonance spectroscopy (NMR) measurement.

As preferred embodiments of Formulas A1 to A3, reference may be made to paragraphs 0044 to 0058 of International Publication No. 2018/179640.

In Formulae A1 to A3, from the viewpoint of sensitivity, the acid-decomposable group is preferably a group having a ring structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, further preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuran group.

The polymer X may have a single type of constituent unit A, or may have two or more types of constituent units A.

The content of the constituent unit A is preferably 10 mass % to 70 mass % relative to the total mass of the polymer X, more preferably 15 mass % to 50 mass % and particularly preferably 20 mass % to 40 mass %. When the content of the constituent unit A is within the above range, the resolution is further improved. When the polymer X contains two or more constituent units A, the content of the constituent unit A above represents the total content of the two or more constituent units A. The content of the constituent unit A can be confirmed by using the intensity ratio of the peak intensity calculated by the conventional method based on ¹³ C-NMR measurement.

- Constituent unit having an acid group- Polymer X may have a constituent unit having an acid group (hereinafter, also referred to as "constituent unit B").

The constituent unit B is a constituent unit having an acid group that is not protected by an acid-decomposable group, i.e., an acid group that does not have a protecting group. The polymer X having the constituent unit B improves the sensitivity during pattern formation. In addition, since it is easily dissolved in an alkaline developer in the development step after exposure, the development time can be shortened.

The acid group in the structural unit B is a proton dissociative group having a pKa of 12 or less. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Furthermore, the pKa of the acid group is preferably -5 or more.

Examples of the acid group include a carboxyl group, a sulfonylamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonyl acylimide group. The acid group is preferably a carboxyl group or a phenolic hydroxyl group, and more preferably a carboxyl group.

The polymer X may have a single constituent unit B, or may have two or more constituent units B.

The content of the constituent unit B is preferably 0.01 mass % to 20 mass % relative to the total mass of the polymer X, more preferably 0.01 mass % to 10 mass % and particularly preferably 0.1 mass % to 5 mass %. When the content of the constituent unit B is within the above range, the resolvability becomes better. When the polymer X has two or more constituent units B, the content of the constituent unit B above represents the total content of the two or more constituent units B. The content of the constituent unit B can be confirmed by using the intensity ratio of the peak intensity calculated by a conventional method based on ¹³ C-NMR measurement.

-Other constituent units- It is preferable that polymer X has other constituent units (hereinafter, sometimes referred to as "constituent unit C") other than the constituent units A and B described above. By adjusting at least one of the type and content of constituent unit C, many properties of polymer X can be adjusted. By having constituent unit C in polymer X, the glass transition temperature, acid value and hydrophilicity of polymer X can be easily adjusted.

Examples of the monomer forming the constituent unit C include styrenes, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, aryl (meth)acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, succinimidyl compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic anhydrides.

From the viewpoint of adhesion to the substrate, the monomer forming the constituent unit C is preferably an alkyl (meth)acrylate, and more preferably an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

As the constituent unit C, there can be cited a constituent unit derived from styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, acrylonitrile or ethylene glycol monoacetyl acetate mono(meth)acrylate. As the constitutional unit C, there can be cited constitutional units derived from compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623.

From the viewpoint of analytical properties, it is preferred that the constituent unit C includes a constituent unit having a basic group. Examples of the basic group include a group having a nitrogen atom. Examples of the group having a nitrogen atom include an aliphatic amine group, an aromatic amine group, and a nitrogen-containing heteroaromatic ring group. The basic group is preferably an aliphatic amine group.

The aliphatic amine group may be any of a primary amine group, a secondary amine group, and a tertiary amine group, but from the viewpoint of analytical properties, a secondary amine group or a tertiary amine group is preferred.

Examples of monomers that form a structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl acrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl acrylate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, N-(3-dimethylamino)ethyl methacrylate, Ester, N-(3-dimethylamino)propyl acrylate, N-(3-diethylamino)propyl methacrylate, N-(3-diethylamino)propyl acrylate, 2-(diisopropylamino)ethyl methacrylate, 2-ortho-ortho-ortho-ethyl methacrylate, 2-ortho-ortho-ortho-ethyl acrylate, N-[3-(dimethylamino)propyl]acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1,2,4-triazole. Among the above, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate is preferred.

Furthermore, as the constituent unit C, from the viewpoint of improving electrical characteristics, a constituent unit having an aromatic ring or a constituent unit having an aliphatic cyclic skeleton is preferred. Examples of monomers forming these constituent units include styrene, α-methylstyrene, dicyclopentyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, and benzyl (meth)acrylate. Among the above, cyclohexyl (meth)acrylate is preferred.

The polymer X may have a single type of constituent unit C, or may have two or more types of constituent units C.

The content of the constituent unit C is preferably 90 mass % or less, 85 mass % or less, and particularly preferably 80 mass % or less relative to the total mass of the polymer X. The content of the constituent unit C is preferably 10 mass % or more, and 20 mass % or more relative to the total mass of the polymer X. When the content of the constituent unit C is within the above range, the resolution and the adhesion to the substrate are further improved. When the polymer X has two or more constituent units C, the above content of the constituent unit C represents the total content of the two or more constituent units C. The content of the constituent unit C can be confirmed by the intensity ratio of the peak intensity calculated by the conventional method based on ¹³ C-NMR measurement.

Preferred examples of polymer X are shown below. However, polymer X is not limited to the following examples. In order to obtain better physical properties, the ratio and weight average molecular weight of each constituent unit in the polymer X shown below can be appropriately selected.

[Chemical formula 16]

-Glass transition temperature- The glass transition temperature (Tg) of polymer X is preferably below 90°C, more preferably 20°C to 60°C, and particularly preferably 30°C to 50°C. When the positive photosensitive layer is formed using the transfer material described later, the transferability of the positive photosensitive layer can be improved by the glass transition temperature of polymer X being within the above range.

As a method for adjusting the Tg of polymer X within the above range, for example, a method using the FOX formula can be cited. According to the FOX formula, the Tg of the target polymer X can be adjusted according to, for example, the Tg of the homopolymer of each constituent unit in the target polymer X and the mass fraction of each constituent unit.

The following is an explanation of the FOX formula using a copolymer having a first constituent unit and a second constituent unit as an example. When the glass transition temperature of the homopolymer of the first constituent unit is set to Tg1, the mass fraction of the first constituent unit in the copolymer is set to W1, the glass transition temperature of the homopolymer of the second constituent unit is set to Tg2, and the mass fraction of the second constituent unit in the copolymer is set to W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first constituent unit and the second constituent unit can be estimated according to the following formula. FOX formula: 1/Tg0=(W1/Tg1)+(W2/Tg2)

Furthermore, the Tg of the polymer can be adjusted by adjusting the weight average molecular weight of the polymer.

-Acid value- From the perspective of analytical properties, the acid value of polymer X is preferably 0 mgKOH/g to 50 mgKOH/g, more preferably 0 mgKOH/g to 20 mgKOH/g, and particularly preferably 0 mgKOH/g to 10 mgKOH/g.

The acid value of a polymer is expressed as the mass of potassium hydroxide required to neutralize the acidic components in 1g of the polymer. The specific measurement method is described below. First, the test sample is dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water = 9/1). Using a potentiometric titrator (e.g., trade name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.), the resulting solution is neutralized and titrated with a 0.1 mol/L sodium hydroxide aqueous solution at 25°C. The inflection point of the titration pH curve is taken as the titration end point, and the acid value is calculated by the following formula. A=56.11×Vs×0.1×f/w A: Acid value (mgKOH/g) Vs: Amount of 0.1mol/L sodium hydroxide aqueous solution required for titration (mL) f: Valency of 0.1mol/L sodium hydroxide aqueous solution w: Mass of the sample to be measured (g) (converted to solid content)

-Weight average molecular weight- The weight average molecular weight (Mw) of polymer X is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. When the positive photosensitive layer is formed using the transfer material described below, the weight average molecular weight of polymer X is 60,000 or less, so that the positive photosensitive layer can be transferred at a low temperature (e.g., below 130°C).

The weight average molecular weight of polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The ratio of the number average molecular weight to the weight average molecular weight (dispersity) of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

The weight average molecular weight of polymer X is measured by GPC (gel permeation chromatography). As a measuring device, various commercially available devices can be used. The following is a specific description of the method for measuring the weight average molecular weight of polymer X based on GPC. As a measuring device, HLC (registered trademark)-8220GPC (manufactured by TOSOH CORPORATION) is used. As the column, TSKgel (registered trademark) Super HZM-M (4.6 mm ID × 15 cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6 mm ID × 15 cm, manufactured by TOSOH CORPORATION), Super HZ3000 (4.6 mm ID × 15 cm, manufactured by TOSOH CORPORATION), and Super HZ2000 (4.6 mm ID × 15 cm, manufactured by TOSOH CORPORATION) were used, each connected in series. As the eluent, THF (tetrahydrofuran) was used. Regarding the measurement conditions, the sample concentration was set to 0.2 mass %, the flow rate was set to 0.35 mL/min, the sample injection volume was set to 10 μL, and the measurement temperature was set to 40°C. As the detector, a differential refractive index (RI) detector was used. The calibration curve can be created using any of the seven samples of "TSK standard, polystyrene" manufactured by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000".

-Content- From the perspective of high resolution, the content of polymer X is preferably 50% to 99.9% by mass, and more preferably 70% to 98% by mass, relative to the total mass of the positive photosensitive layer.

-Production method- The production method of polymer X is not limited, and a known method can be used. For example, a polymerization initiator can be used in an organic solvent to polymerize a monomer for forming constituent unit A, and further, as needed, a monomer for forming constituent unit B and a monomer for forming constituent unit C to produce polymer X. In addition, polymer X can also be produced by a so-called polymer reaction.

《Other polymers》 When the positive photosensitive layer includes a polymer having a constituent unit having an acid group protected by an acid-decomposable group, in addition to the polymer having a constituent unit having an acid group protected by an acid-decomposable group, a polymer not having a constituent unit having an acid group protected by an acid-decomposable group (hereinafter, sometimes referred to as "other polymers") may be included.

As other polymers, for example, polyhydroxystyrene can be cited. Commercially available products of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F manufactured by Sartomer Company, Inc., ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 manufactured by TOAGOSEI CO., LTD., and Joncryl 690, Joncryl 678, Joncryl 67, and Joncryl 586 manufactured by BASF.

The positive photosensitive layer may contain a single other polymer or may contain two or more other polymers.

When the positive photosensitive layer contains other polymers, the content of the other polymers is preferably 50 mass % or less, more preferably 30 mass % or less, and particularly preferably 20 mass % or less, relative to the total mass of the polymer components.

In the present disclosure, "polymer component" refers to the general term for all polymers contained in the positive photosensitive layer. For example, when the positive photosensitive layer contains polymer X and other polymers, polymer X and other polymers are collectively referred to as "polymer components". In addition, compounds corresponding to the crosslinking agent, dispersant and surfactant described later are not included in the polymer component even if they are high molecular weight compounds.

The content of the polymer component is preferably 50 mass % to 99.9 mass % with respect to the total mass of the positive photosensitive layer, and more preferably 70 mass % to 98 mass %.

《Alkali-soluble resin (positive type)》 The positive type photosensitive layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinone diazide compound, and particularly preferably contains a resin having a constituent unit having a phenolic hydroxyl group and a quinone diazide compound.

Examples of the alkali-soluble resin include resins having a hydroxyl group, a carboxyl group or a sulfonic acid group in the main chain or the side chain. Examples of the alkali-soluble resin include polyamide resins, polyhydroxystyrene, derivatives of polyhydroxystyrene, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoate, carboxyl-containing (meth) acrylic resins and novolac resins. Examples of preferred alkali-soluble resins include condensates of m-/p-mixed cresol and formaldehyde, and condensates of phenol, cresol and formaldehyde.

The alkali-soluble resin may have a phenolic hydroxyl group (-Ar-OH), a carboxyl group (-CO ₂ H), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H), a sulfonamide group (-SO ₂ NH-R), or a substituted sulfonamide acid group (e.g., an active imide group, -SO ₂ NHCOR, -SO ₂ NHSO ₂ R, and -CONHSO ₂ R). Here, Ar represents a divalent aromatic group which may have a substituent, and R represents a alkyl group which may have a substituent.

Novolac resins are obtained, for example, by condensing a phenolic compound with an aldehyde compound in the presence of an acid catalyst. Examples of phenolic compounds include o-, m- or p-cresol, 2,5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, 2-tert-butyl-5-methylphenol and tert-butylhydroquinone. Examples of aldehyde compounds include aliphatic aldehydes (e.g., formaldehyde, acetaldehyde and glyoxal) and aromatic aldehydes (e.g., benzaldehyde and salicylaldehyde). Examples of acid catalysts include inorganic acids (e.g., hydrochloric acid, sulfuric acid and phosphoric acid), organic acids (e.g., oxalic acid, acetic acid and p-toluenesulfonic acid) and divalent metal salts (e.g., zinc acetate). The condensation reaction can be carried out by a conventional method. The condensation reaction is carried out, for example, at a temperature in the range of 60° C. to 120° C. and for 2 hours to 30 hours. The condensation reaction can be carried out in an appropriate solvent.

Among them, as the alkali-soluble resin, a resin having a constituent unit having a phenolic hydroxyl group, such as a novolac resin, is preferred.

From the viewpoint of pattern forming properties, the weight average molecular weight of the alkali-soluble resin is preferably 5.0×10 ² to 2.0×10 ^5. From the viewpoint of pattern forming properties, the number average molecular weight of the alkali-soluble resin is preferably 2.0×10 ² to 1.0×10 ⁵ .

For example, a condensate of phenol and formaldehyde having an alkyl group with 3 to 8 carbon atoms as a substituent, such as a condensate of tertiary butylphenol and formaldehyde and a condensate of octylphenol and formaldehyde described in the specification of U.S. Patent No. 4123279, can be used in combination. A condensate of phenol and formaldehyde having an alkyl group with 3 to 8 carbon atoms as a substituent, such as a tertiary butylphenol formaldehyde resin and an octylphenol formaldehyde resin described in the specification of U.S. Patent No. 4123279, can also be used in combination.

The positive photosensitive layer may contain one or more alkali-soluble resins. The content of the alkali-soluble resin is preferably 30% to 99.9% by mass, more preferably 40% to 99.5% by mass, and particularly preferably 70% to 99% by mass relative to the total mass of the positive photosensitive layer.

《Photoacid generator》 It is preferred that the positive photosensitive layer contains a photoacid generator as a photosensitive compound. The photoacid generator is a compound that can generate an acid by irradiation with active light (e.g., ultraviolet light, far ultraviolet light, X-rays, and electron beams).

As the photoacid generator, a compound that generates an acid by being responsive to active light having a wavelength of 300 nm or more, preferably 300 nm to 450 nm is preferred. In addition, as for a photoacid generator that does not directly respond to active light having a wavelength of 300 nm or more, as long as it is a compound that responds to active light having a wavelength of 300 nm or more by being used in combination with a sensitizer and generates an acid, it can also be preferably used in combination with a sensitizer.

The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid with a pKa of 2 or less. The lower limit of the pKa of the acid derived from the photoacid generator is not limited. The pKa of the acid derived from the photoacid generator is preferably, for example, -10.0 or more.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

Examples of the ionic photoacid generator include onium salt compounds. Examples of the onium salt compound include diaryl iodonium salt compounds, triaryl siron salt compounds, and quaternary ammonium salt compounds. The ionic photoacid generator is preferably an onium salt compound, and at least one of a triaryl siron salt compound and a diaryl iodonium salt compound is particularly preferred.

As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

Examples of nonionic photoacid generators include trichloromethyl-s-trisinium compounds, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. From the perspective of sensitivity, resolution, and adhesion to the substrate, the nonionic photoacid generator is preferably an oximesulfonate compound.

Specific examples of trichloromethyl-s-trioxanthate compounds, diazomethane compounds, and imidosulfonate compounds include compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494.

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be preferably used.

From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and an oxime sulfonate compound is more preferably.

As a preferred example of the photoacid generator, a photoacid generator having the following structure can be cited.

[Chemical formula 17]

As a photoacid generator having absorption at a wavelength of 405 nm, for example, ADEKA ARKLS (registered trademark) SP-601 (manufactured by ADEKA CORPORATION) can be cited.

From the viewpoint of heat resistance and dimensional stability, it is preferable that the positive photosensitive layer contains a quinone diazide compound as an acid generator (preferably a photoacid generator). The quinone diazide compound can be synthesized, for example, by allowing a compound having a phenolic hydroxyl group to undergo a condensation reaction with a quinone diazide sulfonyl halide in the presence of a dehydrohalogenating agent.

Examples of the quinone diazide compound include 1,2-benzoquinone diazide-4-sulfonate, 1,2-naphthoquinone diazide-4-sulfonate, 1,2-naphthoquinone diazide-5-sulfonate, 1,2-naphthoquinone diazide-6-sulfonate, 2,1-naphthoquinone diazide-4-sulfonate, 2,1-naphthoquinone diazide-5-sulfonate, 2,1-naphthoquinone diazide-6-sulfonate, and other Sulfonic acid esters of quinonediazide derivatives, 1,2-benzoquinonediazide-4-sulfonic acid acyl chloride, 1,2-naphthoquinonediazide-4-sulfonic acid acyl chloride, 1,2-naphthoquinonediazide-5-sulfonic acid acyl chloride, 1,2-naphthoquinonediazide-6-sulfonic acid acyl chloride, 2,1-naphthoquinonediazide-4-sulfonic acid acyl chloride, 2,1-naphthoquinonediazide-5-sulfonic acid acyl chloride and 2,1-naphthoquinonediazide-6-sulfonic acid acyl chloride.

The positive photosensitive layer may contain a single photoacid generator or may contain two or more photoacid generators. From the perspective of sensitivity and resolution, the content of the photoacid generator is preferably 0.1 mass% to 10 mass% relative to the total mass of the positive photosensitive layer, and more preferably 0.5 mass% to 5 mass%.

《Other ingredients》 The photosensitive layer may contain ingredients other than those listed above.

-Surfactant- From the viewpoint of thickness uniformity, it is preferable that the photosensitive layer contains a surfactant. As the surfactant, for example, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be cited, and nonionic surfactants are preferred. As the surfactant, for example, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Publication No. 2009-237362 can be cited.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferred. Commercially available products of fluorine-based surfactants include, for example, MEGAFACE (registered trademark: the same below) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F- 558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, 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 (all DIC Corporation), Fluorad (trade name) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by Neos Corporation), etc. In addition, the fluorine-based surfactant can also preferably use an acrylic compound, which has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cut off, thereby volatilizing the fluorine atom. Examples of such fluorine-based surfactants include the MEGAFACE (trade name) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016)), such as MEGAFACE (trade name) DS-21.

In addition, the fluorine-based surfactant preferably uses a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound. The fluorine-based surfactant can also use a capped polymer. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains a constituent unit from a (meth)acrylate compound having a fluorine atom and a constituent unit from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkylene groups (preferably ethoxy and propoxy). The fluorine-based surfactant can also use a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Examples include MEGAFACE (trade name) RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation), etc.

Examples of the nonionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solsperse (trade name) 20000 (all manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Co., Ltd.), etc. In recent years, the environmental suitability of compounds with linear perfluoroalkyl groups with a carbon number of 7 or more has become a concern, so it is better to use a surfactant that uses an alternative material to perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS).

As silicone-based surfactants, there are linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or the ends. Specific examples of silicone-based surfactants include 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, Toray Silicone SH8400 (all of which are Dow Corning Toray 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 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (all manufactured by BYK Chemie), etc.

The photosensitive layer may contain one surfactant alone or two or more surfactants. The content of the surfactant is preferably 0.001 mass % to 10 mass % relative to the total mass of the photosensitive layer, and more preferably 0.01 mass % to 3 mass %.

-Additives- In addition to the above-mentioned components, the photosensitive layer may contain known additives as needed. As additives, for example, polymerization inhibitors, sensitizers, plasticizers, alkoxysilane compounds and solvents can be cited. The photosensitive layer may contain one type of each additive alone, or may contain two or more types. In addition, as additives, metal oxide particles, antioxidants, dispersants, acid proliferation agents, development accelerators, conductive fibers, thermal free radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners and organic or inorganic precipitation inhibitors can be cited. The preferred forms of these additives are described in paragraphs 0165 to 0184 of Japanese Patent Application No. 2014-85643, and these contents are incorporated into this manual by reference.

The photosensitive layer may contain a polymerization inhibitor. As the polymerization inhibitor, a free radical polymerization inhibitor is preferred. As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be cited. Among them, phenanthrene, phenanthrene or 4-methoxyphenol is preferred. As other polymerization inhibitors, naphthylamine, copper (I) chloride, N-nitrosophenyl hydroxylamine aluminum salt, diphenyl nitrosoamine, etc. can be cited. In order not to damage the sensitivity of the composition for forming the photosensitive layer, it is preferred to use N-nitrosophenyl hydroxylamine aluminum salt as the polymerization inhibitor.

The content of the polymerization inhibitor is preferably 0.01% to 3% by mass, more preferably 0.05% to 1% by mass, relative to the total mass of the photosensitive layer. From the viewpoint of imparting storage stability to the photosensitive layer-forming composition, the content is preferably 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity, the content is preferably 3% by mass or less.

The photosensitive layer may contain a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, trioxane compounds, thiophene compounds, naphthalene diimide compounds, triarylamine compounds, and aminoacridine compounds.

The photosensitive layer may contain one sensitizer alone or two or more. When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the perspective of improving sensitivity to light sources and improving the curing speed by balancing the polymerization speed and chain transfer, it is preferably 0.01 mass% to 5 mass% relative to the total mass of the photosensitive layer, and 0.05 mass% to 1 mass% is more preferably.

The photosensitive layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. As the plasticizer and the heterocyclic compound, the compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018/179640 can be cited.

The photosensitive layer (preferably a positive photosensitive layer) may contain an alkoxysilane compound. As the alkoxysilane compound, for example, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidoxypropyl trialkoxysilane, γ-glycidoxypropyl alkyl dialkoxysilane, γ-methacryloxypropyl trialkoxysilane, γ-methacryloxypropyl alkyl dialkoxysilane, γ-chloropropyl trialkoxysilane, γ-butyl propyl trialkoxysilane, β-(3,4-epoxycyclohexyl)ethyl trialkoxysilane and vinyl trialkoxysilane can be cited.

Among the above, the alkoxysilane compound is preferably a trialkoxysilane compound, γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane is more preferably, γ-glycidoxypropyltrialkoxysilane is further preferably, and 3-glycidoxypropyltrimethoxysilane is particularly preferably.

The photosensitive layer may contain a single alkoxysilane compound or may contain two or more alkoxysilane compounds. From the viewpoint of adhesion to the substrate and etching resistance, the content of the alkoxysilane compound is preferably 0.1% to 50% by mass, more preferably 0.5% to 40% by mass, and particularly preferably 1.0% to 30% by mass relative to the total mass of the photosensitive layer.

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

《Impurities, etc.》 The photosensitive layer may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halogenide ions, sodium ions, and potassium ions are easily mixed in as impurities, so the following contents are preferred.

The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis. The content of impurities can be set to 1 ppb or more on a mass basis, and can also be set to 0.1 ppm or more.

As a method of setting the impurity content within the above range, there can be cited the following methods: selecting a material with a low impurity content as a raw material of the composition, preventing the impurities from mixing in during the preparation of the photosensitive layer, and removing the impurities by washing. By this method, the impurity amount can be set within the above range.

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

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 preferably small. As for the content of these compounds relative to the total mass of the photosensitive layer, it is preferably 100ppm or less, 20ppm or less is more preferably, and 4ppm or less is further preferably. The lower limit can be set to 10ppb or more, or 100ppb or more, relative to the total mass of the photosensitive layer. The content of these compounds can be suppressed by the same method as the above-mentioned metal impurities. In addition, it can be quantified by a known measurement method.

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

《Residual monomers》 The photosensitive layer sometimes contains residual monomers corresponding to the constituent units of the above-mentioned alkali-soluble resin. From the viewpoint of patterning and reliability, the content of residual monomers is preferably 5,000 mass ppm or less, 2,000 mass ppm or less, and 500 mass ppm or less relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but 1 mass ppm or more is preferred, and 10 mass ppm or more is more preferred. From the viewpoint of patterning and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, 600 mass ppm or less, and 100 mass ppm or less relative to the total mass of the photosensitive layer. The lower limit is not particularly limited, but 0.1 mass ppm or more is preferred, and 1 mass ppm or more is more preferred.

The residual monomer amount of the monomer when synthesizing the alkali-soluble resin by polymer reaction is also preferably set within the above range. For example, when synthesizing the alkali-soluble resin by reacting glycidyl acrylate with the carboxylic acid side chain, it is preferred to set the content of glycidyl acrylate within the above range. The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

《Physical properties, etc.》 The thickness of the photosensitive layer is preferably 0.1μm to 300μm, more preferably 0.2μm to 100μm, further preferably 0.5μm to 50μm, further preferably 0.5μm to 15μm, particularly preferably 0.5μm to 10μm, and best 0.5μm to 8μm. This can improve the developing property of the photosensitive layer and improve the resolution. In addition, from the perspective of further exerting the resolution and the effects of the present disclosure, the thickness (thickness) of the photosensitive layer is preferably 10μm or less, more preferably 5.0μm or less, further preferably 0.5μm to 4.0μm, and particularly preferably 0.5μm to 3.0μm. The thickness of each layer of the photosensitive transfer material is measured by observing the cross section of the photosensitive transfer material in the direction perpendicular to the main surface using a scanning electron microscope (SEM) and measuring the thickness of each layer at more than 10 points based on the observed image and calculating the average value.

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

《Formation method》 The method for forming the photosensitive layer is not particularly limited as long as it is a method that can form a layer containing the above-mentioned components. As a method for forming a photosensitive layer, for example, in the case of a negative photosensitive layer, there can be cited a method of preparing a photosensitive layer forming composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and applying the photosensitive layer forming composition on the surface of a pseudo support, etc., and drying the coating of the photosensitive layer forming composition.

As the photosensitive layer forming composition used in the formation of the photosensitive layer, for example, there can be cited a composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, any of the above components, and a solvent. In order to adjust the viscosity of the photosensitive layer forming composition and make it easier to form the photosensitive layer, it is preferable that the photosensitive layer forming composition contains a solvent.

-Solvent- The solvent contained in the photosensitive layer forming composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, polymerizable compound, photopolymerization initiator and any of the above-mentioned components, and a known solvent can be used. As the solvent, for example, there can be cited alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of them. In the case of preparing a photosensitive transfer material having a pseudo-support, a thermoplastic resin layer, an intermediate layer, a photosensitive layer and a cover film, it is preferred that the composition for forming the photosensitive layer contains at least one selected from the group including alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, a mixed solvent containing at least one selected from the group including alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group including ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least one selected from the group including alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents and cyclic ether solvents is further preferred.

As the alkylene glycol ether solvent, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether can be cited. As the alkylene glycol ether acetate solvent, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate can be cited. As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvents described in paragraph 0014 of Japanese Patent Publication No. 2018-177889 can be used, and these contents are incorporated into this specification.

The photosensitive layer forming composition may contain one type of solvent alone or two or more types. The content of the solvent when applying the photosensitive layer forming composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive layer forming composition.

The method for preparing the photosensitive layer-forming composition is not particularly limited. For example, a method of preparing the photosensitive layer-forming composition by preparing a solution in advance by dissolving each component in the above-mentioned solvent and mixing the obtained solution in a predetermined ratio can be cited. From the viewpoint of particle removal, it is preferred that the photosensitive layer-forming composition be filtered using a filter before forming the photosensitive layer, and it is more preferred to filter using a filter with a pore size of 0.2 μm to 10 μm, and it is further preferred to filter using a filter with a pore size of 0.2 μm to 7 μm, and it is particularly preferred to filter using a filter with a pore size of 0.2 μm to 5 μm. There is no particular limitation on the material and shape of the filter, and known ones can be used. Furthermore, it is preferred that the above-mentioned filtering be performed more than once, and it is also preferred that the filtering be performed multiple times.

The method for applying the photosensitive layer forming composition is not particularly limited, and the composition may be applied by a known method. Examples of the application method include slit coating, spin coating, curtain coating, and inkjet coating. In addition, the photosensitive layer can be formed by applying the photosensitive layer forming composition on a cover film described later and drying it.

In addition, from the perspective of analytical properties and the peeling property of the pseudo-support, the photosensitive transfer material in the present disclosure preferably has other layers between the above-mentioned particle layer and the above-mentioned photosensitive layer. As other layers, an intermediate layer, a thermoplastic resin layer, etc. can be preferably cited. Among them, as the above-mentioned transfer layer, it is preferred to have an intermediate layer, and it is more preferred to have a thermoplastic resin layer and an intermediate layer.

[Intermediate layer] The second embodiment of the photosensitive transfer material disclosed herein is an embodiment in which, when a thermoplastic resin layer described below is provided between the particle layer and the photosensitive layer, an intermediate layer is provided between the thermoplastic resin layer and the photosensitive layer. By providing an intermediate layer, mixing of components contained in each layer when forming a plurality of layers and during storage can be suppressed.

From the viewpoint of developing properties and suppressing mixing of components when applying multiple layers and storing after application, it is preferred that the intermediate layer is a water-soluble layer. In the present disclosure, "water-soluble" means that the solubility in 100g of water with a pH of 7.0 at a liquid temperature of 22°C is 0.1g or more.

As an intermediate layer, for example, an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese Patent Gazette No. 5-72724 can be cited. By using the intermediate layer as an oxygen barrier layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved. The oxygen barrier layer used as the intermediate layer can be appropriately selected from known layers. The oxygen barrier layer used as the intermediate layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (a 1 mass % aqueous solution of sodium carbonate at 22°C). In addition, from the viewpoints of oxygen barrier properties, analytical properties, and pattern formation properties, it is preferred that the intermediate layer contains an inorganic layered compound. Examples of inorganic layered compounds are particles having a thin plate shape, such as natural mica, synthetic mica and other mica compounds, talc, montmorillonite, saponite, lithium bentonite, zirconium phosphate and the like represented by the formula: 3MgO·4SiO·H ₂ O. Examples of mica compounds include natural mica, synthetic mica and other mica groups represented by the formula: A(B,C) _2-5 D ₄ O ₁₀ (OH,F,O) ₂ [wherein A is any one of K, Na and Ca, B and C are any one of Fe(II), Fe(III), Mn, Al, Mg and V, and D is Si or Al.].

Among the micas, natural micas include muscovite, sodium micas, phlogopite, biotite, and scalyx micas. Synthetic micas include non-swelling micas such as fluorphlogopite KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ and potassium tetrasilicon micas KMg _2.5 Si ₄ O ₁₀ ) F ₂ , and swelling micas such as Na tetrasilicon micas NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li banded micas (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , and montmorillonite-based Na or Li lithium bentonite (Na, Li) _1/8 Mg _2/5 Li _1/8 (Si ₄ O ₁₀ ) F ₂ . Furthermore, synthetic smectite is also useful.

As for the shape of the inorganic layered compound, from the viewpoint of controlling diffusion, the thinner the thickness, the better. As long as the plane size does not hinder the smoothness of the coating surface or the transmittance of the active light, the larger the plane size, the better. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the length of the particle to the thickness, and can be measured, for example, based on the projection diagram obtained from the microscopic photograph of the particle. The larger the aspect ratio, the greater the effect obtained.

Regarding the particle size of the inorganic layered compound, the average length is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swelling synthetic mica as a representative compound, as a preferred embodiment, the thickness is about 1 nm to 50 nm, and the surface size (length) is about 1 μm to 20 μm.

From the viewpoints of oxygen barrier properties, resolution and pattern formation, the content of the inorganic layered compound is preferably 0.1% by mass to 50% by mass, and more preferably 1% by mass to 20% by mass, based on the total mass of the intermediate layer.

The middle layer preferably contains a resin. Examples of the resin contained in the middle layer include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. The resin contained in the middle layer is preferably a water-soluble resin.

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

Furthermore, from the viewpoints of oxygen barrier properties, developing properties, resolvability and pattern formation properties, the intermediate layer preferably contains a water-soluble compound, and more preferably contains a water-soluble resin. There is no particular limitation on the water-soluble compound, but from the viewpoints of oxygen barrier properties, developing properties, resolvability and pattern formation properties, it is preferred to use at least one compound selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives and amide compounds, and it is more preferred to use at least one water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl cellulose and hydroxypropyl methyl cellulose. As water-soluble resins, for example, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof can be cited. Among them, from the viewpoints of oxygen barrier properties, developing properties, resolvability, and pattern formation, it is preferred that the water-soluble compound (preferably a water-soluble resin) contains polyvinyl alcohol, and polyvinyl alcohol is more preferred. The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but from the viewpoints of oxygen barrier properties, developing properties, resolvability, and pattern formation, 73 mol% to 99 mol% is preferred. Furthermore, from the viewpoints of oxygen barrier properties, developing properties, resolvability, and pattern formation, it is preferred that polyvinyl alcohol contains ethylene as a monomer unit.

From the viewpoint of oxygen barrier properties and suppression of mixing of components when applying multiple layers and during storage after application, the intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinyl pyrrolidone.

The middle layer may contain a single resin or two or more resins.

From the viewpoint of oxygen barrier properties and suppression of mixing of components when applying multiple layers and storing after application, the content of the water-soluble compound in the intermediate layer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass relative to the total mass of the intermediate layer.

Furthermore, the intermediate layer may contain additives as necessary. Examples of additives include surfactants.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property will not be reduced, and the mixing of components during the formation of multiple layers and during storage can be suppressed, and the increase in the removal time of the intermediate layer during development can be suppressed.

The method for forming the intermediate layer is not limited as long as it is a method that can form a layer containing the above-mentioned components. As a method for forming the intermediate layer, for example, there can be cited a method of applying the intermediate layer forming composition on the surface of the thermoplastic resin layer or the photosensitive layer and then drying the applied film of the intermediate layer forming composition.

As the composition for forming the intermediate layer, for example, there can be cited a composition containing a resin and any additive. In order to adjust the viscosity of the composition for forming the intermediate layer so that the intermediate layer can be easily formed, it is preferable that the composition for forming the intermediate layer contains a solvent. As the solvent, there is no limitation as long as it is a solvent that can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and water or a mixed solvent of water and a water-miscible organic solvent is more preferable.

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

[Thermoplastic resin layer] The second embodiment of the photosensitive transfer material disclosed herein may have a thermoplastic resin layer. The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

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

From the viewpoint of developing property and adhesion to the layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is preferably an acrylic resin. Here, "acrylic resin" refers to a resin having at least one selected from the group consisting of a constituent unit derived from (meth)acrylic acid, a constituent unit derived from (meth)acrylate, and a constituent unit derived from (meth)acrylic amide.

In the acrylic resin, the total content of the constituent units derived from (meth)acrylic acid, the constituent units derived from (meth)acrylic acid ester and the constituent units derived from (meth)acrylic acid amide is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, the total content of the constituent units derived from (meth)acrylic acid and the constituent units derived from (meth)acrylic acid ester is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass relative to the total mass of the acrylic resin.

Furthermore, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferred.

From the viewpoint of developing properties, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and an acrylic resin containing a carboxyl group having an acid value of 60 mgKOH/g or more is more preferred. The upper limit of the acid value is not limited. The acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not limited and can be appropriately selected from known resins for use. Examples of the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more include the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers described in paragraph 0025 of Japanese Patent Publication No. 2011-95716, the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of Japanese Patent Publication No. 2010-237589, and the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the adhesive polymers described in paragraphs 0053 to 0068 of Japanese Patent Publication No. 2016-224162.

The content of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and particularly preferably 12 to 30 mass % relative to the total mass of the carboxyl group-containing acrylic resin.

From the viewpoint of developing properties and adhesion to a layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid.

The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include ethylenically unsaturated groups, condensation polymerizable groups (e.g., hydroxyl groups and carboxyl groups), and polyaddition reactive groups (e.g., epoxy groups and (blocked) isocyanate groups).

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

The thermoplastic resin layer may also include one or more alkali-soluble resins.

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

The thermoplastic resin layer preferably contains a pigment (hereinafter sometimes referred to as "pigment B") whose maximum absorption wavelength is 450 nm or more in the wavelength range of 400 nm to 780 nm when developing color, and whose maximum absorption wavelength changes by acid, alkali or free radical. The preferred embodiment of pigment B is the same as the preferred embodiment of pigment N described above except for the following points.

From the viewpoint of visibility of the exposed part, visibility of the non-exposed part, and resolvability, it is preferable that the dye B is a dye whose maximum absorption wavelength is changed by acid or free radicals, and it is more preferable that the dye whose maximum absorption wavelength is changed by acid.

From the viewpoint of visibility of the exposed part, visibility of the non-exposed part, and resolution, it is preferred that the thermoplastic resin layer contains a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound C described later.

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

From the viewpoint of visibility of the exposed portion and the non-exposed portion, the content of the pigment B is preferably 0.2 mass % or more, more preferably 0.2 mass % to 6 mass %, further preferably 0.2 mass % to 5 mass %, and particularly preferably 0.25 mass % to 3.0 mass % relative to the total mass of the thermoplastic resin layer.

Here, the content of pigment B refers to the content of pigment when all pigments B contained in the thermoplastic resin layer are in a colored state. Below, the quantitative method of the content of pigment B is explained by taking the pigment that develops color by free radicals as an example. Two solutions are prepared by dissolving the pigment (0.001g) and the pigment (0.01g) in methyl ethyl ketone (100mL). After adding IRGACURE OXE01 (manufactured by BASF) as a photoradical polymerization initiator to each of the obtained solutions, free radicals are generated by irradiating 365nm light to make all the pigments in a colored state. Then, in an atmospheric environment, the absorbance of each solution at a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared. Next, the absorbance of the solution in which the pigment is completely colored was measured in the same manner as above except that the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone instead of the pigment. The amount of pigment contained in the thermoplastic resin layer was calculated based on the calibration curve from the absorbance of the solution containing the thermoplastic resin layer obtained.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a free radical by light (hereinafter, sometimes referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a free radical by active light (e.g., ultraviolet light and visible light). Examples of compound C include known photoacid generators, photoalkali generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

From the analytical point of view, it is preferable that the thermoplastic resin layer contains a photoacid generator. As the photoacid generator, the photocationic ion polymerization initiator that can be contained in the above-mentioned photosensitive layer can be cited. Except for the points described below, the preferred embodiment is the same.

From the viewpoint of sensitivity and resolvability, the photoacid generator preferably comprises at least one selected from the group consisting of an onium salt compound and an oxime sulfonate compound. From the viewpoint of sensitivity, resolvability and adhesion, it is more preferably comprises an oxime sulfonate compound.

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

[Chemical formula 18]

The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-aminoformylhydroxyamide, O-aminoformyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-mercaptoethane, (4-mercaptobenzoyl)-1-benzyl-1- Dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-hydroxy-1-nitrophenyl)butanone, 2,6-dimethyl-3,5-diethyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diethyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

The thermoplastic resin layer may contain a photo-radical polymerization initiator. Examples of the photo-radical polymerization initiator include the photo-radical polymerization initiator that may be contained in the above-mentioned photosensitive layer, and the preferred embodiments are the same.

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

From the viewpoint of visibility of the exposed part, visibility of the non-exposed part, and resolution, the content of the compound C is preferably 0.1 mass % to 10 mass %, and more preferably 0.5 mass % to 5 mass %, based on the total mass of the thermoplastic resin layer.

From the viewpoints of resolvability, adhesion to a layer adjacent to the thermoplastic resin layer, and developability, it is preferred that the thermoplastic resin layer contain a plasticizer.

The molecular weight of the plasticizer (for the molecular weight of an oligomer or polymer, it refers to the weight average molecular weight (Mw). The same applies to this paragraph below) is preferably less than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkoxy group in the molecule, and a polyalkylene glycol compound is more preferably. The alkoxy group contained in the plasticizer preferably has at least one structure selected from a polyethoxy structure and a polypropoxy structure.

From the viewpoints of resolvability and storage stability, it is preferred that the plasticizer contains a (meth)acrylate compound. From the viewpoints of compatibility, resolvability, and adhesion to a layer adjacent to a thermoplastic resin layer, it is more preferred that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

As the (meth)acrylate compound used as the plasticizer, for example, the (meth)acrylate compounds listed in the above-mentioned ethylenically unsaturated compounds can be cited. In the case where the thermoplastic resin layer and the photosensitive layer are directly in contact with each other in the photosensitive transfer material, it is preferred that the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the photosensitive layer contain the same (meth)acrylate compound, the diffusion of components between the layers can be suppressed, thereby improving the storage stability.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferred that the (meth)acrylate compound is not polymerized in the exposed portion after exposure from the viewpoint of adhesion with the layer adjacent to the thermoplastic resin layer.

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

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

The thermoplastic resin layer may contain one or more plasticizers.

From the viewpoint of resolvability, adhesion to the layer adjacent to the thermoplastic resin layer, and developability, the content of the plasticizer is preferably 1 mass % to 70 mass % relative to the total mass of the thermoplastic resin layer, more preferably 10 mass % to 60 mass % and particularly preferably 20 mass % to 50 mass %

From the perspective of thickness uniformity, it is preferred that the thermoplastic resin layer contains a surfactant. Examples of the surfactant include the surfactants that can be contained in the above-mentioned photosensitive layer, and the preferred embodiments are the same.

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

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

The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizers that may be contained in the negative photosensitive layer.

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

From the viewpoint of improving the sensitivity to the light source, the visibility of the exposed part and the visibility of the non-exposed part, the content of the sensitizer is preferably 0.01 mass % to 5 mass %, and more preferably 0.05 mass % to 1 mass % relative to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may contain known additives in addition to the above-mentioned components as necessary.

The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643, the contents of which are incorporated herein by reference.

The thickness of the thermoplastic resin layer is not limited. From the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer, the average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolvability, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

The method for forming the thermoplastic resin layer is not limited as long as it is a method that can form a layer containing the above-mentioned components. As a method for forming the thermoplastic resin layer, for example, a method of coating a thermoplastic resin composition on the surface of the pseudo-support and drying the coating of the thermoplastic resin composition can be cited.

As the thermoplastic resin composition, for example, there can be mentioned a composition containing the above-mentioned components. In order to adjust the viscosity of the thermoplastic resin composition and make it easy to form a thermoplastic resin layer, it is preferable that the thermoplastic resin composition contains a solvent.

The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. As the solvent, the solvent that can be contained in the above-mentioned photosensitive layer forming composition can be cited, and the preferred embodiment is the same.

The thermoplastic resin composition may also contain one or more solvents.

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

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be carried out according to the preparation method of the composition for forming the photosensitive layer and the formation method of the negative photosensitive layer described above. For example, after preparing a solution in which each component included in the thermoplastic resin layer is dissolved in a solvent and the obtained solutions are mixed in a predetermined ratio to prepare the thermoplastic resin composition, the obtained thermoplastic resin composition is applied to the surface of the pseudo-support, and the applied film of the thermoplastic resin composition is dried to form the thermoplastic resin layer. Alternatively, after forming the photosensitive layer on the cover film, the thermoplastic resin layer can be formed on the surface of the photosensitive layer.

[Coating film] The photosensitive transfer material preferably has a coating film. In addition, the coating film is not included in the above-mentioned transfer layer. It is preferred that the photosensitive layer and the coating film are in direct contact.

As materials constituting the covering film, resin films and paper can be cited. From the viewpoint of strength and flexibility, resin films are preferred. As resin films, polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films can be cited. Among them, polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred.

The thickness (layer thickness) of the covering film is not particularly limited, but 5μm to 100μm is preferred, and 10μm to 50μm is more preferred. From the perspective of transportability, defect suppression of the resin pattern, and analytical performance, the arithmetic average roughness Ra of the surface on the side opposite to the photosensitive layer side in the covering film is preferably less than the arithmetic average roughness Ra of the surface on the photosensitive layer side in the covering film, and more preferably less than the arithmetic average roughness Ra of the surface on the photosensitive layer side in the covering film. From the perspective of transportability and winding performance, the arithmetic average roughness Ra of the surface on the side opposite to the photosensitive layer in the covering film is preferably 300nm or less, more preferably 100nm or less, further preferably 70nm or less, and particularly preferably 50nm or less. In addition, from the perspective of better resolution, the arithmetic average roughness Ra of the surface on the photosensitive layer side in the covering film is preferably 300nm or less, more preferably 100nm or less, further preferably 70nm or less, and particularly preferably 50nm or less. This is believed to be because the uniformity of the thickness of the photosensitive layer and the formed resin pattern is improved by the Ra value of the surface of the covering film being within the above range. The lower limit of the Ra value of the surface of the covering film is not particularly limited, but it is preferably 1 nm or more on both sides, more preferably 10 nm or more, and particularly preferably 20 nm or more. In addition, it is preferred that the peeling force of the covering film is smaller than the peeling force of the pseudo-support.

The photosensitive transfer material may have layers other than the above layers (hereinafter, also referred to as "other layers"). As other layers, for example, a contrast enhancement layer can be cited. The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018/179640. In addition, other layers are described in paragraphs 0194 to 0196 of Japanese Patent Publication No. 2014-85643. The contents of these publications are incorporated into this specification.

The total thickness of the photosensitive transfer material is preferably 5μm to 55μm, more preferably 10μm to 50μm, and particularly preferably 20μm to 40μm. The total thickness of the photosensitive transfer material is measured by the method for measuring the thickness of each layer described above. From the perspective of further exerting the effects of the present disclosure, the total thickness of each layer in the photosensitive transfer material except the pseudo-support and the covering film is preferably 20μm or less, more preferably 10μm or less, further preferably 8μm or less, and particularly preferably 2μm or more and 8μm or less. Furthermore, from the perspective of further exerting the effects of the present disclosure, the total thickness of the photosensitive layer, the intermediate layer, and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

<Pigment> The photosensitive layer may be a colored resin layer containing a pigment. In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back of a transparent glass substrate or the like is sometimes installed on the liquid crystal display window of electronic equipment to protect the liquid crystal display window. A colored resin layer can be used to form such a light-shielding layer. As a pigment, it is sufficient to select it appropriately according to the desired hue, and it can be selected from black pigment, white pigment, and color pigments other than black and white. Among them, when forming a black pattern, it is preferable to select a black pigment as a pigment.

As the black pigment, a known black pigment (organic pigment or inorganic pigment, etc.) can be appropriately selected as long as the effects of the present disclosure are not impaired. Among them, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide and graphite can be preferably cited as the black pigment, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a part of the surface is coated with resin is preferred.

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

As pigments other than black pigments, white pigments described in paragraphs 0015 and 0114 of Japanese Patent Publication No. 2005-007765 can 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, titanium oxide or zinc oxide is more preferred, and titanium oxide is further preferred. As inorganic pigments, rutile or ferroxene titanium oxide is further preferred, and rutile titanium oxide is particularly preferred. In addition, the surface of titanium oxide can be treated with silicon dioxide, aluminum oxide, titanium dioxide, zirconia or organic matter, or two or more treatments can be performed. In this way, the catalytic activity of titanium oxide can be suppressed, and heat resistance and fading properties can be improved. From the perspective of reducing the thickness of the photosensitive layer after heating, as the surface treatment of the titanium oxide surface, at least one of aluminum oxide treatment and zirconia treatment is preferred, and a surface treatment including both aluminum oxide treatment and zirconia treatment is particularly preferred.

Furthermore, when the photosensitive layer is a colored resin layer, it is also preferable from the perspective of transferability that the photosensitive layer further includes color pigments other than black pigments and white pigments. When color pigments are included, the particle size of the color pigment is preferably less than 0.1 μm, and more preferably less than 0.08 μm, from the perspective of better dispersibility. Examples of color pigments include Victoria Blue BO (Color Index (C.I.) 42595), aureum (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 Purple 19), permanent ruby FBH (C.I. Pigment Red 11), and pastel pink (C.I. Pigment Red 83). Pink) B supura (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite 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 Purple 23. Among them, C.I. Pigment Red 177 is the best.

When the photosensitive layer contains a pigment, the content of the pigment is preferably greater than 3 mass % and less than 40 mass %, more preferably greater than 3 mass % and less than 35 mass %, further preferably greater than 5 mass % and less than 35 mass %, and particularly preferably greater than 10 mass % and less than 35 mass %, relative to the total mass of the photosensitive layer.

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

In addition, when the photosensitive layer includes a black pigment and the photosensitive layer is formed of a photosensitive resin composition, it is preferred that the black pigment (preferably carbon black) is introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion can be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing it with a disperser. The pigment dispersant can be selected according to the pigment and the solvent, for example, a commercially available dispersant can be used. In addition, the vehicle refers to the medium part that disperses the pigment when the pigment dispersion is prepared, which is in a liquid state and includes a binder component that keeps the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

There is no particular limitation on the dispersing machine, and examples thereof include kneaders, roller mills, attritors, super mills, dissolvers, homomixers, sand mills, and other known dispersing machines. Furthermore, mechanical grinding may be used to perform fine pulverization using friction. For dispersing machines and fine pulverization, reference may be made to the description of "Dictionary of Pigments" (written by Kunizo Asakura, first edition, Asakura Bookstore, 2000, pages 438 and 310).

(Manufacturing method of photosensitive transfer material) The first embodiment of the manufacturing method of the photosensitive transfer material disclosed herein includes the following steps: a step of providing a photosensitive layer-forming composition on a cover film to form a photosensitive layer; a step of providing a particle layer-forming composition on the photosensitive layer to form a particle layer having a convex structure on the surface; and a step of attaching a pseudo-support to the surface of the particle layer having the convex structure in a manner of contacting the particle layer, wherein the average layer thickness of the portion of the particle layer where the convex structure does not exist is less than the arithmetic average particle size of the particles contained in the particle layer. The second embodiment of the method for manufacturing the photosensitive transfer material disclosed herein includes the following steps: a step of providing a photosensitive layer-forming composition on a cover film to form a photosensitive layer; a step of providing an intermediate layer-forming composition on the photosensitive layer to form an intermediate layer; a step of providing a particle layer-forming composition on the intermediate layer to form a particle layer; and a step of attaching a pseudo-support to the particle layer in a manner that the pseudo-support is in contact with the particle layer.

In addition, in this specification, when it is not particularly specified and is simply referred to as "the method for producing the photosensitive transfer material disclosed in the present invention", both the first embodiment and the second embodiment are described. In addition, when it is not particularly specified and is simply referred to as "the step of forming a photosensitive layer", the step of forming a photosensitive layer, etc. of both the first embodiment and the second embodiment are described.

The second embodiment of the method for manufacturing the photosensitive transfer material disclosed in the present invention is described below with reference to FIG. 1. However, the photosensitive transfer material disclosed in the present invention is not limited to the one having the structure shown in FIG. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure in the second embodiment of the photosensitive transfer material disclosed in the present invention. The photosensitive transfer material 20 shown in FIG. 1 has a structure in which a pseudo-support 11, a particle layer 18, a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive layer 17 and a covering film 19 are sequentially layered.

As a method for manufacturing the above-mentioned photosensitive transfer material 20, for example, there can be cited a method including the following steps: after coating a photosensitive layer forming composition on the cover film 19, the coating of the photosensitive layer forming composition is dried to form a photosensitive layer 17; after coating an intermediate layer forming composition on the surface of the photosensitive layer 17, the coating of the intermediate layer forming composition is dried to form an intermediate layer; The step of forming a layer 15; the step of drying the film of the thermoplastic resin composition after coating the surface of the intermediate layer 15 to form a thermoplastic resin layer 13; the step of drying the film of the particle layer forming layer composition after coating the surface of the thermoplastic resin layer 13 to form a particle layer 18; and the step of pressing the pseudo support 11 to the particle layer 18. In the above-mentioned manufacturing method, it is preferred to use a particle layer forming composition containing at least one selected from the group including water and water-miscible organic solvents, a thermoplastic resin composition containing at least one selected from the group including alkylene glycol ether solvents and alkylene glycol ether acetate solvents, an intermediate layer forming composition containing at least one selected from the group including water and water-miscible organic solvents, and a photosensitive layer forming composition containing a superposition compound, a polymerization initiator, and at least one selected from the group including alkylene glycol ether solvents and alkylene glycol ether acetate solvents. In this way, mixing of the components of each layer when forming each layer can be suppressed.

The photosensitive transfer material 20 is manufactured by pressing the pseudo support 11 against the particle layer 18 of the laminate manufactured by the above-mentioned manufacturing method. After the photosensitive transfer material 20 is manufactured by the above-mentioned manufacturing method, the photosensitive transfer material 20 can be rolled up to manufacture and store the roll-shaped photosensitive transfer material. The roll-shaped photosensitive transfer material can be directly provided in this form to the step of laminating with the substrate based on the roll-to-roll method described later.

Furthermore, as a first embodiment of the method for manufacturing the photosensitive transfer material disclosed herein, there can be cited a method comprising the following steps: after coating a photosensitive layer forming composition on a covering film, drying the coating of the photosensitive layer forming composition to form a photosensitive layer; after coating a particle layer forming layer composition on the surface of the photosensitive layer, drying the coating of the particle layer forming layer composition to form a particle layer having a convex structure on the surface; and pressing a pseudo-support body against the surface of the particle layer having a convex structure.

The photosensitive transfer material disclosed herein can be preferably used for various applications that require precision micro-processing based on photolithography. After the photosensitive layer is patterned, the photosensitive layer can be etched as a coating, or electroplating can be performed. In addition, the cured film obtained by patterning can be used as a permanent film, for example, it can be used as an interlayer insulation film, a wiring protection film, a wiring protection film with a refractive index matching layer, etc. In addition, the photosensitive transfer material disclosed herein can be preferably used for various wiring formation purposes of semiconductor packaging, printed circuit boards, sensor substrates, 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 micro-machines or micro-electronics.

In addition, the photosensitive transfer material disclosed in the present invention can also preferably be used in a state where the photosensitive layer is a colored resin layer containing a pigment. In addition to the above-mentioned uses of the colored resin layer, for example, it is suitable for forming colored pixels or black matrices such as filters for liquid crystal display devices (LCDs) and solid-state imaging devices [for example, CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors)]. Regarding the state other than the pigment in the colored resin layer, it is the same as the above-mentioned state.

(Manufacturing method of resin pattern and manufacturing method of circuit wiring) The manufacturing method of resin pattern disclosed herein is a manufacturing method of resin pattern that forms a resin pattern on a substrate using the photosensitive transfer material disclosed herein. As the manufacturing method of resin pattern disclosed herein, it is preferred to include the following steps in sequence: a step of peeling off the above-mentioned covering film in the photosensitive transfer material disclosed herein (hereinafter, also referred to as "covering film peeling step"); a step of bringing the outermost layer of the above-mentioned photosensitive layer side in the above-mentioned photosensitive transfer material from which the above-mentioned covering film has been peeled into contact with and laminating with a support having a conductive layer (hereinafter, also referred to as "laminating step"). ”); a step of peeling off the pseudo-support from the particle layer (hereinafter, also referred to as the “pseudo-support peeling step”); a step of bringing an exposure mask into contact with the particle layer and exposing the photosensitive layer in a pattern through the exposure mask (hereinafter, also referred to as the “exposure step”); and a step of developing the photosensitive layer to form a resin pattern (hereinafter, also referred to as the “pattern forming step”). In addition, the photosensitive transfer material bonded to the substrate in the bonding step in the resin pattern manufacturing method, the circuit wiring manufacturing method, and the electronic device manufacturing method is set to have no covering film. In the case of a photosensitive transfer material having a cover film, the method for manufacturing a resin pattern, the method for manufacturing a laminate, the method for manufacturing a circuit wiring, or the method for manufacturing an electronic device includes a step of peeling off the cover film before the lamination step.

The manufacturing method of the circuit wiring disclosed in the present invention is not particularly limited as long as it is a method using the photosensitive transfer material disclosed in the present invention. The manufacturing method of the circuit wiring disclosed in the present invention sequentially includes the steps of peeling off the above-mentioned covering film in the photosensitive transfer material disclosed in the present invention, making the outermost layer of the above-mentioned photosensitive layer side of the above-mentioned photosensitive transfer material from which the above-mentioned covering film is peeled off contact with and bonded to a support having a conductive layer, peeling off the above-mentioned pseudo support from the above-mentioned particle layer, and making an exposure mask A method for manufacturing a circuit wiring comprising the steps of exposing the photosensitive layer in a pattern in contact with the particle layer and through the exposure mask, developing the photosensitive layer to form a resin pattern, and etching the conductive layer using the formed resin pattern as a mask (hereinafter also referred to as an "etching step") or sequentially stripping the conductive layer of the present invention. The step of removing the cover film from the photosensitive transfer material, the step of bringing the outermost layer of the photosensitive layer side of the photosensitive transfer material from which the cover film is peeled off into contact with a support having a conductive layer and laminating the outermost layer, the step of peeling the pseudo support from the particle layer, the step of bringing an exposure mask into contact with the particle layer and exposing the photosensitive layer through the exposure mask. A method for manufacturing circuit wiring that includes a step of exposing a pattern, a step of developing the photosensitive layer to form a resin pattern, a step of electroplating the conductive layer using the formed resin pattern as a mask (hereinafter also referred to as a "plating step"), a step of peeling the formed resin pattern, and a step of etching the conductive layer is preferred. Below, the steps included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring are described, but except for the cases specifically mentioned, the contents of the description of the steps included in the method for manufacturing a resin pattern are also applicable to the steps included in the method for manufacturing a circuit wiring.

<Step of peeling off the covering film> The method for producing the resin pattern preferably includes the step of peeling off the covering film from the photosensitive transfer material disclosed herein. The method of peeling off the covering film is not limited, and a known method can be applied.

<Laminating step> The method for manufacturing a resin pattern preferably includes a laminating step. In the laminating step, the substrate (the conductive layer when a conductive layer is provided on the surface of the substrate) is brought into contact with the outermost layer of the photosensitive transfer material having one side of the photosensitive layer relative to the above-mentioned pseudo support, so that the photosensitive transfer material and the substrate are pressed. In the above-mentioned embodiment, the outermost layer of the photosensitive transfer material having one side of the photosensitive layer relative to the above-mentioned pseudo support is more closely attached to the substrate, so that the photosensitive layer formed with the pattern after exposure and development can be preferably used as an etching resist when etching the conductive layer.

In addition, when the photosensitive transfer material further has a layer other than the covering film (for example, a high refractive index layer and/or a low refractive index layer) on the surface of the photosensitive layer on the side not opposite to the pseudo-support, the bonding step becomes a state in which the surface of the photosensitive layer on the side not having the pseudo-support is bonded to the substrate via the layer.

The method of pressing the substrate and the photosensitive transfer material is not particularly limited, and known transfer methods and lamination methods can be used. The lamination of the photosensitive transfer material to the substrate is preferably performed by overlapping the outermost layer of the photosensitive transfer material having one side of the photosensitive layer relative to the pseudo support and the substrate, and applying pressure and heating using a roller or other means. For lamination, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used. The lamination temperature is not particularly limited, but for example, 70°C to 130°C is preferred.

The method for manufacturing a resin pattern and a method for manufacturing a laminated body including a lamination step are preferably performed by a roll-to-roll method. The roll-to-roll method is described below. The roll-to-roll method refers to a method in which a substrate that can be rolled up and unrolled is used as a substrate, and before any step included in the method for manufacturing a resin pattern or an etching method, a step of unrolling the substrate or a structure including the substrate (also referred to as a "rolling-out step") is included, and after any step, a step of rolling up the substrate or a structure including the substrate (also referred to as a "rolling-up step") is included, and at least any step (preferably all steps or all steps except the heating step) is performed while transporting the substrate or the structure including the substrate. The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method can be used in a manufacturing method that applies a roll-to-roll method.

<Support> As a support having a conductive layer used in the method for manufacturing a resin pattern disclosed herein, a support having a known conductive layer may be used, but it is preferred that the surface of the support has a conductive layer. The support may have any layer other than the conductive layer as required. As a support, for example, a resin substrate, a glass substrate, and a semiconductor substrate may be cited. As a preferred embodiment of the support, for example, the description in paragraph 0140 of International Publication No. 2018/155193 may be cited, and the content is incorporated into this specification.

As the substrate constituting the support body, for example, glass, silicon and thin film can be cited. The substrate constituting the support body is preferably transparent. In this specification, "transparent" means that the transmittance of light with a wavelength of 400nm to 700nm is more than 80%. In addition, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

As the transparent glass substrate, there can be cited tempered glass represented by Gorilla Glass of Corning Incorporated Co., Ltd. Also, as the transparent glass substrate, materials used in Japanese Patent Application Publication No. 2010-86684, Japanese Patent Application Publication No. 2010-152809, and Japanese Patent Application Publication No. 2010-257492 can be used.

When a film substrate is used as a support, it is preferred to use a film substrate with small optical strain and/or high transparency. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

When manufacturing the support by roll-to-roll method, a film substrate is preferred. When manufacturing the circuit wiring for the touch panel by roll-to-roll method, the substrate is preferably a sheet-like resin composition.

As the conductive layer, a conductive layer used for general circuit wiring or touch panel wiring can be cited. As the conductive layer, from the viewpoint of conductivity and fine line formation, at least one layer selected from the group including a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer and a conductive polymer layer is preferred, a metal layer is more preferred, and a copper layer or a silver layer is further preferred. The substrate may have a single conductive layer or may have two or more layers. When having two or more conductive layers, conductive layers having different materials are preferred.

As materials for the conductive layer, metals and conductive metal oxides can be cited. As metals, Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au can be cited. As conductive metal oxides, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO ₂ can be cited. In addition, in this specification, "conductivity" means that the volume resistivity is less than 1×10 ⁶ Ωcm. It is preferred that the volume resistivity of the conductive metal oxide is less than 1×10 ⁴ Ωcm.

When a resin pattern is manufactured using a substrate having a plurality of conductive layers, it is preferred that at least one of the plurality of conductive layers contains a conductive metal oxide. As a conductive layer, it is preferred to be an electrode pattern of a sensor used in a visual recognition portion of an electrostatic capacitive touch panel or a wiring of a peripheral lead portion. As a preferred embodiment of the conductive layer, for example, the description in paragraph 0141 of International Publication No. 2018/155193 can be cited, and the content is incorporated into this specification.

As a substrate having a conductive layer, a substrate having at least one of a transparent electrode and a routing wiring is preferred. The substrate as described above can be preferably used as a substrate for a touch panel. The transparent electrode can preferably 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) and IZO (indium zinc oxide) and a metal fine wire such as a metal mesh and a silver nanowire. As the metal fine wire, fine wires of silver, copper, etc. can be cited. Among them, silver conductive materials such as a silver mesh and a silver nanowire are preferred.

As the material of the lead wiring, metal is preferred. As the metal of the lead wiring, gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese and alloys composed of two or more of these metal elements can be cited. As the material of the lead wiring, copper, molybdenum, aluminum or titanium is preferred, and copper is particularly preferred.

For the purpose of protecting electrodes, etc. (i.e., at least one of electrodes for a touch panel and wiring for a touch panel), it is preferred that the electrode protection film for a touch panel formed using the photosensitive transfer material disclosed herein is provided in a manner that covers the electrodes, etc. directly or through other layers.

<Dummy support stripping step> The method for manufacturing the resin pattern preferably includes a dummy support stripping step of stripping the dummy support between the laminating step and the exposure step. The dummy support stripping method is not particularly limited, and the same mechanism as the cover film stripping mechanism described in paragraphs 0161 to 0162 of Japanese Patent Application Publication No. 2010-072589 can be used.

<Exposure step> The method for manufacturing a resin pattern preferably includes a step (exposure step) of bringing an exposure mask into contact with the particle layer and performing pattern exposure on the photosensitive layer through the exposure mask. The exposure process is a pattern-like exposure process (also referred to as "pattern exposure"), that is, an exposure process in a form in which there are exposed parts and non-exposed parts. The positional relationship between the exposed area and the non-exposed area in the pattern exposure is not particularly limited and can be adjusted appropriately.

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 an etching method and reduce the area occupied by the lead wiring, at least a portion of the pattern (preferably the electrode pattern of the touch panel and/or the lead wiring portion) preferably includes a fine line with a width of 20 μm or less, and more preferably includes a fine line 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 irradiates light of a wavelength capable of exposing the photosensitive layer (for example, 365nm or 405nm). Specifically, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes) can be cited. As the exposure amount, 5mJ/ ^cm2 to 200mJ/ ^cm2 is preferred, and 10mJ/ ^cm2 to 100mJ/ ^cm2 is more preferred. As preferred aspects of the light source, exposure amount, and exposure method used in the exposure, for example, the description of paragraphs 0146 to 0147 of International Publication No. 2018/155193 can be cited, and these contents are incorporated into this specification.

In the exposure step, it is preferred to make the exposure mask contact with the photosensitive layer and perform the exposure. The exposure method can preferably be a contact exposure method. In the case of projection exposure of a lens system or a reflector system, an exposure machine with an appropriate lens aperture number (NA) can be used according to the required resolution and focus depth. In addition, the exposure can be performed not only in the atmosphere but also in a reduced pressure or vacuum, and the exposure can be performed by placing a liquid such as water between the light source and the photosensitive layer.

<Pattern forming step> In the pattern forming step, the exposed photosensitive layer is developed to form a resin pattern.

The development of the exposed photosensitive layer in the pattern forming step can be performed using a developer. As a developer, there is no particular limitation as long as the non-image portion of the photosensitive layer can be removed. For example, a known developer such as the developer described in Japanese Patent Publication No. 5-72724 can be used. As a developer, an alkaline aqueous solution containing a compound with pKa=7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter) is preferred. The developer may contain a water-soluble organic solvent and/or a surfactant. As alkaline compounds that can be contained in the alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide) can be cited. As a developer, the developer described in paragraph 0194 of International Publication No. 2015/093271 can also be preferably cited. As a developing method that can be preferably used, for example, the developing method described in paragraph 0195 of International Publication No. 2015/093271 can be cited.

The developing method is not particularly limited, and may be any of puddle development, shower development, shower and rotation development, and immersion development. Spray development refers to a developing process in which a developer is sprayed onto the exposed photosensitive layer to remove the non-image portion. After the pattern forming step, it is preferred to spray a cleaning agent by spraying and remove the development residue while wiping with a brush. The liquid temperature of the developer is not particularly limited, but 20°C to 40°C is preferred.

<Post-exposure step and post-baking step> The method for manufacturing a resin pattern or the method for manufacturing a laminate may include a step of exposing the resin pattern obtained by the above-mentioned pattern forming step (post-exposure step) and/or a step of heating (post-baking step). When both the post-exposure step and the post-baking step are included, it is preferable to perform the post-baking after the post-exposure.

<Etching step> The method for manufacturing circuit wiring preferably includes a step of etching the conductive layer (etching step), and more preferably includes a step of etching the conductive layer using the formed resin pattern as a mask.

In the etching step, the resin pattern formed by the photosensitive layer is used as an etching resist to etch the conductive layer, or the resin pattern is removed after the electroplating process described later, and the conductive layer is etched using the plated pattern as a resist. As an etching process method, a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of Japanese Patent Publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Publication No. 2010-152155, a wet etching method by immersion in an etching solution, and a dry etching method based on plasma etching, etc. can be cited.

The etching solution used for wet etching can be an acidic or alkaline etching solution appropriately selected according to the etching object. As an acidic etching solution, for example, there can be cited an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, fluoric acid, oxalic acid and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride and potassium permanganate. The acidic component can also be a component composed of a plurality of acidic components. As an alkaline etching solution, there can be cited an aqueous solution of an alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines and salts of organic amines (tetramethylammonium hydroxide, etc.), and a mixed aqueous solution of an alkaline component and a salt (potassium permanganate, etc.). The alkaline component may also be a component formed by combining multiple alkaline components.

<Coating step> The method for manufacturing circuit wiring preferably includes the step of performing electroplating on the conductive layer using the formed resin pattern as a mask.

As the plating method, a known method can be applied, for example, electroplating is preferred, and electrolytic copper plating is more preferred.

As a component of the plating solution used in the electroplating, for example, a water-soluble copper salt can be cited. As the water-soluble copper salt, a water-soluble copper salt commonly used as a component of the plating solution can be used. As the water-soluble copper salt, for example, at least one selected from the group consisting of inorganic copper salts, alkanesulfonate copper salts, alkanolsulfonate copper salts and organic acid copper salts is preferred. As the inorganic copper salt, for example, copper sulfate, copper oxide, copper chloride and copper carbonate can be cited. As the alkanesulfonate copper salt, for example, copper methanesulfonate and copper propanesulfonate can be cited. As the alkanolsulfonate copper salt, for example, copper hydroxyethanesulfonate and copper propanolsulfonate can be cited. Examples of organic acid copper salts include copper acetate, copper citrate, and copper tartrate. In addition, as a component of the plating solution used in electroplating, instead of the above copper, salts of other corresponding metals may be used.

The plating solution may contain sulfuric acid. By containing sulfuric acid in the plating solution, the pH and sulfuric acid ion concentration of the plating solution can be adjusted.

The method and conditions of electroplating are not limited. For example, by supplying the conductive substrate after the development step to a plating tank filled with a plating solution, a conductive pattern can be formed on the conductive layer located in the area where the resin pattern is not arranged. In the electroplating, for example, by controlling the current density and the conveying speed of the conductive substrate, a conductive pattern can be formed.

The temperature of the plating solution used in electroplating is preferably below 70°C, more preferably 10°C to 40°C. The current density in electroplating is preferably 0.1A/ ^dm2 to 100A/ ^dm2 , more preferably 0.5A/ ^dm2 to 20A/ ^dm2 . By increasing the current density, the productivity of the conductive pattern can be improved. By reducing the current density, the uniformity of the thickness of the conductive pattern can be improved.

<Stripping step> The method for manufacturing circuit wiring preferably includes a stripping step of stripping the above-mentioned resin pattern. As a method for stripping the remaining resin pattern, there is no particular limitation, and a method of stripping by chemical treatment and a method of stripping using a removal liquid are preferably cited. As a method for removing the resin pattern, a method of immersing a conductive substrate having a residual resin pattern in a stirring removal liquid having a liquid temperature of preferably 30°C to 80°C, more preferably 50°C to 80°C for 1 minute to 30 minutes can be cited.

As a removal liquid, for example, a removal liquid obtained by dissolving an inorganic alkali component or an organic alkali component in water, dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof can be cited. As an inorganic alkali component, for example, sodium hydroxide and potassium hydroxide can be cited. As an organic alkali component, a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound can be cited. In addition, the removal liquid can also be used and removed by a known method such as a spraying method, a spraying method and a spinning immersion method.

<Other steps> The method for manufacturing a resin pattern, the method for manufacturing a laminate, and the method for manufacturing a circuit wiring may include any steps (other steps) other than the above steps. For example, the following steps can be cited, but are not limited to these steps. In addition, as pattern forming steps and other steps applicable to the method for manufacturing a circuit wiring, the steps described in paragraphs 0035 to 0051 of Japanese Patent Publication No. 2006-23696 can be cited. Furthermore, as other steps, for example, the step of reducing the visible light reflectivity described in paragraph 0172 of International Publication No. 2019/022089, the step of forming a new conductive layer on the insulating film described in paragraph 0172 of International Publication No. 2019/022089, etc. can be cited, but it is not limited to these steps.

-Step of reducing visible light reflectivity- The manufacturing method of circuit wiring may include a step of reducing the visible light reflectivity of a part or all of the plurality of conductive layers of the substrate. As a treatment for reducing the visible light reflectivity, an 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. Regarding the treatment of reducing the reflectivity of visible light, it is described in paragraphs 0017 to 0025 of Japanese Patent Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Publication No. 2013-206315. The contents described in these publications are incorporated into this manual.

- Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film- It is also preferred that the method for manufacturing circuit wiring includes the step of forming an insulating film on the surface of the circuit wiring and the step of forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. As the step of forming the insulating film, there is no particular limitation, and a known method of forming a permanent film can be cited. In addition, a photosensitive material having insulating properties can be used to form an insulating film of a desired pattern by photolithography. The step of forming a new conductive layer on the insulating film is not particularly limited. For example, a new conductive layer of a desired pattern can be formed by using a photosensitive material having conductivity through photolithography.

In the method for manufacturing circuit wiring, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and to form circuits on the conductive layers formed on the two surfaces of the substrate sequentially or simultaneously. With this structure, it is possible to form a circuit wiring for a touch panel having a first conductive pattern formed on one surface of the substrate and a second conductive pattern formed on the other surface. It is also preferable to form the circuit wiring for a touch panel having this structure from both sides of the substrate in a roll-to-roll manner.

<Application> The resin pattern produced by the method for producing the resin pattern disclosed herein and the circuit wiring produced by the method for producing the circuit wiring disclosed herein can be applied to various devices. As the above-mentioned device, for example, an input device can be cited, and a touch panel is preferred, and an electrostatic capacitive touch panel is more preferred. In addition, the above-mentioned input device can be applied to display devices such as organic electroluminescent display devices and liquid crystal display devices. When applied to a touch panel, the formed resin pattern is preferably used as a protective film for an electrode for a touch panel or a wiring for a touch panel. That is, the photosensitive transfer material disclosed herein is preferably used for forming a protective film for an electrode for a touch panel or a wiring for a touch panel.

(Method for manufacturing electronic device) The method for manufacturing the electronic device disclosed herein is not particularly limited as long as it is a method using the photosensitive transfer material disclosed herein. The method for manufacturing the electronic device disclosed herein includes, in sequence, the steps of peeling off the above-mentioned covering film in the photosensitive transfer material disclosed herein, bringing the outermost layer of the above-mentioned photosensitive layer side of the above-mentioned photosensitive transfer material from which the above-mentioned covering film has been peeled off into contact with and laminating a support having a conductive layer, peeling off the above-mentioned pseudo-support from the above-mentioned particle layer, and then laminating the outermost layer of the above-mentioned pseudo-support. The method comprises the steps of: making an exposure mask contact the particle layer and exposing the photosensitive layer through the exposure mask; developing the photosensitive layer to form a resin pattern; and etching the conductive layer using the formed resin pattern as a mask. The step of removing the cover film from the photosensitive transfer material, the step of bringing the outermost layer of the photosensitive layer side of the photosensitive transfer material from which the cover film is peeled off into contact with and laminating the support having a conductive layer, the step of peeling the pseudo support from the particle layer, the step of bringing an exposure mask into contact with the particle layer and interposing the exposure mask on the particle layer. A method is preferably a step of exposing the photosensitive layer to a pattern using a mask, a step of developing the photosensitive layer to form a resin pattern, a step of electroplating the conductive layer using the formed resin pattern as a mask, a step of peeling off the formed resin pattern, and a step of etching the conductive layer. In addition, as a manufacturing method of the electronic device disclosed in the present invention, it is preferred to include a step of peeling off the covering film before the laminating step.

The specific aspects of each step in the method for manufacturing an electronic device and the implementation aspects of the order of performing each step are as described above, and the preferred aspects are also the same. Regarding the method for manufacturing an electronic device, in addition to forming the wiring for the electronic device by the above method, it is sufficient to refer to the known method for manufacturing an electronic device. In addition, the method for manufacturing an electronic device may include any steps (other steps) other than the above.

As electronic devices, there are no particular restrictions, and preferably, semiconductor packages, printed circuit boards, various wiring formation uses of sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as thin film heaters, liquid crystal sealing materials, micro-machines or structures in the field of microelectronics can be cited. The above-mentioned resin pattern is preferably used as a permanent film in the above-mentioned electronic devices, such as an interlayer insulation film, a wiring protection film, a wiring protection film with a refractive index matching layer, etc. Among them, as an electronic device, a touch panel can be cited as a particularly preferred example.

An example of a mask pattern used for manufacturing a touch panel is shown in FIG. 2 and FIG. 3. In the pattern A shown in FIG. 2 and the pattern B shown in FIG. 3, GR is a non-image portion (light shielding portion), EX is an image portion (exposure portion), and DL is a virtually indicated alignment frame. In the manufacturing method of the touch panel, for example, the above-mentioned photosensitive layer is exposed through a mask having the pattern A shown in FIG. 2, thereby manufacturing a touch panel having a circuit wiring having the pattern A corresponding to EX. Specifically, it can be manufactured using the method described in FIG. 1 of International Publication No. 2016/190405. In an example of a manufactured touch panel, the central portion of the exposure portion EX (the pattern portion formed by connecting the four corners) is the portion where the transparent electrode (electrode for the touch panel) is formed, and the peripheral portion of the exposure portion EX (the thin line portion) is the portion where the wiring of the peripheral lead portion is formed.

By using the manufacturing method of the electronic device, an electronic device having at least wiring for the electronic device is manufactured, preferably a touch panel having at least wiring for the touch panel is manufactured. The touch panel preferably has a transparent substrate, an electrode, and an insulating layer or a protective layer. As a detection method in the touch panel, known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method can be cited. Among them, the electrostatic capacitance method is preferred.

As the touch panel type, there can be cited the so-called in-cell type (for example, those described in FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of Japanese Patent Publication No. 2012-517051), the so-called on-cell type (for example, those described in FIG. 19 of Japanese Patent Publication No. 2013-168125 and those described in FIG. 1 and FIG. 5 of Japanese Patent Publication No. 2012-89102), OGS (One Glass Solution: single-piece glass touch) type, TOL (Touch-on-Lens: cover layer touch) type (for example, those described in FIG. 2 of Japanese Patent Publication No. 2013-54727), various out-cell types ( type) (so-called GG, G1·G2, GFF, GF2, GF1 and G1F, etc.) and other structures (for example, those described in FIG. 6 of Japanese Patent Publication No. 2013-164871). As a touch panel, for example, those described in paragraph 0229 of Japanese Patent Publication No. 2017-120435 can be cited. [Implementation Example]

The following examples are given to further illustrate the implementation of the present invention. The materials, usage amounts, ratios, processing contents and processing steps shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the implementation of the present invention. Therefore, the scope of the implementation of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are mass standards.

(Examples 1 to 6 and 19, and Comparative Examples 1 and 2) <Preparation of Photosensitive Layer Forming Composition 1> The following components were mixed and filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm to obtain a photosensitive layer forming composition 1. Propylene glycol-1-monomethyl ether-2-acetate (PGMEA): 425.1 parts by mass Polymer A-3: 236.0 parts by mass Photoacid generator B-1: 5.0 parts by mass Surfactant E-1: 0.1 parts by mass Alkaline compound F-1: 0.5 parts by mass Additive G-1: 0.17 parts by mass

[Synthesis Example of Polymer A-3] PGMEA (75.0 parts by mass) was placed in a three-necked flask and heated to 90°C in a nitrogen atmosphere. A solution containing ATHF (25.0 parts by mass), MAA (10.0 parts by mass), CHMA (35.0 parts by mass), CHA (30.0 parts by mass), V-601 (4.1 parts by mass) and PGMEA (75.0 parts by mass) was added dropwise over 2 hours to the solution in the three-necked flask maintained at a temperature range of 90°C±2°C. After the addition was completed, the mixture was stirred at a temperature range of 90°C±2°C for 2 hours to obtain polymer A-3 (solid content concentration 40.0% by mass). Polymer A-3 is a binder polymer having an acid group protected by an acid-decomposable group.

ATHF: Tetrahydrofuran-2-yl acrylate (synthetic product) MAA: Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) CHMA: Cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) CHA: Cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) V-601: Dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

-Synthesis of ATHF- Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to a three-necked flask and cooled to 20°C. Camphorsulfonic acid (0.0070 parts by mass, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent) were added dropwise, and then stirred at 20°C±2°C for 1.5 hours, then heated to 35°C and stirred for 2 hours. KYOWARD 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and KYOWARD 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) were inserted into the suction filter in this order, and the reaction solution was filtered to obtain a filtrate. After adding hydroquinone monomethyl ether (MEHQ, 0.0012 parts by mass) to the obtained filtrate, the mixture was concentrated under reduced pressure at 40°C to obtain 140.8 parts by mass of tetrahydrofuran-2-yl acrylate (ATHF) as a colorless oil (yield 99.0%).

[Photoacid generator] Photoacid generator B-1: A compound having the structure shown below (the compound described in paragraph 0227 of Japanese Patent Application Laid-Open No. 2013-047765, synthesized according to the method described in paragraph 0204.)

[Chemical formula 19]

[Surfactant] Surfactant E-1: Compound with the structure shown below

[Chemical formula 20]

[Alkaline compound] Alkaline compound F-1: A compound having the structure shown below

[Chemical formula 21]

[Additives] Additive G-1: BT-120 (1,2,3-benzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.)

<Preparation of Particle Layer Forming Compositions 1 to 9> The components listed in Table 1 were mixed and filtered using a polytetrafluoroethylene filter having a pore size of 5.0 μm to obtain Particle Layer Forming Composition 1. In addition, Particle Layer Forming Compositions 2 to 9 were obtained in the same manner.

[Table 1] Particle layer forming composition 1 Particle layer forming composition 2 Particle layer forming composition 3 Particle layer forming composition 4 Particle layer forming composition 5 Particle layer forming composition 6 Particle layer forming composition 7 Particle layer forming composition 8 Particle layer forming composition 9 Resin KURARAY POVAL 4-88LA - - - - - - - 5.94 - METOLOSE 60SH-03 - - - - - - - 0.09 - METOLOSE 60SH-06 9.00 9.00 9.00 10.00 - - - - - Polyvinylpyrrolidone K-30 - - - - - - - 2.97 - Polymer A-1 - - - - 29.71 - - - - Polymer A-2 - - - - - 29.71 29.71 - 33.04 particle SNOWTEX OZL-35 2.86 - - - - - - 2.86 - SNOWTEX OYL - 5.00 - - - - - - - EPOSTAR MX100W - - 10.00 - - - - - - MEK-ST-ZL - - - - 3.33 3.33 - - - MEK-ST-L - - - - - - 3.33 - - Surfactant MEGAFACE F-444 0.10 0.10 0.10 0.10 - - - 0.10 - MEGAFACE F-552 - - - - 0.09 0.09 0.09 - 0.09 Solvent water 493.14 491.00 486.00 495.00 - - - 493.14 - Methanol 495.00 495.00 495.00 495.00 - - - 495.00 - MEK - - - - 690.67 690.67 690.67 - 693.00 PGMEA - - - - 127.70 127.70 127.70 - 125.37 PGME - - - - 148.50 148.50 148.50 - 148.50

The numerical values of the components in Table 1 represent mass ratios. The amounts of polymers A-1 and A-2 described in Table 1 are amounts as 30 mass % solutions.

The following is a detailed description of each component listed in Table 1. KURARAY POVAL 4-88LA: (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) METOLOSE 60SH-03: (hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.) METOLOSE 60SH-06: (hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.) Polyvinylpyrrolidone K-30: (polyvinylpyrrolidone, manufactured by NIPPON SHOKUBAI CO., LTD.) Polymer A-1: The polymer shown below Polymer A-2: The polymer shown below SNOWTEX OZL-35: (silicon dioxide particles, arithmetic average particle size 80 nm, solid content 35% by mass, manufactured by Nissan Chemical Corporation) SNOWTEX OYL: (silicon dioxide particles, arithmetic average particle size 60nm, solid content 20% by mass, manufactured by Nissan Chemical Corporation) EPOSTAR MX100W: (acrylic crosslinked particles, arithmetic average particle size: 150nm, solid content 10% by mass, manufactured by NIPPON SHOKUBAI CO., LTD.) MEK-ST-ZL: (silicon dioxide particles, arithmetic average particle size 80nm, solid content 30% by mass, manufactured by Nissan Chemical Corporation) MEK-ST-L: (silicon dioxide particles, arithmetic average particle size 45nm, solid content 30% by mass, manufactured by Nissan Chemical Corporation) MEGAFACE F-444 (surfactant, manufactured by DIC Corporation) MEGAFACE F-552 (surfactant, manufactured by DIC Corporation) Water Methanol MEK: methyl ethyl ketone (SANKYO CHEMICAL CO.,LTD.) PGME: Propylene glycol monomethyl ether acetate (SHOWA DENKO K.K.) PGME: Propylene glycol monomethyl ether (SHOWA DENKO K.K.)

[Polymer A-1] Polymer A-1 was synthesized according to the following method. In the synthesis method of polymer A-1, the following abbreviations represent the following compounds respectively. St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation) MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation) MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) AA: Acrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation) BzMA: Benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) V-601: 2,2'-azobis(isobutyric acid) dimethyl ester (manufactured by FUJIFILM Wako Pure Chemical Corporation, polymerization initiator) PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

PGMEA (58.25 parts) and PGME (58.25 parts) were placed in a three-necked flask and heated to 90°C in a nitrogen atmosphere. While the liquid temperature in the three-necked flask was maintained at 90°C±2°C, a mixed liquid of St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), PGMEA (58.25 parts) and PGME (58.25 parts) was dripped into the three-necked flask over 2 hours. After the dripping was completed, the mixed liquid was stirred for 2 hours while the liquid temperature was maintained at 90°C±2°C, thereby obtaining a composition containing 30.0% by mass of polymer A. The acid value of polymer A was 189 mgKOH/g, the weight average molecular weight was 60,000, and the glass transition temperature was 131°C.

[Polymer A-2] Polymer A-2 was synthesized in the same manner as polymer A-1. Polymer A-2 is a 1:1 mixed solution (solid content concentration: 30.0 mass %) of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether of a copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (content of each monomer: 78 mass %/14.5 mass %/7.5 mass %, Mw: 30000, Tg 75°C, acid value 153 mgKOH/g)

<Preparation of photosensitive transfer material> Using a slit nozzle, the photosensitive layer-forming composition 1 was applied to the cover film (16KS40, manufactured by Toray Industries, Inc., a biaxially oriented polyethylene terephthalate (PET) film with a film thickness of 16 μm) listed in Table 2 in a manner such that the dry film thickness was 3.0 μm. After the above-mentioned application, it was dried in a convection oven at 100°C for 1 minute to form a photosensitive layer. After the above-mentioned photosensitive layer was formed, the intermediate layer-forming composition 1 was applied to the above-mentioned photosensitive layer in a manner such that the dry film thickness was 1.0 μm. Thereafter, it was dried in a convection oven at 100°C for 1 minute to form an intermediate layer on the photosensitive layer. After forming the intermediate layer, the particle layer forming composition 1 was applied to the intermediate layer in a manner that the dry film thickness was 0.1 μm. Thereafter, it was dried in a convection oven at 100°C for 1 minute, thereby producing a film A having an intermediate layer and a particle layer in sequence on a photosensitive layer. In addition, PANAPROTECT HP25 manufactured by PANAC CO., LTD. was prepared as a pseudo support with an adhesive layer containing an acrylic adhesive as film B. Finally, the film A and the film B were laminated at a speed of 14 m/min at room temperature in a manner that the particle layer of the film A was in contact with the adhesive layer of the film B, thereby producing the photosensitive transfer material 1 of Example 1. In the same manner, as shown in Table 2, photosensitive transfer materials 2 to 6, 1' and 2' of Examples 2 to 6 and Comparative Examples 1 and 2 were prepared respectively. In addition, photosensitive transfer material 19 of Example 19 was prepared as shown in Table 5 described later.

The photosensitive transfer material of each embodiment produced was taken out in the form of a slice (thin slice) with a film thickness of 100nm by focused ion beam (FIB) processing, and the cross section was observed using a transmission electron microscope (TEM). The length diameter of any 100 observed particles was measured, and the arithmetic average was used as the arithmetic average particle diameter. In addition, regarding the particle layer, it was confirmed that there was a structure containing particles and having a layer thickness relatively large relative to the surrounding area. The structure with a locally large layer thickness protruded toward the pseudo-support body side.

[Table 2] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Comparison Example 1 Comparison Example 2 Substrate Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Photosensitive transfer materials Photosensitive transfer material 1 Photosensitive transfer material 2 Photosensitive transfer material 3 Photosensitive transfer material 4 Photosensitive transfer material 5 Photosensitive transfer material 6 Photosensitive transfer material 1' Photosensitive transfer material 2' Covering film 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 Transfer layer Photosensitive layer Prescription Photosensitive layer forming composition 1 Photosensitive layer forming composition 1 Photosensitive layer forming composition 1 Photosensitive layer forming composition 1 Photosensitive layer forming composition 1 Photosensitive layer forming composition 1 Photosensitive layer forming composition 1 Photosensitive layer forming composition 1 Type just just just just just just just just Layer thickness 3μm 3μm 3μm 3μm 3μm 3μm 3μm 3μm Particle layer Compositions used Particle layer forming composition 1 Particle layer forming composition 1 Particle layer forming composition 2 Particle layer forming composition 2 Particle layer forming composition 3 Particle layer forming composition 3 without Particle layer forming composition 4 Particle size 80nm 80nm 60nm 60nm 150nm 150nm without without Layer thickness 30nm 60nm 20nm 40nm 60nm 100nm without 60nm Pseudo-support Name PANAPROTECT HP25 PANAPROTECT HP25 PANAPROTECT HP25 PANAPROTECT HP25 PANAPROTECT HP25 PANAPROTECT HP25 without PANAPROTECT HP25 Substrate film PET25μm PET25μm PET25μm PET25μm PET25μm PET25μm PET25μm PET25μm Adhesive layer Adhesive Acrylic Adhesive Acrylic Adhesive Acrylic Adhesive Acrylic Adhesive Acrylic Adhesive Acrylic Adhesive Acrylic Adhesive Acrylic Adhesive Layer thickness 1μm 1μm 1μm 1μm 1μm 1μm 1μm 1μm Smoothness 5 5 5 4 5 5 1 1 Line width uniformity 5 5 5 5 5 5 2 2 Linearity 5 5 5 5 4 3 5 5

In addition, the layer thickness of the particle layer in Table 2 represents the average layer thickness of the portion where no convex structure exists in the particle layer.

<Production of PET substrate with copper layer> A copper layer with a thickness of 200 nm was formed on both sides of a 100 μm thick polyethylene terephthalate (PET) film by sputtering, thereby producing a PET substrate with a copper layer (substrate 1).

<Preparation of samples for evaluation of smoothness> After peeling off the cover film, the photosensitive transfer materials of the prepared embodiments and comparative examples were laminated on one side of a PET substrate with a copper layer under lamination conditions of a linear pressure of 0.6 MPa and a linear speed (lamination speed) of 4 m/min. The PET substrate with a copper layer laminated with the prepared photosensitive transfer material was autoclaved for 120 minutes under conditions of an air pressure of 0.5 MPa and a temperature of 50°C, and then the pseudo support with an adhesive layer was peeled off and humidified in an environment of 25°C and 50%RH for 1 hour to prepare samples for evaluation of smoothness. For the smoothness evaluation samples of each embodiment, the surface was observed using a scanning electron microscope (SEM), and it was confirmed that there was a particle layer having a convex structure containing particles. In other words, it was confirmed that the particle layer and the pseudo-support body can be peeled off. In addition, it was confirmed that even after the covering film of the photosensitive transfer material was peeled off and it was thermally laminated on the substrate and the pseudo-support body was further peeled off, the surface of the pseudo-support body side of the particle layer also had a convex structure containing particles.

<Smoothness evaluation> The outermost layer of the prepared smoothness evaluation sample was brought into contact with a transparent sodium calcium glass (200mm×200mm) with a film thickness of 5mm. The static friction coefficient and dynamic friction coefficient were measured using a Tensilon universal material 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 plastic-film and sheet friction coefficient test method (JIS K7125:1999). The test conditions are shown below. Load: 200g Contact area: 63mm×63mm Test speed: 100mm/min

<Smoothness (static friction)> Smoothness was evaluated based on the static friction coefficient according to the following criteria. 5: Less than 0.4 4: 0.4 or more and less than 0.6 3: 0.6 or more and less than 1.0 2: 1.0 or more and less than 2.0 1: 2.0 or more or cannot be measured

<Preparation of resin pattern> After peeling off the cover film, the photosensitive transfer material of each embodiment and comparative example was laminated on both sides of a PET substrate with a copper layer under lamination conditions of a linear pressure of 0.6 MPa and a linear speed (lamination speed) of 4 m/min. The PET substrate with copper layer laminated with the prepared photosensitive transfer material was sterilized under high pressure for 120 minutes at an air pressure of 0.5 MPa and a temperature of 50°C. Then, the dummy support with adhesive layer was peeled off from both sides at the same time. A mask contact exposure machine (MA-1200A, manufactured by Japan Science Engineering Co., Ltd.) capable of vacuum-tight double-sided exposure was used to expose the topmost layer of the photosensitive transfer material peeled off from the dummy support and the line and space (line and space) of 4.5μm/1.5μm, 4μm/2μm, 5μm/5μm, 2μm/4μm, and 1.5μm/4.5μm. Two glass chromium masks with a test pattern of -50 kPa (space) were placed in vacuum contact for 8 seconds at a maximum gauge pressure of -50 kPa, and exposed with an ultra-high pressure mercury lamp through the mask. After standing for 30 minutes, the pattern was developed to form a resin pattern. The development was performed by spraying a 1.0 mass% sodium carbonate aqueous solution at 28°C for 40 seconds. The exposure was performed at an exposure amount of 5 μm/5 μm so that the line width of the line and space was 5 μm.

<Evaluation of line width uniformity> In the obtained resin pattern, if it is a negative photosensitive material, the part of the mask corresponding to the 1.5μm/4.5μm line and space is observed, and if it is a positive photosensitive material, the part of the mask corresponding to the 4.5μm/1.5μm line and space is observed, and the space width of 16 points in the opposite surface at 2cm intervals (the part dissolved in the developer) is measured, and its standard deviation is calculated. When the space is not resolved, the line width of the part is set to 0μm and the standard deviation is calculated. 5: Standard deviation is less than 0.10um 4: Standard deviation is 0.10μm or more and less than 0.20μm 3: Standard deviation is 0.20μm or more and less than 0.30μm 2: Standard deviation is 0.30μm or more and less than 0.50μm 1: Standard deviation is 0.50 or more or there is no analyzed part

<Evaluation of linearity> The sample with pattern was etched at 25°C for 80 seconds using copper etchant (Mec Bright SF-5404: manufactured by MEC Co., Ltd.), and photoresist was stripped using 4 mass% sodium hydroxide solution to produce a circuit wiring pattern. The line width of the 100-point 5μm/5μm line and space pattern was measured, and the LWR (i.e., the standard deviation of the line width) was calculated. Based on the LWR, the linearity of the wiring was evaluated according to the following criteria. The larger the value of the criteria 1 to 5 shown below, the better the linearity of the wiring pattern. 5: Less than 150nm 4: 150nm or more and less than 200nm 3: 200nm or more and less than 300nm 2: 300nm or more and less than 500nm 1: 500nm or more

<Production of circuit wiring pattern: subtractive method> The sample with pattern was etched at 25°C for 80 seconds using copper etching solution (Mec Bright SF-5404: manufactured by MEC Co., Ltd.), and the photoresist was stripped using 4 mass% sodium hydroxide solution to produce a circuit wiring pattern. The circuit wiring substrate obtained in each embodiment was observed under a microscope, and the result showed that there was no peeling or missing, and the pattern was complete.

<Production of circuit wiring pattern: semi-additive method> The sample with the pattern was electrolytically plated with copper to a thickness of 2.5μm, and after photoresist stripping using a 4 mass% sodium hydroxide solution, the circuit wiring pattern was produced by etching at 25°C for 80 seconds using a copper etchant (Mec Bright SF-5404: manufactured by MEC Co., Ltd.). The circuit wiring substrate obtained in each embodiment was observed under a microscope, and the result showed that there was no peeling or missing, and the pattern was complete.

(Examples 7 to 18, 20 and 21, and Comparative Examples 3 to 5) <Preparation of Photosensitive Layer Forming Composition 2> In addition to the above, the components used to prepare the photosensitive layer forming composition 2 are as follows.

[Ethylenically unsaturated compound B] ·B-1: NK Ester BPE-500 (2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.) ·B-2: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.)

[Photopolymerization initiator] ·B-CIM (photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Hampford)

[Sensitizer] ·SB-PI 701 (4,4'-bis(diethylamino)benzophenone, obtained from Sanyo Trading Co., Ltd.)

[Color developer] · N-1: 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-proofing agent] ·CBT-1 (Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.)

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

[Antioxidant] Phenidone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Surfactant] MEGAFACE F-552 (fluorine-based surfactant, manufactured by DIC Corporation)

The following components were mixed to prepare a photosensitive layer-forming composition 2. · Polymer A-1 (solid content concentration 30.0%): 50.00 parts · B-1: 36.20 parts · B-2: 5.00 parts · Photopolymerization initiator: 7.00 parts · Sensitizer: 0.50 parts · N-1: 0.40 parts · Chain transfer agent: 0.20 parts · Rust inhibitor: 0.10 parts · Polymerization inhibitor: 0.30 parts · Antioxidant: 0.01 parts · Surfactant: 0.29 parts · Methyl ethyl ketone (manufactured by SANKYO CHEMICAL CO., LTD.): 396.00 parts · PGMEA (manufactured by SHOWA DENKO K.K.): 170.00 parts

<Preparation of composition 1 for forming an intermediate layer> The following composition was prepared and filtered using a polytetrafluoroethylene filter with a pore size of 3.0 μm to obtain composition 1 for forming an intermediate layer. · Water: 435.0 parts by mass · Methanol: 475.0 parts by mass · KURARAY POVAL 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 26.33 parts by mass · Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 13.17 parts by mass · METOLOSE 60SH-03 (manufactured by Shin-Etsu Chemical Co., Ltd.): 0.50 parts by mass · SNOWTEX O (silicon dioxide particles, average particle size 12nm, manufactured by Nissan Chemical Corporation): 50.0 parts by mass · MEGAFACE F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.05 parts by mass

Intermediate layer-forming compositions 2 and 3 were obtained in the same manner as in the preparation of the intermediate layer-forming composition 1 except that the compositions were changed to those shown in Table 3 below.

[table 3] Intermediate layer forming composition 1 Intermediate layer forming composition 2 Intermediate layer forming composition 3 Resin KURARAY POVAL 4-88LA 26.33 - - GOHSENX CKS-50 - 16.48 - JMR-3H - 16.48 - METOLOSE 60SH-03 0.50 0.50 - HPC-SSL - - 40.00 Polyvinylpyrrolidone K-30 13.17 8.24 - Polyvinylpyrrolidone K-90 - 8.24 - filler SNOWTEX O 50.00 - 50.00 Surfactant MEGAFACE F-444 0.05 0.05 0.05 Solvent water 435.00 475.00 435.00 Methanol 475.00 475.00 475.00

<Preparation of Adhesive Layer Forming Composition 1> The following composition was prepared and filtered using a polytetrafluoroethylene filter with a pore size of 3.0 μm to obtain an adhesive layer forming composition 1. ·VYLON BX-1001 (polyester resin, Tg = -18 ° C, Mn = 28,000, manufactured by TOYOBO CO., LTD.): 60.4 parts by mass ·VYLON GK-800 (polyester resin, Tg = 50 ° C, Mn = 27,000, manufactured by TOYOBO CO., LTD.): 89.2 parts by mass ·MEGAFACE F-552 (manufactured by DIC Corporation): 0.39 parts by mass ·Methyl ethyl ketone (manufactured by SANKYO CHEMICAL CO., LTD.): 765.0 parts ·PGMEA (manufactured by SHOWA DENKO K.K.): 85.0 parts

<Preparation of photosensitive transfer material> Using a slit nozzle, the composition 1 for forming a photosensitive layer was applied to the cover film (16KS40, manufactured by Toray Industries, Inc.) listed in Table 4 in such a manner that the dry film thickness was 3.0 μm. After the above application, it was dried in a convection oven at 100°C for 1 minute to form a photosensitive layer. After the above photosensitive layer was formed, the composition 1 for forming an intermediate layer was applied to the above photosensitive layer in such a manner that the dry film thickness was 1.0 μm. Thereafter, it was dried in a convection oven at 100°C for 1 minute to form an intermediate layer on the photosensitive layer. After forming the intermediate layer, the particle layer forming composition 10 was applied to the intermediate layer in a manner that the dry film thickness was 0.1 μm. Thereafter, it was dried in a convection oven at 100°C for 1 minute, thereby producing a film A having a photosensitive layer, an intermediate layer, and a particle layer in order on a covering film. Using a slit nozzle, the adhesive layer forming composition 1 was applied to a PET support (16KS40, manufactured by Toray Industries, Inc.) in a manner that the dry film thickness was 3.0 μm. After the above application, it was dried in a convection oven at 100°C for 1 minute, thereby producing a film B (pseudo-support) having an adhesive layer on a PET support. The particle layer of the film A and the adhesive layer of the film B were brought into contact with each other and thermally laminated at 70°C at a speed of 14 m/min, thereby producing the photosensitive transfer material 7 of Example 7.

In the same manner, as shown in Table 4, Table 5 or Table 6, each photosensitive transfer material of Examples 7 to 18, 20 and 21 and Comparative Examples 3 to 5 was prepared. For these photosensitive transfer materials, the same measurement and evaluation as in Example 1 were performed. As a result, for the particle layer of the photosensitive transfer material of each embodiment prepared, it was confirmed that there was a structure containing particles and having a layer thickness relatively thick relative to the surrounding area. The structure with a locally large layer thickness protruded toward the pseudo-support body side. In addition, for the photosensitive transfer material of each embodiment, it was confirmed that the particle layer and the pseudo-support body could be peeled off. Furthermore, it was confirmed that even after the covering film of the photosensitive transfer material of each embodiment was peeled off and thermally laminated on the substrate, and the pseudo-support was further peeled off, the surface of the pseudo-support side of the particle layer also had a convex structure containing particles.

[Table 4] Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Substrate Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Photosensitive transfer materials Photosensitive transfer material 7 Photosensitive transfer material 8 Photosensitive transfer material 9 Photosensitive transfer material 10 Photosensitive transfer material 11 Photosensitive transfer material 12 Photosensitive transfer material 13 Photosensitive transfer material 14 Covering film 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 Transfer layer Photosensitive layer Compositions used Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Type Negative Negative Negative Negative Negative Negative Negative Negative Layer thickness 3μm 3μm 3μm 3μm 3μm 3μm 3μm 3μm Middle layer Compositions used Intermediate layer forming composition 1 Intermediate layer forming composition 1 Intermediate layer forming composition 1 Intermediate layer forming composition 1 Intermediate layer forming composition 2 Intermediate layer forming composition 2 Intermediate layer forming composition 2 Intermediate layer forming composition 2 Layer thickness 1μm 1μm 1μm 1μm 1μm 1μm 1μm 1μm Particle layer Compositions used Particle layer forming composition 5 Particle layer forming composition 5 Particle layer forming composition 5 Particle layer forming composition 5 Particle layer forming composition 6 Particle layer forming composition 6 Particle layer forming composition 6 Particle layer forming composition 6 Particle size 80nm 80nm 80nm 80nm 80nm 80nm 80nm 80nm Layer thickness 30nm 60nm 80nm 100nm 30nm 60nm 80nm 100nm Pseudo-support Substrate film 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 Adhesive layer Compositions used Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Layer thickness 3μm 3μm 3μm 3μm 3μm 3μm 3μm 3μm Oxygen permeability twenty two twenty two twenty two twenty two 25 25 25 25 Smoothness 5 5 5 4 5 5 5 4 Line width uniformity 5 5 5 4 5 5 5 4 Linearity 4 5 5 4 4 5 5 4

[table 5] Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Comparison Example 3 Comparison Example 4 Comparison Example 5 Substrate Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Substrate 1 Photosensitive transfer materials Photosensitive transfer material 15 Photosensitive transfer material 16 Photosensitive transfer material 17 Photosensitive transfer material 18 Photosensitive transfer material 19 Photosensitive transfer material 3' Photosensitive transfer material 4' Photosensitive transfer material 5' Covering film 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 Transfer layer Photosensitive layer Compositions used Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 1 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Type Negative Negative Negative Negative just Negative Negative Negative Layer thickness 3μm 3μm 3μm 3μm 3μm 3μm 3μm 3μm Middle layer Compositions used Intermediate layer forming composition 2 Intermediate layer forming composition 2 Intermediate layer forming composition 2 without Intermediate layer forming composition 3 Intermediate layer forming composition 2 Intermediate layer forming composition 2 without Layer thickness 1μm 1μm 1μm without 1μm 1μm 1μm 1μm Particle layer Compositions used Particle layer forming composition 7 Particle layer forming composition 7 Particle layer forming composition 7 Particle layer forming composition 8 Particle layer forming composition 5 without Particle layer forming composition 9 without Particle size 45nm 45nm 45nm 80nm 80nm without without without Layer thickness 20nm 45nm 60nm 30nm 60nm without 60nm without Pseudo-support Substrate film 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 16KS40 Adhesive layer Compositions used Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Adhesive layer forming composition 1 Layer thickness 3μm 3μm 3μm 3μm 3μm 3μm 3μm 3μm Oxygen permeability 25 25 25 9,200 8,400 25 25 26,000 Smoothness 4 4 3 4 5 1 1 1 Line width uniformity 4 4 4 3 5 2 2 1 Linearity 5 5 4 3 4 5 5 1

[Table 6] Embodiment 20 Embodiment 21 Substrate Substrate 1 Substrate 1 Photosensitive transfer materials Photosensitive transfer material 20 Photosensitive transfer material 21 Covering film 16KS40 16KS40 Transfer layer Photosensitive layer Compositions used Photosensitive layer forming composition 2 Photosensitive layer forming composition 2 Type Negative Negative Layer thickness 6μm 10μm Middle layer Compositions used Intermediate layer forming composition 2 Intermediate layer forming composition 2 Layer thickness 1μm 1μm Particle layer Compositions used Particle layer forming composition 6 Particle layer forming composition 6 Particle size 80nm 80nm Layer thickness 60nm 60nm Pseudo-support Substrate film 16KS40 16KS40 Adhesive layer Compositions used Adhesive layer forming composition 1 Adhesive layer forming composition 1 Layer thickness 3μm 3μm Oxygen permeability 25 25 Smoothness 5 5 Line width uniformity 5 4 Linearity 4 3

In addition, the layer thickness of the particle layer in Tables 4 to 6 represents the average layer thickness of a portion of the particle layer where no convex structure exists, and the unit of oxygen permeability is cc/m ² ·day·atm.

As shown in Table 2 and Table 4 to Table 6 above, the photosensitive transfer materials of Examples 1 to 21 are superior in smoothness compared to the photosensitive transfer materials of Comparative Examples 1 to 5. In addition, as shown in Table 2 and Table 4 to Table 6 above, the photosensitive transfer materials of Examples 1 to 21 are also superior in line width uniformity and linearity.

11: Pseudo-support body 12: Transfer layer 13: Thermoplastic resin layer 15: Intermediate layer 17: Photosensitive layer 18: Particle layer 18a: Convex structure 19: Cover film 20: Photosensitive transfer material GR: Light shielding part (non-image part) EX: Exposure part (image part) DL: Alignment frame

The disclosure of Japanese Patent Application No. 2022-120582 filed on July 28, 2022 is incorporated by reference into this disclosure All documents, patent applications, and technical standards described in this disclosure are incorporated by reference into this disclosure to the same extent as if each document, patent application, and technical standard were specifically and individually described as being incorporated by reference

FIG1 is a schematic diagram showing an example of the structure of a photosensitive transfer material. FIG2 is a schematic top view showing pattern A. FIG3 is a schematic top view showing pattern B.

without.

Claims (15)

A photosensitive transfer material having a transfer layer and a pseudo-support in sequence on a cover film, the transfer layer having a photosensitive layer and a particle layer containing particles in sequence, the particle layer is in contact with the pseudo-support, the particle layer and the pseudo-support can be peeled off, the surface of the pseudo-support side of the particle layer has a convex structure containing the particles, the average layer thickness of the portion of the particle layer where the convex structure does not exist is less than the arithmetic average particle size of the particles contained in the particle layer. A photosensitive transfer material, which has a transfer layer and a pseudo-support in sequence on a cover film, the transfer layer has a photosensitive layer, an intermediate layer and a particle layer containing particles in sequence, the particle layer is in contact with the pseudo-support, the particle layer and the pseudo-support can be peeled off, the surface of the pseudo-support side of the particle layer has a convex structure containing the particles. The photosensitive transfer material as described in claim 1 or claim 2, wherein the pseudo-support has an adhesive layer on the surface in contact with the particle layer. The photosensitive transfer material as described in claim 3, wherein the adhesive layer comprises a polyester resin. The photosensitive transfer material as described in claim 1 or claim 2, wherein the aforementioned photosensitive layer is a negative photosensitive layer. The photosensitive transfer material according to claim 1 or claim 2, wherein the oxygen permeability of the transfer layer is less than 25,000 cc/m ² ·day·atm. The photosensitive transfer material as described in claim 2, wherein the intermediate layer comprises polyvinyl alcohol. The photosensitive transfer material as described in claim 1 or claim 2, wherein the aforementioned particle layer comprises an alkali-soluble resin. The photosensitive transfer material as described in claim 1 or claim 2, wherein the arithmetic average particle size of the aforementioned particles is 10nm to 200nm. The photosensitive transfer material as described in claim 1 or claim 2, wherein the average layer thickness of the portion of the particle layer where the convex structure does not exist is 10nm to 200nm. A method for manufacturing a photosensitive transfer material, comprising the following steps: a step of providing a photosensitive layer-forming composition on a cover film to form a photosensitive layer; a step of providing a particle layer-forming composition on the aforementioned photosensitive layer to form a particle layer having a convex structure containing particles on the surface; and a step of attaching a pseudo-support to the surface of the aforementioned particle layer on one side having the aforementioned convex structure in a manner of contacting the aforementioned particle layer, wherein the average layer thickness of a portion of the aforementioned particle layer where the aforementioned convex structure does not exist is smaller than the arithmetic average particle size of the particles contained in the aforementioned particle layer. A method for manufacturing a photosensitive transfer material, comprising the following steps: A step of providing a photosensitive layer-forming composition on a cover film to form a photosensitive layer; A step of providing an intermediate layer-forming composition on the photosensitive layer to form an intermediate layer; A step of providing a particle layer-forming composition on the intermediate layer to form a particle layer; and A step of attaching a pseudo-support to the particle layer in contact with the particle layer. A method for manufacturing a resin pattern comprises the following steps in order: A step of peeling off the aforementioned covering film in the photosensitive transfer material described in claim 1 or claim 2; A step of bringing the outermost layer on the photosensitive layer side of the aforementioned photosensitive transfer material from which the aforementioned covering film has been peeled into contact with a support having a conductive layer and laminating them; A step of peeling off the aforementioned pseudo support from the aforementioned particle layer; A step of bringing an exposure mask into contact with the aforementioned particle layer and exposing the aforementioned photosensitive layer to a pattern through the aforementioned exposure mask; and A step of developing the aforementioned photosensitive layer to form a resin pattern. A method for manufacturing circuit wiring, which comprises the following steps in sequence: A step of peeling off the aforementioned covering film in the photosensitive transfer material described in claim 1 or claim 2; A step of bringing the outermost layer on the photosensitive layer side of the aforementioned photosensitive transfer material from which the aforementioned covering film has been peeled into contact with a support having a conductive layer and bonding them; A step of peeling off the aforementioned pseudo-support from the aforementioned particle layer; A step of bringing an exposure mask into contact with the aforementioned particle layer and exposing the aforementioned photosensitive layer in a pattern through the aforementioned exposure mask; A step of developing the aforementioned photosensitive layer to form a resin pattern; and The step of using the aforementioned resin pattern as a mask to perform etching on the aforementioned conductive layer. A method for manufacturing circuit wiring, which comprises the following steps in sequence: A step of peeling off the aforementioned covering film in the photosensitive transfer material described in claim 1 or claim 2; A step of bringing the outermost layer on the photosensitive layer side of the aforementioned photosensitive transfer material from which the aforementioned covering film has been peeled into contact with a support having a conductive layer and bonding them; A step of peeling off the aforementioned pseudo support from the aforementioned particle layer; A step of bringing an exposure mask into contact with the aforementioned particle layer and exposing the aforementioned photosensitive layer in a pattern through the aforementioned exposure mask; A step of developing the aforementioned photosensitive layer to form a resin pattern; A step of electroplating the conductive layer using the previously formed resin pattern as a mask; A step of stripping the previously formed resin pattern; and A step of etching the conductive layer.