JP2022184719A - Transfer film, laminate, patterning method, and method for producing circuit wiring - Google Patents

Abstract

To provide a transfer film applied to both sides of a transparent conductive layer-bearing substrate, which comprises a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate, wherein, when a laminate comprising the transfer film disposed on both sides of the transparent conductive layer-bearing substrate is exposed to light from its both sides, exposure fogging is suppressed, and a resin pattern formed therefrom has excellent resolution; and also provide a laminate, a patterning method, and a method for producing circuit wiring.SOLUTION: A transfer film is applied to a transparent conductive layer-bearing substrate, which comprises a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate. The transfer film comprises a temporary support, and a composition layer at least comprising a photosensitive layer. The composition layer comprises a dye having a maximum absorption wavelength at a different wavelength from a maximum sensitivity wavelength of the photosensitive layer. The difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40 nm or more.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a transfer film, a laminate, a pattern forming method, and a circuit wiring manufacturing method.

Since the number of steps for obtaining a predetermined pattern is small, a method of disposing a photosensitive layer on an arbitrary substrate using a transfer film, exposing the photosensitive layer through a mask, and then developing it is preferred. It is widely used (see Patent Document 1).

Japanese Patent Application Laid-Open No. 2020-086238

Recently, the present inventors have studied a method of forming patterned conductive layers on both sides of a transparent substrate by a double-sided lithography process using a transfer film. When double-sided exposure is performed on a laminate having a conductive layer and a photosensitive layer in order from the transparent substrate side on the surface, the other photosensitive layer is also exposed by the exposure light when one photosensitive layer is exposed. It has been clarified that a phenomenon of exposure (hereinafter also referred to as "exposure fogging") may occur. When exposure fogging occurs, there is a possibility that the photosensitive layer cannot be formed into a desired shape.
In addition, the present inventors have further studied a method for forming patterned conductive layers on both sides of a transparent substrate by a double-sided lithography process, and found that a patterned conductive layer is formed from each photosensitive layer by exposure and development processing. It has also been found that the resolution of the resin pattern may be inferior.

Accordingly, the present invention provides a transfer film to be applied to both sides of a substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate, the transfer film being applied to both sides of the substrate with the transparent conductive layer. To provide a transfer film which suppresses exposure fogging and has excellent resolution of a formed resin pattern when a laminate formed by arranging transfer films on both sides of a layer is exposed from both sides (double-sided exposure). The challenge is to
Another object of the present invention is to provide a laminate, a pattern forming method, and a circuit wiring manufacturing method.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that the above problems can be solved by the following configuration.

[1] A transfer film applied to a substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate,
Having a temporary support and a composition layer containing at least a photosensitive layer,
The composition layer contains a dye having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer,
The transfer film, wherein the difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40 nm or more.
[2] The transfer film according to [1], wherein the transparent conductive layer contains at least one selected from the group consisting of metal nanowires and metal nanoparticles.
[3] The transfer film of [1] or [2], wherein the photosensitive layer has a maximum sensitivity wavelength of 300 to 395 nm, and the dye has a maximum absorption wavelength of more than 395 nm and 500 nm or less.
[4] The transfer film of [1] or [2], wherein the photosensitive layer has a maximum sensitivity wavelength of more than 395 nm and 500 nm or less, and the dye has a maximum absorption wavelength of 300 to 395 nm.
[5] The transfer film according to any one of [1] to [4], wherein the dye is not sensitized.
[6] The transfer film according to any one of [1] to [5], wherein the dye has an absorbance of 1 or less at the maximum sensitivity wavelength of the photosensitive layer.
[7] The composition layer contains a sensitizer,
Any one of [1] to [6], wherein the sensitizer is at least one selected from the group consisting of benzophenone-based compounds, thioxanthone-based compounds, cyanine-based compounds, coumarin-based compounds, and merocyanine-based compounds. Transfer film as described.
[8] The transfer film according to any one of [1] to [7], wherein the photosensitive layer contains the dye.
[9] The transfer film according to any one of [1] to [8], wherein the composition layer further has a thermoplastic resin layer closer to the temporary support than the photosensitive layer.
[10] The transfer film according to [9], wherein the thermoplastic resin layer contains the dye [11] The photosensitive layer further contains a polymerization inhibitor,
The transfer film according to any one of [1] to [10], wherein the polymerization inhibitor is at least one selected from the group consisting of phenothiazine compounds, hindered phenol compounds, and phenoxazine compounds.
[12] A substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate, and [1] to [1] to [ 11], and the transfer film according to any one of the above.
[13] In one of the transfer films in the laminate, the photosensitive layer has a maximum sensitivity wavelength of 300 to 395 nm, and the dye has a maximum absorption wavelength of more than 395 nm and 500 nm or less,
The laminate according to [12], wherein in the other transfer film, the photosensitive layer has a maximum sensitivity wavelength of more than 395 nm and 500 nm or less, and the dye has a maximum absorption wavelength of 300 to 395 nm.
[14] A method of forming a pattern by exposing and developing the transfer film in the laminate of [12] or [13], comprising:
A first exposure step of exposing the photosensitive layer in one transfer film in the laminate;
a second exposure step of exposing the photosensitive layer in the other transfer film in the laminate;
a first development step of developing the photosensitive layer exposed through the first exposure step to form a resin pattern;
A pattern forming method, comprising: a second developing step of developing the photosensitive layer exposed through the second exposing step to form a resin pattern.
[15] The pattern forming method of [14], wherein the first exposure step and the second exposure step are performed simultaneously or sequentially.
[16] The pattern forming method of [14] or [15], wherein the first developing step and the second developing step are performed simultaneously or sequentially.
[17] Using the resin pattern formed through the first developing step as a mask, etching the transparent conductive layer disposed between the transparent substrate and the resin pattern formed through the first developing step. a first etching step;
using the resin pattern formed through the second developing step as a mask to etch the transparent conductive layer disposed between the transparent substrate and the resin pattern formed through the second developing step; 1 etching step, and the pattern forming method according to any one of [14] to [16].
[18] A method for manufacturing a circuit board, comprising the pattern forming method according to any one of [14] to [17].

According to the present invention, there is provided a transfer film applied to both sides of a transparent conductive layer-attached substrate having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate, the substrate having the transparent conductive layer. It is possible to provide a transfer film that suppresses exposure fogging and has excellent resolution of the resin pattern formed when a laminate formed by arranging transfer films on both sides of is exposed from both sides (double-sided exposure). .
Further, according to the present invention, it is possible to provide a laminate, a pattern forming method, and a circuit wiring manufacturing method.

FIG. 4 is a schematic diagram for explaining the mechanism of action of the transfer film of the present invention when a laminate obtained by arranging the transfer film of the present invention on both sides of a substrate with a transparent conductive layer is subjected to double-sided exposure. . FIG. 4 is a schematic diagram for explaining the mechanism of action of the transfer film of the present invention when a laminate obtained by arranging the transfer film of the present invention on both sides of a substrate with a transparent conductive layer is subjected to double-sided exposure. . It is a mimetic diagram for explaining a 1st embodiment of a transfer film. It is a schematic diagram for describing 2nd Embodiment of a transfer film.

The present invention will be described in detail below.
In this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
In the present specification, in the numerical ranges described stepwise, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. . Moreover, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.

In this specification, the term "process" is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term as long as the intended purpose of the process is achieved. .

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). ), using THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, it is a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer. .
In this specification, unless otherwise specified, the molecular weight of compounds having a molecular weight distribution is the weight average molecular weight (Mw).
In this specification, unless otherwise specified, the ratio of polymer constitutional units is the mass ratio.
In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer.
In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

As used herein, "(meth)acryl" is a concept that includes both acryl and methacryl, and "(meth)acryloxy group" is a concept that includes both acryloxy and methacryloxy groups, and "( "Meth)acrylate" is a concept that includes both acrylate and methacrylate.

In this specification, the term “alkali-soluble” means that the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at 22° C. is 0.1 g or more.

As used herein, the term “water-soluble” means that the solubility in 100 g of water having a liquid temperature of 22° C. and a pH of 7.0 is 0.1 g or more. Thus, for example, by water-soluble resin is intended a resin that satisfies the solubility conditions set forth above.

As used herein, the “solid content” of the composition means a component that forms a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent means all ingredients except In addition, as long as it is a component that forms a composition layer, a liquid component is also regarded as a solid content.

In this specification, when the photosensitive layer is referred to as "maximum sensitivity wavelength", the "maximum sensitivity wavelength" is the minimum exposure amount at which the photosensitive layer reacts for each wavelength of light. It refers to the wavelength that becomes smaller.
The "maximum sensitivity wavelength" can be determined, for example, by the following method. When the photosensitive layer is irradiated with light of a specific wavelength in the range of 250 to 500 nm through a Stouffer 4105 step wedge tablet, Emin is the minimum exposure amount at which the photosensitive material in the photosensitive layer reacts. By changing the irradiation wavelength, a spectral sensitivity curve can be obtained. Since Emin is different for each wavelength, the wavelength with the minimum value is the "maximum sensitivity wavelength".
In the negative photosensitive layer, Emin can be the minimum exposure amount at which the exposed portion remains. On the other hand, in the positive photosensitive layer, the minimum exposure amount at which the exposed portion is removed can be Emin.

As used herein, the term “exposure wavelength” refers to the wavelength of light with which the photosensitive layer is exposed to light, and the wavelength of light that reaches the photosensitive layer. For example, when the photosensitive layer is exposed through a filter having wavelength selectivity, the wavelength of light before passing through the filter does not correspond to the exposure wavelength. Here, "wavelength selectivity" means the property of transmitting light in a specific wavelength range. As used herein, the wavelength and intensity of light are measured using a known spectroscope (eg, RPS900-R, manufactured by International Light Technologies).

As used herein, the term "dominant wavelength" refers to the wavelength of light with the highest intensity among the wavelengths of light reaching the photosensitive layer (that is, the exposure wavelength). For example, when the light reaching the photosensitive layer is exposure light having a wavelength of 365 nm and a wavelength of 436 nm, and the intensity of the wavelength of 365 nm is greater than that of the wavelength of 436 nm, the dominant wavelength of the exposure light is 365 nm. As used herein, "exposure light" means light used to expose the photosensitive layer.

In the present invention, the term "transparent" means that the transmittance at the dominant wavelength of exposure wavelengths is 30% or more. The transmittance is preferably 50% or more, more preferably 60% or more, still more preferably 80% or more, and particularly preferably 90% or more. The upper limit of the transmittance is not particularly limited, and is, for example, 100% or less.
The transmittance is measured using a known transmittance measuring instrument (eg V-700 series manufactured by JASCO Corporation).

[Transfer film]
The transfer film of the present invention is
A transfer film applied to a substrate with a transparent conductive layer (hereinafter also simply referred to as "substrate with a transparent conductive layer") having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate. There is
Having a temporary support and a composition layer containing at least a photosensitive layer,
The composition layer contains a dye having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer,
The difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40 nm or more.
In the following, the dye has a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer, and the difference between the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer is 40 nm or more. A dye is also called a “specific dye”.
Further, the specific dye preferably has a maximum absorption wavelength in any wavelength band from the ultraviolet to the visible region, more preferably has a maximum absorption wavelength in the wavelength band of 300 to 780 nm. More preferably, it has a maximum absorption wavelength in the wavelength band of ~500 nm.

According to the transfer film of the present invention having the above-described structure, fogging due to exposure is suppressed when the laminate obtained by arranging the transfer film of the present invention on both sides of the base material with the transparent conductive layer is exposed from both sides (double-sided exposure). obtain. In other words, when the photosensitive layer in one transfer film is exposed, the phenomenon in which the photosensitive layer in the other transfer film is also exposed by the exposure light is less likely to occur.
Furthermore, the resin pattern formed from the transfer film of the present invention also has excellent resolution.

Although this is not clear in detail, the present inventor presumes as follows. Hereinafter, the configuration and mechanism of action of the transfer film of the present invention will be described more specifically with reference to the drawings.
Here, as an example of the transfer film of the present invention, a transfer film in which the composition layer is composed of a photosensitive layer and the photosensitive layer contains a specific dye will be described.
FIG. 1 is a diagram showing an embodiment of a laminate in which the transfer film of the present invention is arranged on both sides of a substrate with a transparent conductive layer.
A laminate 20 shown in FIGS. 1 and 2 has a first transfer film 5A, a base material 11 with a transparent conductive layer, and a second transfer film 5B in this order. 5 A of 1st transfer films have 3 A of 1st photosensitive layers and 1 A of 1st temporary support bodies in order from the base material 11 side with a transparent conductive layer. The second transfer film 5B has a second photosensitive layer 3B and a second temporary support 1B in order from the substrate 11 side with the transparent conductive layer. The base material 11 with the transparent conductive layer is in contact with the transparent base material 9, the transparent conductive layer 7A arranged on the side of the transparent base material 9 in contact with the first transfer film, and the second transfer film of the transparent base material 9. and a transparent conductive layer 7B disposed on the side surface.
Here, the maximum sensitivity wavelength of the first photosensitive layer 3A is in the range of 300-395 nm. In addition, the first photosensitive layer 3A contains a dye, the maximum absorption wavelength of the dye is in the range of more than 395 nm and 500 nm or less, and the maximum sensitivity wavelength of the first photosensitive layer 3A and the maximum absorption wavelength of the dye is 40 nm or more. Moreover, the maximum sensitivity wavelength of the second photosensitive layer 3B is in the range of more than 395 nm and 500 nm or less. Furthermore, the second photosensitive layer 3B contains a dye, the maximum absorption wavelength of the dye is in the range of 300 to 395 nm, and the difference between the maximum sensitivity wavelength of the second photosensitive layer 3B and the maximum absorption wavelength of the dye is greater than or equal to 40 nm.

(Mechanism of Action for Suppressing Exposure Fogging and Exhibiting Excellent Resolution)
A first action mechanism for suppressing exposure fogging and exhibiting excellent resolution will be described below with reference to FIG.
For example, when exposing the first photosensitive layer 3A of the laminate 20 using a light source light having a discrete light amount distribution (like g-line, h-line, and i-line) like a high-pressure mercury lamp, 1 is absorbed by the dye in the first photosensitive layer 3A and is suppressed from entering the second photosensitive layer 3B ( L12 in the figure). The maximum absorption wavelength of this dye is the same as or close to the maximum sensitivity wavelength of the second photosensitive layer 3B. That is, due to the presence of the dye in the first photosensitive layer 3A, in the exposure light reaching the second photosensitive layer 3B, the unit area of light with a wavelength that is the same as or similar to the maximum sensitivity wavelength of the second photosensitive layer 3B Hit strength is reduced. As a result, various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) due to exposure of the second photosensitive layer 3B are suppressed, so that exposure fogging is suppressed. On the other hand, even if the light (L21 in FIG. 1) having a wavelength that is the same as or similar to the maximum sensitivity wavelength of the first photosensitive layer 3A enters the second photosensitive layer 3B, the second photosensitive layer usually It does not contribute to various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) upon exposure of the layer 3B.
Further, for example, when exposing the second photosensitive layer 3B of the laminate 20 using light source light having a discrete light amount distribution (like g-line, h-line, i-line) such as a high-pressure mercury lamp , part of the exposure light incident on the mask opening from the direction of the black arrow in FIG. L22 in the figure). The maximum absorption wavelength of this dye is the same as or close to the maximum sensitivity wavelength of the first photosensitive layer 3A. That is, due to the presence of the dye in the second photosensitive layer 3B, in the exposure light reaching the first photosensitive layer 3A, the unit area of light with a wavelength that is the same as or similar to the maximum sensitivity wavelength of the first photosensitive layer 3A Hit strength is reduced. As a result, various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) due to exposure of the first photosensitive layer 3A are suppressed, so that exposure fogging is suppressed. On the other hand, light having a wavelength (L22 in FIG. 1) that is the same as or similar to the maximum sensitivity wavelength of the second photosensitive layer 3B, even if it enters the first photosensitive layer 3A, usually the first photosensitive layer It does not contribute to various reactions caused by exposure of the layer 3A (for example, polymerization reaction in the case of a negative photosensitive layer).

In addition, since the difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40 nm or more, various reactions caused by exposure of the photosensitive layer (for example, polymerization reaction in the case of a negative photosensitive layer). Reduction of the necessary exposure dose due to absorption by the dye is suppressed. In other words, the dye suppresses the decrease in sensitivity of the photosensitive layer. As a result, the resin pattern formed from the transfer film of the present invention has excellent resolution.

Next, the second action mechanism for suppressing exposure fogging and exhibiting excellent resolution will be described with reference to FIG.
For example, using a light source light having a discrete light amount distribution (like g-line, h-line, and i-line) such as a high-pressure mercury lamp, wavelength control is performed by a filter or the like, and the first photosensitive layer 3A is formed. When exposing the first photosensitive layer 3A of the laminate 20 using only a wavelength that is the same as or similar to the maximum sensitivity wavelength as exposure light, the exposure light that enters the mask opening from the white arrow direction in FIG. may enter the second photosensitive layer 3B and be reflected by the filter 15 or the like having wavelength selectivity. Since this reflected light is the same as or close to the maximum absorption wavelength of the dye in the second photosensitive layer 3B, it is absorbed by the dye in the second photosensitive layer 3B and re-directed to the first photosensitive layer 3A. Entry is suppressed (L21 in FIG. 2). As a result, deterioration in the resolution of the resin pattern due to reflected light can be suppressed. In addition, even if light (L21 in FIG. 2) having a wavelength that is the same as or similar to the maximum sensitivity wavelength of the first photosensitive layer 3A enters the second photosensitive layer 3B, the second photosensitive layer usually It does not contribute to various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) due to exposure of 3B. Therefore, exposure fogging can also be suppressed.
Further, for example, using a light source light having a discrete light amount distribution (like g-line, h-line, i-line) such as a high-pressure mercury lamp, wavelength control is performed by a filter or the like, and the second photosensitive layer When exposing the second photosensitive layer 3B of the laminate 20 using only a wavelength that is the same as or similar to the maximum sensitivity wavelength of 3B, the exposure light that enters the mask opening from the direction of the black arrow in FIG. may enter the first photosensitive layer 3A and be reflected by the filter 13 or the like having wavelength selectivity. Since this reflected light is the same as or close to the maximum absorption wavelength of the dye in the first photosensitive layer 3A, it is absorbed by the dye in the first photosensitive layer 3A and re-directed to the second photosensitive layer 3B. Entry is suppressed (L11 in FIG. 2). As a result, deterioration in the resolution of the resin pattern due to reflected light can be suppressed. In addition, even if light of a wavelength (L11 in FIG. 2) that is the same as or similar to the maximum sensitivity wavelength of the second photosensitive layer 3B enters the first photosensitive layer 3A, the first photosensitive layer usually It does not contribute to various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) due to 3A exposure. Therefore, exposure fogging can also be suppressed.
Furthermore, since the difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40 nm or more, various reactions caused by exposure of the photosensitive layer (for example, polymerization reaction in the case of a negative photosensitive layer). Reduction of the necessary exposure dose due to absorption by the dye is suppressed. In other words, the dye suppresses the decrease in sensitivity of the photosensitive layer. From this point as well, it is presumed that the resin pattern formed from the transfer film of the present invention also contributes to the development of excellent resolution.

In the following, better exposure fogging of the transfer film and/or better resolution of the resin pattern formed from the transfer film may be referred to as "more excellent effect of the present invention".

The transfer film of the present invention is described below.
The transfer film of the present invention includes a temporary support and a composition layer including at least a photosensitive layer.
Further, the composition layer may have a single layer structure, or may have a structure of two or more layers. When the composition layer includes a composition layer other than the photosensitive layer, examples of the composition layer include a thermoplastic resin layer and an intermediate layer.
Further, the composition layer is a dye having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer, and the difference between the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer is 40 nm. The above dyes (specific dyes) are included. The layer containing the specific dye is not limited and includes, for example, a photosensitive layer and a thermoplastic resin layer.
Furthermore, the specific dye may be contained in one or more layers in the composition layer, and may be contained in two or more layers.

The composition layer may contain only the photosensitive layer, or may contain the photosensitive layer and other layers. However, when the composition layer consists of only a photosensitive layer, the photosensitive layer contains a specific dye.
Also, the transfer film may have a configuration in which a protective film (hereinafter sometimes referred to as “cover film”) is provided on the composition layer.

Examples of embodiments of the transfer film of the present invention are shown below, but are not limited thereto.
(1) "Temporary support/intermediate layer (intermediate layer A)/photosensitive layer/protective film"
(2) "Temporary support/thermoplastic resin layer/intermediate layer/photosensitive layer/protective film"
(3) "Temporary support/photosensitive layer/protective film"
In addition, in each of the above structures, the photosensitive layer is preferably a negative photosensitive layer. It is also preferred that the photosensitive layer is a colored resin layer.
The transfer film of the present invention will be described below by giving an example of a specific embodiment.

[Transfer film of the first embodiment]
An example of an embodiment of the transfer film of the first embodiment will be described below.
The transfer film 30 shown in FIG. , in that order. The photosensitive layer 37 contains a specific dye.
Although the transfer film 30 shown in FIG. 3 has the protective film 41 disposed thereon, the protective film 41 may not be disposed. Further, the transfer film 30 shown in FIG. 3 has a form in which the thermoplastic resin layer 33 and the intermediate layer 35 are arranged, but the thermoplastic resin layer 33 and the intermediate layer 35 may not be arranged. In other words, the composition layer 39 may consist of the photosensitive layer 37 only.
Each element constituting the transfer film will be described below.

<Temporary support>
The transfer film has a temporary support.
Temporary supports include, for example, glass substrates, resin films, and paper. The temporary support is preferably a resin film from the viewpoint of strength and flexibility. Examples of resin films include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. The temporary support is preferably a polyethylene terephthalate film, more preferably a biaxially oriented polyethylene terephthalate film.

As the temporary support, a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat can be used. Such films include, for example, polyethylene terephthalate films (eg, biaxially oriented polyethylene terephthalate films), cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable as the temporary support. In addition, it is preferable that the film used as the temporary support is free from deformation such as wrinkles and scratches.

The temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support. The temporary support preferably has a transmittance of 60% or more, more preferably 70% or more, at the dominant wavelength of the exposure wavelengths.

From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the haze of the temporary support is preferably as small as possible. Specifically, the haze defined by JIS-K-7136 of the temporary support is preferably 2% or less, more preferably 0.5% or less, and 0.3% or less. is more preferred.

From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably as small as possible. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, and further preferably 3/10 mm ² or less. 0 pieces/10 mm ² is particularly preferred.

Although the thickness of the temporary support is not particularly limited, it is preferably 5 to 200 μm, more preferably 10 to 150 μm, more preferably 10 to 50 μm from the viewpoint of ease of handling and versatility. preferable.

Preferred embodiments of the temporary support include, for example, paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to WO 2012/081680 paragraph 0057, and paragraphs 0029-0040 of WO 2018/179370, the contents of which are incorporated herein.

<Protective film>
The transfer film may have a protective film.
As the protective film, a resin film having heat resistance and solvent resistance can be used. Examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. be done.
Also, as the protective film, a resin film made of the same material as the temporary support may be used.
Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and still more preferably a polyethylene film.

The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 40 μm, particularly preferably 15 to 30 μm.
The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of being relatively inexpensive.

In the protective film, the number of fisheyes having a diameter of 80 μm or more contained in the protective film is preferably 5/m ² or less.
In addition, "fish eye" refers to foreign matter, undissolved matter, and oxidative degradation products of the material when producing a film by methods such as heat melting, kneading, extrusion, biaxial stretching and casting. is captured in the film.

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, and even more preferably 5 particles/mm ² or less.
This makes it possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the photosensitive layer or the conductive layer.

From the viewpoint of imparting windability, the surface of the protective film opposite to the surface in contact with the composition layer preferably has an arithmetic mean roughness Ra of 0.01 μm or more, more preferably 0.02 μm or more, and 0.03 μm. The above is more preferable. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.
From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface in contact with the composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

<Composition layer>
A transfer film comprises a composition layer on a temporary support. The composition layer includes at least a photosensitive layer. The transfer film of the first embodiment has a single photosensitive layer as a composition layer. First, the photosensitive layer will be described below.
As the photosensitive layer, when the transfer film is used as an etching resist, it is preferable to use the photosensitive layer (photosensitive layer A) of the following first embodiment, and when the transfer film is used as a wiring protective film, the following is preferable. It is preferable to use the photosensitive layer (photosensitive layer B) of the second embodiment.
Among them, the photosensitive layer A is preferable as the photosensitive layer of the transfer film of the first embodiment.

(Photosensitive layer of the first embodiment (photosensitive layer A))
The photosensitive layer A will be described below.
The photosensitive layer preferably contains a resin, a polymerizable compound, a polymerization initiator, and a specific dye, and more preferably contains a resin, a polymerizable compound, a polymerization initiator, a sensitizer, and a specific dye. More preferably, it contains a polymerizable compound, a polymerization initiator, a sensitizer, a polymerization inhibitor, and a specific dye.
Further, the resin preferably contains an alkali-soluble resin.
A suitable example of the content of each of the above components in the photosensitive layer is, for example, 10.0 to 90.0% by weight of the resin and 5.0 to 5.0% of the polymerizable compound with respect to the total weight of the photosensitive layer. 70.0% by mass, 0.01 to 15.0% by mass of a polymerization initiator, and 0.01 to 15.0% by mass of a specific dye.
Further, another preferred example of the content of each of the components in the photosensitive layer is, for example, 10.0 to 90.0% by weight of the resin and the polymerizable compound with respect to the total weight of the photosensitive layer. 5.0 to 70.0% by mass, 0.01 to 10.0% by mass of a polymerization initiator, 0.01 to 5.0% by mass of a sensitizer, and 0.01 to 15.0% by mass of a specific dye The aspect containing mass % is mentioned.
Further, another preferred example of the content of each of the components in the photosensitive layer is, for example, 10.0 to 90.0% by weight of the resin and the polymerizable compound with respect to the total weight of the photosensitive layer. 5.0 to 70.0% by mass, 0.01 to 10.0% by mass of polymerization initiator, 0.01 to 5.0% by mass of sensitizer, 0.001 to 0.5% by mass of polymerization inhibitor %, and an embodiment containing 0.01 to 15.0% by mass of the specific dye.
Each component that the photosensitive layer may contain will be described below.

-resin-
The photosensitive layer may contain a resin.
As the resin, an alkali-soluble resin is preferable.
As the resin, an alkali-soluble resin contained in the thermoplastic resin layer, which will be described later, may be used.

The resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focus position shifts during exposure.
Examples of the aromatic hydrocarbon group include an optionally substituted phenyl group and an optionally substituted aralkyl group.
The content of structural units derived from a monomer having an aromatic hydrocarbon group is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, more preferably 30.0% by mass, based on the total mass of the resin. % or more by mass is more preferable. The upper limit is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and even more preferably 55.0% by mass or less, relative to the total mass of the resin. When the photosensitive layer contains a plurality of resins, the weight average content of structural units derived from monomers having aromatic hydrocarbon groups is preferably within the above range.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.), preferably an aralkyl group-containing monomer or styrene, more preferably styrene.
When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units derived from styrene is preferably 10.0 to 80.0% by mass, preferably 20.0%, based on the total mass of the resin. ~60.0% by mass is more preferable, and 30.0 to 55.0% by mass is even more preferable. When the photosensitive layer contains a plurality of resins, it is preferable that the mass-average content of structural units having an aromatic hydrocarbon group is within the above range.

Examples of the aralkyl group include a phenylalkyl group optionally having a substituent (excluding a benzyl group) and a benzyl group optionally having a substituent. A benzyl group with a higher molecular weight is preferred.

Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol. and preferably a (meth)acrylate having a benzyl group, more preferably a benzyl (meth)acrylate.
When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of structural units derived from benzyl (meth)acrylate is 10.0 to 90.0 with respect to the total mass of the resin. % by mass is preferable, 20.0 to 85.0% by mass is more preferable, and 30.0 to 85.0% by mass is even more preferable.

The resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one first monomer described later and/or a second monomer described later. It is preferably obtained by polymerizing at least one monomer.

The resin that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and at least More preferably, it is obtained by polymerizing one of the monomers and at least one of the second monomers described below.

A 1st monomer is a monomer which has a carboxy group in a molecule|numerator.
Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride and maleic acid half ester. ) acrylic acid is preferred.
The content of structural units derived from the first monomer is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, based on the total mass of the resin. 0 to 30.0% by mass is more preferable.
When the content is 5.0% by mass or more, excellent developability and control of edge fuse properties can be achieved. When the content is 50.0% by mass or less, high resolution of the resist pattern, control of the groove shape, and high chemical resistance of the resist pattern can be realized.

The second monomer is a monomer that is non-acidic (has no acidic group) and has a polymerizable group in its molecule.
The polymerizable group has the same meaning as the polymerizable group possessed by the polymerizable compound described below, and the preferred embodiments are also the same.
Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth)acrylates such as tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; vinyl acetate, etc. vinyl alcohol esters; (meth)acrylonitrile.
Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate and ethyl (meth)acrylate are more preferred.
10. The content of structural units derived from the second monomer is preferably 1.0 to 80.0% by mass, more preferably 1.0 to 60.0% by mass, relative to the total mass of the resin. 0 to 50.0% by mass is more preferable.

The resin may have any one of a linear structure, a branched structure and an alicyclic structure in the side chain.
By using a monomer containing a group having a branched structure in its side chain or a monomer containing a group having an alicyclic structure in its side chain, a branched structure or alicyclic structure can be introduced into the side chain of the resin. can. A group having an alicyclic structure may be either monocyclic or polycyclic.
"Side chain" means an atomic group branched off from the main chain. The “main chain” means the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin.
Examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, Isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert- (meth)acrylate octyl. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl methacrylate are preferred, and isopropyl methacrylate and tert-butyl methacrylate are more preferred.
The monomer containing a group having an alicyclic structure in its side chain includes, for example, a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also included.
Specifically, (meth) acrylic acid (bicyclo[2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic acid- 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, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-menthanoinden-5-yl (meth) acrylate, ( Octahydro-4,7-menthanoinden-1-ylmethyl meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6 (meth)acrylate ,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acrylic acid (nor ) bornyl, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate. Among them, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (meth)acrylate Fentyl acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate is preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth) ) 2-adamantyl acrylate or tricyclodecane (meth)acrylate is more preferred.

The resin preferably has a polymerizable group, more preferably contains a structural unit having a polymerizable group, and contains a structural unit having an ethylenically unsaturated group in the side chain, from the viewpoint that the effects of the present invention are more excellent. is more preferred.
Examples of the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later, preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
Further, the polymerizable group is preferably a polymerizable group capable of undergoing a polymerization reaction with the polymerizable group of the polymerizable compound.

The resin containing a structural unit having a polymerizable group is preferably obtained by reacting a resin containing a structural unit derived from the first monomer with the third monomer.

The third monomer is a monomer having two or more polymerizable groups in its molecule, preferably a monomer having two polymerizable groups in its molecule.
Examples of the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later. Among them, the third monomer preferably has two types of polymerizable groups, more preferably has an ethylenically unsaturated group and a cationic polymerizable group, an acryloyl group or a methacryloyl group and an epoxy It is more preferred to have a group.
Examples of the third monomer include glycidyl (meth)acrylate.

When the resin contains a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5.0 to 70.0% by mass, preferably 10.0 to 50%, based on the total mass of the resin. 0% by mass is more preferable, 15.0 to 40.0% by mass is even more preferable, and 20.0 to 40.0% by mass is particularly preferable.

As a method for introducing a polymerizable group into a resin, for example, epoxy compounds, epoxy compounds, A method of reacting a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound and a carboxylic acid anhydride can be mentioned.
As a preferred embodiment of the method of introducing a polymerizable group into a resin, for example, after synthesizing a first monomer by a polymerization reaction, A method of introducing a polymerizable group (preferably (meth)acryloxy group) into the resin by causing a polymer reaction with a third monomer (preferably glycidyl (meth)acrylate) in the part. The reaction temperature for the polymer reaction is preferably 80 to 110.degree. The polymer reaction preferably uses a catalyst, more preferably an ammonium salt (tetraethylammonium bromide).
The reaction temperature of the polymerization reaction is preferably 70 to 100°C, more preferably 80 to 90°C. The polymerization reaction preferably uses a polymerization initiator, more preferably an azo initiator as the polymerization initiator, V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) or V-65 ( Fuji Film Wako Pure Chemical Industries, Ltd.) is more preferable.

As the resin, a resin containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from styrene or a structural unit derived from benzyl methacrylate, and a structural unit derived from methacrylic acid and a structural unit derived from styrene A resin containing a structural unit having a polymerizable group is preferable, and a resin containing a structural unit having a polymerizable group is more preferable.
In the above, it is also preferable to set the content of each structural unit to the above-mentioned suitable aspect.

The Tg of the resin is preferably 60 to 135°C, more preferably 70 to 115°C, still more preferably 75 to 105°C, and particularly preferably 80 to 100°C.

The acid value of the resin is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, even more preferably less than 170 mgKOH/g. The lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
"Acid number (mg KOH/g)" means the mass (mg) of potassium hydroxide required to neutralize 1 g of sample. The acid value can be determined according to JIS K0070:1992, for example.
The acid value of the resin can be adjusted by the type of structural unit contained in the resin and/or the content of the structural unit containing an acid group.

The weight average molecular weight of the resin is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 60,000.
When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. Also. When the weight-average molecular weight is 5,000 or more, properties of development aggregates and properties of unexposed films such as edge-fuse properties and cut-chip properties of transfer films can be controlled. The “edge fuse property” means the degree of easiness of protrusion of the photosensitive layer from the end face of the roll when the transfer film is wound into a roll. “Cut chip resistance” means the degree of easiness of chip flying when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the transfer film or the like, it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products.
The dispersity (Mw/Mn) of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, even more preferably 1.0 to 3.0.

The photosensitive layer may contain other resins in addition to the above resins.
Other resins include, for example, acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, Polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols are included.

You may use resin individually by 1 type or in 2 or more types.

The resin content is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, and 30.0 to 70.0% by mass with respect to the total mass of the photosensitive layer. is more preferred. When the resin content is 90.0% by mass or less with respect to the total mass of the photosensitive layer, the development time can be controlled. Moreover, when the content of the resin is 10.0% by mass or more with respect to the total mass of the photosensitive layer, the edge fuse resistance can be improved.

As a method for synthesizing the resin, for example, a suitable amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the above-mentioned monomer with a solvent such as acetone, methyl ethyl ketone and isopropanol, A method of heating and stirring can be used. You may synthesize|combine, dripping a part of mixture to a reaction liquid. Further, after the completion of the reaction, a solvent may be further added to adjust the desired concentration.
In addition to the methods described above, examples of resin synthesizing methods include bulk polymerization, suspension polymerization, and emulsion polymerization.

-Polymerizable compound-
The photosensitive layer preferably contains a polymerizable compound.
The polymerizable compound is intended to be a compound that has one or more polymerizable groups and is polymerized by the action of a polymerization initiator, which will be described later. Moreover, the polymerizable compound is a compound different from the above resin.

The polymerizable group possessed by the polymerizable compound may be any group that participates in the polymerization reaction. and groups having cationic polymerizable groups such as oxetane groups.
As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (hereinafter, also referred to as "ethylenically unsaturated compound") is preferable, since the photosensitivity of the photosensitive layer is more excellent. Compounds having two or more ethylenically unsaturated groups (hereinafter also referred to as "polyfunctional ethylenically unsaturated compounds") are more preferred.
Further, from the viewpoint of better resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in the molecule is preferably 1 to 6, more preferably 1 to 3, and 2 to 3. More preferred.

The polymerizable compound may have an alkyleneoxy group.
As the alkylene group, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable from the viewpoint that the effects of the present invention are more excellent. The number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 30, more preferably 2 to 20 per molecule.

The polymerizable compound is a bifunctional or trifunctional ethylenically unsaturated group having 2 or 3 ethylenically unsaturated groups in the molecule from the viewpoint of better balance between photosensitivity, resolution, and releasability of the photosensitive layer. It preferably contains a compound.

The content of the bifunctional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably more than 40.0% by mass, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. 0% by mass or more is more preferable. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive layer may be bifunctional ethylenically unsaturated compounds.
The content of the trifunctional ethylenically unsaturated compound is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, relative to the total mass of the polymerizable compound. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 50.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive layer may be trifunctional ethylenically unsaturated compounds.
Moreover, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.

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

Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring Heterocycle; condensed rings thereof are mentioned, preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.
Polymerizable compound B1 may have one or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive layer due to the developer.
The bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). Bisphenol B structures derived from F structures and bisphenol B (2,2-bis(4-hydroxyphenyl)butane) are included, with bisphenol A structures being preferred.

Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.
Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or bonded via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups (preferably ethyleneoxy groups) added to the bisphenol structure is preferably 2 to 30, more preferably 2 to 20 per molecule.
Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs [0072] to [0080] of JP-A-2016-224162, the contents of which are incorporated herein.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.
2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane includes, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.) ), ethoxylated bisphenol A dimethacrylates (BPE series, Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-(methacryloxide decaethoxytetrapropoxy) phenyl) propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate ( NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

A compound represented by formula (B1) is also preferable as the polymerizable compound B1.

In formula (B1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents an ethylene group. B represents a propylene group. n1 and n3 each independently represent an integer of 1 to 39; n1+n3 represents an integer of 2-40. n2 and n4 each independently represent an integer of 0 to 29; n2+n4 represents an integer of 0-30.
The arrangement of -(AO)- and -(B-O)- constitutional units may be either random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group.
n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Also, n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.

The content of the polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, more preferably 25.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of better resolution. % or more by mass is more preferable. The upper limit is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which the photosensitive composition exudes from the edge of the transfer member).

The content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, more preferably 55.0% by mass, based on the total mass of the polymerizable compound, from the viewpoint of better resolution. % or more by mass is more preferable. The upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, and even more preferably 95.0% by mass or less, based on the total mass of the polymerizable compound, from the viewpoint of releasability.

-Other polymerizable compounds-
The photosensitive layer preferably contains other polymerizable compounds in addition to the above.
Other polymerizable compounds include, for example, known polymerizable compounds.
Specifically, a compound having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound compound.

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

Bifunctional ethylenically unsaturated compounds having no aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.
Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol 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.
Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.
Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products of urethane di(meth)acrylate include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). be done.

Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate and alkylene oxide modified products thereof.
"(Tri/tetra/penta/hexa)(meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate. Moreover, "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

Examples of alkylene oxide-modified tri- or higher ethylenically unsaturated compounds include, for example, caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. -1CL, 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, etc. ), ethoxylated glycerin triacrylate (Shin-Nakamura Chemical Co., Ltd. A-GLY-9E, etc.), 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.).

The polymerizable compound may be a polymerizable compound having an acid group (eg, carboxyl group, etc.). The acid group may form an acid anhydride group.
Examples of the polymerizable compound having an acid group include Aronix (registered trademark) (eg, TO-2349, M-520 and M-510, manufactured by Toagosei Co., Ltd.).
Examples of the polymerizable compound having an acid group include polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942.

The molecular weight of the polymerizable compound is preferably from 200 to 3,000, more preferably from 280 to 2,200, even more preferably from 300 to 2,200.

The viscosity of the polymerizable compound at 25° C. is preferably 1 to 10,000 mPa·s, more preferably 5 to 3,000 mPa·s, even more preferably 10 to 1,500 mPa·s.

You may use a polymerizable compound individually by 1 type or in 2 or more types.
The content of the polymerizable compound is preferably 5.0 to 70.0% by mass, more preferably 15.0 to 70.0% by mass, and 30.0 to 70.0% by mass, based on the total mass of the photosensitive layer. % by mass is more preferred.

-Polymerization initiator-
The photosensitive layer preferably contains a polymerization initiator.
Examples of the polymerization initiator include known polymerization initiators depending on the type of polymerization reaction. Specific examples include thermal polymerization initiators and photopolymerization initiators.
The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.

The photosensitive layer preferably contains a photoinitiator.
A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays.
Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.

Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, and acylphosphine oxide. A photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure are included.

The photoradical polymerization initiator is at least selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof in terms of photosensitivity, visibility of exposed and unexposed areas, and resolution. It preferably contains one. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different.
Derivatives of 2,4,5-triarylimidazole dimer include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di (Methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer and 2-( p-Methoxyphenyl)-4,5-diphenylimidazole dimer.

As the photoradical polymerization initiator, for example, the photoradical polymerization described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064] to [0081] of JP-A-2015-014783 initiators.

Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (manufactured by Midori Chemical Co., Ltd.), TAZ-111 (Midori Chemical company), 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1- {4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethyl amino-1-(4-morpholinophenyl)butanone-1 (Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (Omnirad 184, IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad 651, IGM Resins B.V.), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenyl Phosphine oxide (Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (Lun ar 6, manufactured by DKSH Japan), 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl ]-3-Cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1- [9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (TR-PBG-326, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.) and 3 -cyclohexyl-1-(6-(2-(benzoyloximino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR -PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).

A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving an actinic ray.
Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Examples of the ionic photocationic polymerization initiator include ionic photocationic polymerization initiators described in paragraphs [0114] to [0133] of JP-A-2014-085643.

Examples of nonionic photocationic polymerization initiators include diazomethane compounds, imidosulfonate compounds and oximesulfonate compounds.
Examples of diazomethane compounds and imidosulfonate compounds include compounds described in paragraphs [0083] to [0088] of JP-A-2011-221494.
Oxime sulfonate compounds include, for example, compounds described in paragraphs [0084] to [0088] of WO2018/179640.

A polymerization initiator may be used singly or in combination of two or more.
The content of the polymerization initiator (preferably photopolymerization initiator) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 0.5% by mass, based on the total mass of the photosensitive layer. The above is more preferable. The upper limit is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and even more preferably 10.0% by mass or less, relative to the total mass of the photosensitive layer.

-Polymerization inhibitor-
The photosensitive layer also preferably contains a polymerization inhibitor (preferably a radical polymerization inhibitor).
A polymerization inhibitor means a compound having a function of delaying or inhibiting a polymerization reaction.
When the photosensitive layer contains a polymerization inhibitor, the effects of the present invention can be further improved.

As the polymerization inhibitor, for example, a known polymerization inhibitor can be used. Specific examples of polymerization inhibitors include, for example, phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and phenothiazine compounds such as 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4- hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t- butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4 -hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine and hindered such as pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Phenolic compounds; phenoxazine compounds such as phenoxazine; nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine or salts thereof; methylhydroquinone, t -butylhydroquinone, 2,5-di-t-butylhydroquinone, and quinone compounds such as 4-benzoquinone; 4-methoxyphenol, 4-methoxy-1-naphthol, and phenolic compounds such as t-butylcatechol; dibutyl metal salt compounds such as copper dithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate;
Among them, at least one selected from the group consisting of phenothiazine-based compounds, hindered phenol-based compounds, and phenoxazine-based compounds is preferable as the polymerization inhibitor, because the effects of the present invention are more excellent.

A polymerization inhibitor may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0% by weight, preferably 0.01 to 3.0% by weight, based on the total weight of the photosensitive layer. is more preferable, 0.02 to 2.0% by mass is more preferable, 0.01 to 1.0% by mass is particularly preferable, and 0.01 to 0.5% by mass is most preferable. The content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound. 0% by mass is more preferred.

- Sensitizer -
The photosensitive layer preferably contains a sensitizer.
Sensitizers include, for example, known sensitizers, dyes, and pigments.
Sensitizers include, for example, 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, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds.

The content of the sensitizer is 0.01 to 5.0% by mass based on the total mass of the photosensitive layer, from the viewpoint of improving the sensitivity to light sources and improving the curing speed due to the balance between polymerization speed and chain transfer. Preferably, 0.05 to 1.0% by mass is more preferable.

Sensitizers include, for example, benzophenone compounds (preferably dialkylaminobenzophenone compounds), thioxanthone compounds, cyanine compounds, coumarin compounds, merocyanine compounds, pyrazoline compounds, anthracene compounds, xanthone compounds, oxazole-based compounds, benzoxazole-based compounds, thiazole-based compounds, benzothiazole-based compounds, triazole-based compounds (e.g., 1,2,4-triazole), stilbene-based compounds, triazine-based compounds, thiophene-based compounds, naphthalimide-based compounds, Examples include triarylamine-based compounds and aminoacridine-based compounds.
At least one compound selected from the group consisting of benzophenone-based compounds, thioxanthone-based compounds, cyanine-based compounds, coumarin-based compounds, and merocyanine-based compounds is preferable in that the effects of the present invention are more excellent.

Color-developing dyes can also be used as dye-based sensitizers. A color-developing dye is a compound having a function of developing color by light irradiation. Examples of color-developing dyes include leuco dyes and fluoran dyes.

Specific examples of sensitizers include fuchsine, phthalocyanine green, coumarin 6, coumarin 7, coumarin 102, 3-acetyl-7-(diethylamino)coumarin, 4,4′-bis(diethylamino)benzophenone, DOC iodide, Indomonocarbocyanine sodium, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (manufactured by Hodogaya Chemical Co., Ltd., AIZEN (registered trademark) MALACHITE GREEN), basic blue 20 , and diamond green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH).

The photosensitive layer may contain a single sensitizer, or may contain two or more sensitizers.

The content of the sensitizer is preferably from 0.01 to 5.0% by mass, more preferably from 0.05 to 1.0%, based on the total mass of the photosensitive layer, from the viewpoint that the effects of the present invention are more excellent. % by mass is more preferred.

-Specific dye-
The photosensitive layer contains a specific dye.
The specific dye is a dye that has a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer, and the difference between the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer is 40 nm or more. Say. When the specific dye has multiple maximum absorption wavelengths, the difference between any maximum absorption wavelength and the maximum sensitivity wavelength is 40 nm or more. The difference is a value obtained by subtracting the smaller value from the larger value of the maximum absorption wavelength of the specific dye and the maximum sensitivity wavelength of the photosensitive layer. When the maximum absorption wavelength of the specific dye and the maximum sensitivity wavelength of the photosensitive layer are the same, the difference corresponds to zero.
Further, the specific dye preferably has a maximum absorption wavelength in any wavelength band from the ultraviolet to the visible region, more preferably has a maximum absorption wavelength in the wavelength band of 300 to 780 nm. More preferably, it has a maximum absorption wavelength in a wavelength band of ~500 nm.

The maximum absorption wavelength of a specific dye is determined by measuring the transmission spectrum of a solution containing the specific dye (liquid temperature: 25°C) in the range of 300 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) under atmospheric conditions. can be measured by detecting the wavelength (maximum absorption wavelength) at which the light intensity becomes minimum.
The method for measuring the maximum sensitivity wavelength of the photosensitive layer is as described above.

The specific dye preferably does not contain a dye whose maximum absorption wavelength is changed by acids, bases or radicals. The dye whose maximum absorption wavelength is changed by an acid, a base, or a radical corresponds to, for example, a dye N described later.
The specific dye may or may not be a sensitizing dye, but a non-sensitizing dye is preferred from the viewpoint that the effect of the present invention is more excellent. In other words, the specific dye is preferably not sensitized.
As the non-sensitizing dye, a compound that does not rapidly excite the polymerization initiator by energy transfer or electron transfer after becoming a singlet excited state by light absorption from the ground state, and a compound that does not excite the polymerization initiator in the wavelength range of 300 to 500 nm , the polymerization initiator is not rapidly excited by energy transfer or electron transfer after becoming a singlet excited state by light absorption from the ground state, but in a wavelength range other than the above wavelength range, the singlet excited state by light absorption from the ground state A compound, etc., which immediately makes the polymerization initiator into an excited state by energy transfer or electron transfer after becoming is applicable.

Further, among the sensitizers described in the upper section, a dye having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer, and the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer Dyes with a difference of 40 nm or more can be used as specific dyes.

The difference between the maximum absorption wavelength of the specific dye and the maximum sensitivity wavelength of the photosensitive layer is preferably 50 nm or more, more preferably 60 nm or more. The upper limit is not particularly limited, and is preferably 150 nm or less, for example.
Either the maximum absorption wavelength of the specific dye or the maximum sensitivity wavelength of the photosensitive layer may be larger, and the maximum absorption wavelength of the specific dye may be larger than the maximum sensitivity wavelength of the photosensitive layer. Alternatively, the maximum sensitivity wavelength of the photosensitive layer may be larger than the maximum absorption wavelength of the specific dye.
The maximum absorption wavelength of the specific dye is in the wavelength range of more than 395 nm and 500 nm or less, or preferably in the wavelength range of 300 to 395 nm, and in the wavelength range of 410 to 500 nm, or 300 to 395 nm. More preferably it is a wavelength range.

As an example of a preferred embodiment of the combination of the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the specific dye, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and the maximum absorption wavelength of the specific dye is more than 395 nm and 500 nm or less. A certain aspect is mentioned. In the above embodiment, the maximum absorption wavelength of the specific dye is also preferably 410 to 500 nm.
Further, as another preferred embodiment of the combination of the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the specific dye, the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and the maximum absorption wavelength of the specific dye is is 300 to 395 nm. In the above embodiment, the maximum sensitivity wavelength of the photosensitive layer is preferably from 410 to 500 nm, more preferably from 410 to 450 nm.

As the dye, any of known dyes suitable for the wavelength conditions can be appropriately used.
The dye is not particularly limited, and examples thereof include dyes (including metal complex dyes) and pigments, preferably dyes.

Dyes having a maximum absorption wavelength of more than 395 nm and 500 nm or less include azo dyes, quinoline dyes, nitro dyes, methine dyes, indole dyes, and metal complex dyes.
Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Reactive Yellow 2, C.I. I. Disperse Orange 5, C.I. I. Mordant Yellow 5, C.I. I. Solvent Yellow 16, and C.I. I. Solvent Yellow 56 etc. are mentioned.

Examples of quinoline dyes include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3 and C.I. I. Examples include Disperse Yellow 64 and the like.

Nitro dyes include, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3 and C.I. I. Examples include Disperse Yellow 42 and the like.

Examples of methine dyes include C.I. I. Disperse Yellow 201 etc. are mentioned. Examples of methine-based dyes also include compounds having the following structures.

Examples of indole dyes include Bonasorb UA3912 and UA3912 (manufactured by Orient Chemical Co., Ltd.).

Examples of metal complex dyes include cobalt complex dyes and zinc complex dyes.
Examples of cobalt complex dyes include C.I. I. Solvent Yellow 89 etc. are mentioned.
Examples of zinc complex dyes include compounds having the following structures.

Examples of pigments having a maximum absorption wavelength of more than 395 nm and not more than 500 nm include C.I. I. (Color Index) Pigment Yellow 1, 3, 4, 5, 6, 12, 13, 14, 16, 17, 18, 20, 24, 55, 65, 73, 74, 81, 83, 86, 87, 93, 94, 95, 97, 98, 100, 101, 108, 109, 110, 113, 116, 117, 120, 123, 125, 128, 129, 133, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 156, 166, 168, 169, 170, 171, 172, 173, and 175; I. Pigment Orange 1, 2, 5, 13, 15, 16, 17, 18, 19, 31, 34, 36, 38, 40, 42, 43, 51, 52, 55, 59, 60, 61, and 62; and yellow pigments.

Known ultraviolet absorbers can be used as dyes having a maximum absorption wavelength of 300 to 395 nm. Examples of ultraviolet absorbers having a maximum absorption wavelength of 300 to 395 nm include benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, salicylate-based compounds, and cyanoacrylate-based compounds.

The specific dye preferably has an absorbance of 1 or less at the maximum sensitivity wavelength of the photosensitive layer. When the absorbance is 1 or less, there is an advantage that the decrease in sensitivity due to the inhibition of the dye is less likely to occur when the photosensitive layer is exposed to light. The absorbance of the specific dye at the maximum sensitivity wavelength of the photosensitive layer is more preferably 0.5 or less, still more preferably 0.2 or less, from the viewpoint that the effects of the present invention are more excellent. Note that the lower limit is not particularly limited, and is, for example, 0 or more.
As the absorbance of the specific dye, a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) is used in an atmospheric atmosphere, and a solution with a concentration of 0.01% by weight containing the specific dye in the range of 300 to 780 nm (liquid temperature 25 ° C. ) can be measured using a quartz cell with an optical path length of 1 mm.
When the photosensitive layer contains only one specific dye, the absorbance of the specific dye at the maximum sensitivity wavelength of the photosensitive layer is preferably within the above numerical range. When the photosensitive layer contains two or more specific dyes, it is preferable that the absorbance in a state where the above two or more dyes are mixed so as to satisfy the compounding ratio (mass ratio) in the layer falls within the above numerical range.
Further, in the transfer film of the second embodiment described later, when the thermoplastic resin layer contains only one type of specific dye, it is preferable that the absorbance at the maximum sensitivity wavelength of the photosensitive layer of the specific dye falls within the above numerical range. . When the thermoplastic resin layer contains two or more specific dyes, it is preferable that the absorbance in a state where the above two or more dyes are mixed so as to have the compounding ratio (mass ratio) in the layer falls within the above numerical range. .

The content of the specific dye is preferably from 0.01 to 15.0% by mass, more preferably from 0.05 to 10.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint that the effects of the present invention are more excellent. %, more preferably 0.1 to 10.0% by mass, and particularly preferably 1.0 to 10.0% by mass.

As a preferred embodiment, when the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and the photosensitive layer contains a specific dye having a maximum absorption wavelength of 300 to 395 nm, the maximum absorption wavelength in the photosensitive layer is The content of dyes of more than 395 nm and 500 nm or less (the dyes referred to here preferably do not include “dyes whose maximum absorption wavelength changes due to acids, bases, or radicals (e.g., dye N)”). It is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and 1.0% by mass or less from the viewpoint that the effects of the present invention are more excellent, based on the total mass of the adhesive layer. is more preferably 0.1% by mass or less, and most preferably 0.01% by mass or less. As a lower limit, it is 0 mass % or more.
As a particularly preferred embodiment, the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and when the photosensitive layer contains a specific dye having a maximum absorption wavelength of 300 to 395 nm, the maximum absorption wavelength in the photosensitive layer is more than 395 nm and 500 nm or less (the dye referred to here preferably does not include a "dye whose maximum absorption wavelength changes due to acid, base or radical (e.g., dye N)")). be done.

As a preferred embodiment, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and when the photosensitive layer contains a specific dye having a maximum absorption wavelength of more than 395 nm and 500 nm or less, the maximum absorption wavelength in the photosensitive layer is The content of dyes of 300 to 395 nm (the dyes referred to herein preferably do not include "dyes whose maximum absorption wavelength changes with acids, bases, or radicals (e.g., dye N)") is as follows: It is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, based on the total mass of the layer. 0.1% by mass or less is particularly preferable, and 0.01% by mass or less is most preferable. As a lower limit, it is 0 mass % or more.
As a particularly preferred embodiment, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and when the photosensitive layer contains a specific dye having a maximum absorption wavelength of more than 395 nm and 500 nm or less, the maximum absorption wavelength in the photosensitive layer is 300 to 395 nm (the dye referred to here preferably does not include a “dye whose maximum absorption wavelength changes due to acid, base or radical (e.g., dye N)”)). .

-Dye N-
The photosensitive layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development from the viewpoint of visibility of exposed and unexposed areas, and pattern visibility and resolution after development, and , an acid, a base or a radical may contain a dye whose maximum absorption wavelength is changed (hereinafter also referred to as "dye N").
When the dye N is contained, although the detailed mechanism is unknown, the adhesion to the adjacent layer (for example, the intermediate layer, etc.) is improved and the resolution is improved.

The dye "changes the maximum absorption wavelength by acid, base or radical" means that the dye in the colored state is decolored by acid, base or radical, and the dye in decolored state is colored by acid, base or radical. It may mean either one of the aspect in which the dye in the coloring state changes to the coloring state of another hue.
Specifically, the dye N may be either a compound that changes from a decolored state to develop color upon exposure or a compound that changes from a colored state to decolor upon exposure. In the above case, it may be a dye that changes the state of color development or decoloration by the action of an acid, a base, or a radical generated in the photosensitive layer by exposure, and the photosensitive layer is affected by the acid, the base, or the radical. It may be a dye that changes its coloring or decoloring state by changing the internal state (for example, pH). Further, it may be a dye that changes its coloring or decoloring state by being directly stimulated by an acid, a base, or a radical without being exposed to light.

Among them, from the viewpoint of the visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals. .
From the standpoint of visibility and resolution of exposed and unexposed areas, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator as the dye N. In view of the visibility of the exposed and unexposed areas, the dye N is preferably a dye that develops color with an acid, a base, or a radical.

As the coloring mechanism of the dye N, for example, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive layer, and after exposure, the photoradical polymerization initiator, the photo A radical-reactive dye, an acid-reactive dye, or a base-reactive dye (for example, a leuco dye) develops color by a radical, acid, or base generated from a cationic polymerization initiator or a photobase generator.

From the viewpoint of the visibility of the exposed and unexposed areas, the maximum absorption wavelength in the wavelength range of 400 to 780 nm when dye N develops is preferably 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.
In addition, the dye N may have one or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or more.

The maximum absorption wavelength of Dye N is determined by measuring the transmission spectrum of a solution containing Dye N in the range of 400 to 780 nm (liquid temperature 25°C) using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. can be measured by detecting the wavelength (maximum absorption wavelength) at which the light intensity becomes minimum.

Examples of dyes that develop or decolorize upon exposure include leuco compounds.
Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
As the dye N, a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons. a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco having a leuco auramine skeleton compounds (leuco auramine dyes).
Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.

The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility in exposed and unexposed areas. As a result, the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state. Color can be developed by decolorizing or by changing the leuco compound to a ring-opened state. The leuco compound is preferably a compound that has a lactone ring, a sultine ring or a sultone ring and develops color by opening the lactone ring, sultine ring or sultone ring with a radical or an acid, and has a lactone ring and a radical or an acid. A compound that develops color by opening the lactone ring is more preferred.

Dyes N include, for example, dyes and leuco compounds.
Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, and paramethyl red. , Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd. ), oil blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industry Co., Ltd.), oil scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxanilino-4-p-diethyaminophenyliminonaphthoquinone, 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-pyrazolones.

Leuco compounds include, for example, p,p′,p″-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane , 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6 -methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluor Olan, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino )-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N -diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7 -xyridinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole -3-yl)phthalide, 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-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl- 2-methylindol-3-yl)phthalide and 3′,6′-bis(diphenylamino)spiroisobenzofuran-1(3H),9′-[9H]xanthen-3-one.

As the dye N, a dye whose maximum absorption wavelength is changed by radicals is preferable, and a dye that develops color by radicals is more preferable, from the viewpoint of visibility in exposed and unexposed areas, pattern visibility after development, and resolution. .
Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-naphthalene sulfonate.

You may use the pigment|dye N individually by 1 type or in 2 or more types.
The content of the dye N is based on the total mass of the first photosensitive layer or the second photosensitive layer from the viewpoint of visibility of the exposed area and the non-exposed area, and excellent pattern visibility and resolution after development. is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, and even more preferably 0.1 to 5% by mass.

The content of the dye N means the content of the dye when all of the dye N contained in the total weight of the photosensitive layer is in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described using a dye that develops color by radicals as an example.
A solution of dye N (0.001 g) and a solution of dye N (0.01 g) in 100 mL of methyl ethyl ketone are prepared. A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm, and all dyes N are brought into a colored state. After that, the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to prepare a calibration curve.
Then, in the same manner as described above, except that the first photosensitive layer or the second photosensitive layer (3 g) is dissolved in methyl ethyl ketone instead of the dye N, the absorbance of the solution in which all the dyes are developed is measured. From the absorbance of the obtained solution containing the photosensitive layer, the content of dye N contained in the photosensitive layer is calculated based on the calibration curve.

－Other Additives－
The photosensitive layer may contain other additives, if necessary, in addition to the above components.
Other additives include, for example, benzotriazoles, carboxybenzotriazoles, surfactants, plasticizers, heterocyclic compounds (e.g., triazole, imidazole, etc.), pyridines (e.g., isonicotinamide, etc.) and purine bases ( For example, adenine, etc.).
Other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thickeners, cross-linking agents, organic or inorganic precipitates, and paragraphs [0165] to [0184] of JP 2014-085643, the contents of which are incorporated herein.
Other additives may be used singly or in combination of two or more.

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

-Carboxybenzotriazoles-
Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene Carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole and N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole.
Specific examples of carboxybenzotriazoles include CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.).

The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of sensitivity and suppression of decolorization of the dye are more excellent.

-Surfactant-
Examples of surfactants include surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.

As the surfactant, a nonionic surfactant, a fluorosurfactant or a silicone surfactant is preferred.
Examples of fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F- 437, F-475, F-477, F-479, F-482, F-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 and DS-21 (above, DIC); Florard FC430, FC431 and FC171 (manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393 and KH-40 (manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA); 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683 (manufactured by NEOS).

Further, as the fluorosurfactant, an acrylic compound having a molecular structure with a functional group containing a fluorine atom is also preferable, in which the portion of the functional group containing the fluorine atom is cleaved when heat is applied to volatilize the fluorine atom. .
Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC (The Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)).
As the fluorosurfactant, it is also preferable to use a copolymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
A block polymer can also be used as the fluorosurfactant.
The fluorosurfactant has 2 or more (preferably 5 or more) structural units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (preferably 5 or more). ) and a structural unit derived from an acrylate compound.
Examples of the fluorosurfactant also include fluoropolymers having an ethylenically unsaturated group in the side chain, such as Megafac RS-101, RS-102, RS-718K and RS-72-K ( (manufactured by DIC Corporation).

As the fluorosurfactant, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used from the viewpoint of improving environmental friendliness. Surfactants derived from alternative materials are preferred.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl Ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; Pluronic (registered trademark) L10, L31, L61, L62 , 10R5, 17R2 and 25R2 (manufactured by BASF); Tetronic 304, 701, 704, 901, 904 and 150R1 (manufactured by BASF); Solsperse 20000 (manufactured by Nippon Lubrizol); NCW-101 , NCW-1001 and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Pionin D-6112, D-6112-W and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); 400 and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and/or terminals.

Examples of silicone-based surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Silicone manufactured by Dow Corning); X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF- 4460 and TSF-4452 (manufactured by Momentive Performance Materials); BYK307, BYK323 and BYK330 (manufactured by BYK-Chemie).

The content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.8% by mass, based on the total mass of the photosensitive layer. % by mass is more preferred.

Plasticizers and heterocyclic compounds include, for example, compounds described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of WO2018/179640.

-impurities-
The photosensitive layer may contain impurities.
Impurities include, for example, metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.

-Metal Impurities and Halide Ions-
Metal impurities include, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin and ions thereof, and halide ions.
Among them, sodium ions, potassium ions and halide ions are preferably contained in the following amounts because they are easily mixed.
Metal impurities are compounds different from the particles (eg, metal oxide particles) that may be included in the transfer film.

The content of metal impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, relative to the total mass of the photosensitive layer.

Methods for adjusting the content of impurities include, for example, a method of selecting a material with a low impurity content as a raw material for the photosensitive layer, a method of preventing contamination of impurities during the formation of the photosensitive layer, and a method of removing impurities by washing. method.
The content of impurities can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy and ion chromatography.

- Residual organic solvent -
Residual organic solvents include, for example, benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane.
The content of the residual organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, relative to the total mass of the photosensitive layer.
As a method for adjusting the content of the residual organic solvent, there is a method for adjusting the drying treatment conditions in the transfer film manufacturing method described below. Also, the content of the residual organic solvent can be quantified by a known method such as gas chromatography analysis.

- Residual monomer -
The photosensitive layer may contain residual monomers of the constituent units of the resin.
The content of the residual monomer is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less relative to the total mass of the resin, from the viewpoint of patterning properties and reliability. The lower limit is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, relative to the total mass of the resin.
The residual monomer of each structural unit of the alkali-soluble resin is preferably 3000 ppm by mass or less, more preferably 600 ppm by mass or less, more preferably 100 mass ppm with respect to the total mass of the photosensitive layer from the viewpoint of patterning property and reliability. ppm or less is more preferred. The lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive layer.

The residual amount of the monomer when synthesizing the alkali-soluble resin by polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting a carboxylic acid side chain with glycidyl acrylate, the content of glycidyl acrylate is preferably within the above range.
Examples of the method for adjusting the content of the residual monomer include a method for adjusting the content of the impurities.
The content of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

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

-Characteristics of photosensitive layer (photosensitive layer A)-
The average thickness of the photosensitive layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, even more preferably 1 to 20 μm. Thereby, the developability of the photosensitive layer can be improved, and the resolution can also be improved.
The average thickness of the photosensitive layer is the average of 10 thicknesses measured by observing a cross section perpendicular to the in-plane direction of the photosensitive layer using a scanning electron microscope (SEM). value.

(Photosensitive layer of the second embodiment (photosensitive layer B))
Components that can be contained in the photosensitive layer B are described in detail below.

- Binder polymer -
The photosensitive layer may contain a binder polymer.
Examples of binder polymers include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amidoepoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy resins and (meth)acrylic acid. Epoxy acrylate resin obtained and acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin and acid anhydride are mentioned.

One preferred embodiment of the binder polymer is a (meth)acrylic resin because of its excellent alkali developability and film formability.
In addition, in this specification, the (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. The content of structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on all the structural units of the (meth)acrylic resin. .
The (meth)acrylic resin may be composed only of structural units derived from the (meth)acrylic compound, or may have structural units derived from polymerizable monomers other than the (meth)acrylic compound. . That is, the upper limit of the content of structural units derived from the (meth)acrylic compound is 100% by mass or less with respect to all structural units of the (meth)acrylic resin.

Examples of (meth)acrylic compounds include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, and (meth)acrylonitrile.
Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth) ) glycidyl acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, ( Meth)acrylic acid alkyl esters are preferred.
(Meth)acrylamides include, for example, acrylamides such as diacetone acrylamide.

The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, ( meth)heptyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and (meth)acrylic acid Examples thereof include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
As the (meth)acrylic acid ester, an alkyl (meth)acrylic acid ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferable.

The (meth)acrylic resin may have a structural unit other than the structural unit derived from the (meth)acrylic compound.
The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth)acrylic compound copolymerizable with the (meth)acrylic compound. Examples include styrene, vinyltoluene, and α - Styrene compounds optionally having a substituent at the α-position or aromatic ring such as methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid.
These polymerizable monomers may be used singly or in combination of two or more.

Moreover, the (meth)acrylic resin preferably has a constitutional unit having an acid group from the viewpoint of improving alkali developability. Acid groups include, for example, carboxy groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups.
Among them, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and more preferably has a structural unit derived from the above (meth)acrylic acid.

The content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is excellent in developability, relative to the total mass of the (meth)acrylic resin, 10 mass % or more is preferable. Although the upper limit is not particularly limited, it is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.

Further, the (meth)acrylic resin more preferably has structural units derived from the (meth)acrylic acid alkyl ester described above.
The content of the structural unit derived from the (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, based on the total structural units of the (meth)acrylic resin. More preferably, 65 to 90% by mass is even more preferable.

As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferable, and a structural unit derived from (meth)acrylic acid and A resin composed only of structural units derived from a (meth)acrylic acid alkyl ester is more preferable.
As the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

Further, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and structural units derived from methacrylic acid and It is preferable to have both structural units derived from methacrylic acid alkyl ester.
The total content of the structural units derived from methacrylic acid and the structural units derived from methacrylic acid alkyl esters in the (meth)acrylic resin is preferably 40% by mass or more, with respect to all structural units of the (meth)acrylic resin. % or more by mass is more preferable. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

Further, the (meth)acrylic resin includes at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters, and structural units derived from acrylic acid and acrylic acid alkyl esters. It is also preferable to have at least one selected from the group consisting of structural units derived from.
The total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters is the total content of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. is preferably 60/40 to 80/20.

The (meth)acrylic resin preferably has an ester group at its terminal from the viewpoint of excellent developability of the photosensitive layer after transfer.
In addition, the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at its terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

Another preferred embodiment of the binder polymer is an alkali-soluble resin.
The binder polymer is preferably, for example, a binder polymer having an acid value of 60 mgKOH/g or more from the viewpoint of developability.
Further, the binder polymer is, for example, a resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing resin) because it thermally crosslinks with a cross-linking component by heating and easily forms a strong film. More preferably, it is a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing (meth)acrylic resin).
When the binder polymer is a resin having a carboxyl group, for example, by adding a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking, the three-dimensional crosslinking density can be increased. In addition, when the carboxy group of the resin having a carboxy group is dehydrated and hydrophobized, the wet heat resistance can be improved.

The carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the acid value conditions described above, and can be appropriately selected from known (meth)acrylic resins.
For example, among the polymers described in paragraph [0025] of JP-A-2011-095716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more, paragraphs [0033] to [0052] of JP-A-2010-237589 Among the polymers described in 1., carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more can be preferably used.

Another preferred embodiment of the binder polymer is a styrene-acrylic copolymer.
In this specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and a structural unit derived from the styrene compound. , and the total content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer. The upper limit is often 100% by mass or less.
Also, the content of structural units derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5 to 80% by mass, based on all the structural units of the copolymer.
Further, the content of the structural unit derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20 to 95% by mass, based on the total structural units of the copolymer. is more preferred.

The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure.
Monomers that form structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid , styrene dimers, and styrene trimers). Among them, a monomer having an aralkyl group or styrene is preferred.
Aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and the like, with substituted or unsubstituted benzyl groups being preferred.

Phenylethyl (meth)acrylate etc. are mentioned as a monomer which has a phenylalkyl group.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, and vinyl benzyl alcohol and the like. Among them, benzyl (meth)acrylate is preferred.

Further, the binder polymer more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more than 10 to 70% by mass, based on the total structural units of the binder polymer. Preferably, 20 to 60% by mass is more preferable.
The content of structural units having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, more preferably 20 to 60 mol%, based on the total structural units of the binder polymer. More preferred.
Furthermore, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, more preferably 20 to 70 mol%, based on the total structural units of the binder polymer. 60 mol % is more preferred, and 20 to 50 mol % is particularly preferred.
In addition, in this specification, when the content of the "structural unit" is defined by the molar ratio, the above-mentioned "structural unit" shall be synonymous with the "monomer unit". Further, in the present specification, the above-mentioned "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The binder polymer preferably has an aliphatic hydrocarbon ring structure. That is, the binder polymer preferably has structural units having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. In particular, the binder polymer more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

Examples of rings constituting the aliphatic hydrocarbon ring structure in the constituent unit having the aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane ring, and isoboron ring.
Among them, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 ^2,6 ]decane ring) is more preferable.
Monomers that form structural units having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
Further, the binder polymer more preferably has a structural unit represented by the following formula (Cy). It is more preferable to have

In formula (Cy), ^RM represents a hydrogen atom or a methyl group, and R ^Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

^RM in formula (Cy) is preferably a methyl group.
R ^Cy in formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms. is more preferably a group, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms.
Further, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoboron ring structure, and cyclohexane A ring structure or a tetrahydrodicyclopentadiene ring structure is more preferred, and a tetrahydrodicyclopentadiene ring structure is even more preferred.
Furthermore, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and two to four aliphatic hydrocarbon rings are A condensed ring is more preferred.
Furthermore, R ^Cy in formula (Cy) is a group in which the oxygen atom of -C(=O)O- in formula (Cy) and an aliphatic hydrocarbon ring structure are directly bonded, i.e., an aliphatic hydrocarbon ring group. is preferred, a cyclohexyl group or a dicyclopentanyl group is more preferred, and a dicyclopentanyl group is even more preferred.

The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types.
When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass based on the total structural units of the binder polymer, 10 to 80% by mass is more preferable, and 20 to 70% by mass is even more preferable.
In addition, the content of structural units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, more preferably 20 to 50, based on the total structural units of the binder polymer. Mole % is more preferred.
Furthermore, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, more preferably 20 to 70 mol%, based on the total structural units of the binder polymer. 50 mol % is more preferred.

When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of structural units having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure is It is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass, based on all structural units of the polymer.
Further, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, preferably 20 to 70, with respect to the total structural units of the binder polymer. mol % is more preferred, and 40 to 60 mol % is even more preferred.
Furthermore, the total content of the structural units represented by the formula (S) and the structural units represented by the formula (Cy) in the binder polymer is 10 to 80 mol% based on the total structural units of the binder polymer. Preferably, 20 to 70 mol % is more preferable, and 40 to 60 mol % is even more preferable.

The binder polymer preferably has structural units having acid groups.
Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with the carboxy group being preferred.
As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferable, and a structural unit derived from methacrylic acid is more preferable.

The binder polymer may have one type of structural unit having an acid group, or may have two or more types.
When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, based on the total structural units of the binder polymer. , 10 to 30% by mass is more preferable.
Further, the content of structural units having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, more preferably 20 to 40 mol%, based on the total structural units of the binder polymer. preferable.
Furthermore, the content of structural units derived from (meth)acrylic acid in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and 20 to 40 mol, based on the total structural units of the binder polymer. % is more preferred.

The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group.
The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. Moreover, when the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in its side chain.
As used herein, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branched from the main chain. show.
The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group.
Examples of structural units having a reactive group include, but are not limited to, those shown below.

The binder polymer may have one type of structural unit having a reactive group, or may have two or more types.
When the binder polymer has a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, based on the total structural units of the binder polymer. More preferably, 20 to 40% by mass is even more preferable.
The content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, more preferably 20 to 50 mol%, based on the total structural units of the binder polymer. More preferred.

As means for introducing reactive groups into the binder polymer, functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfo groups may be added to epoxy compounds and blocked isocyanate groups. compounds, isocyanate compounds, vinylsulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides.
As a preferred example of means for introducing a reactive group into a binder polymer, after synthesizing a polymer having a carboxy group by a polymerization reaction, glycidyl (meth)acrylate is added to a part of the carboxy group of the resulting polymer by polymer reaction. to introduce a (meth)acryloxy group into the polymer. By this means, a binder polymer having (meth)acryloxy groups in side chains can be obtained.
The polymerization reaction is preferably carried out under temperature conditions of 70 to 100°C, more preferably under temperature conditions of 80 to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. is more preferable. The above polymer reaction is preferably carried out under temperature conditions of 80 to 110°C. In the polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

As the binder polymer, polymers X1 to X4 shown below are preferred. The content ratio (a to d) of each structural unit shown below, the weight average molecular weight Mw, and the like can be appropriately changed according to the purpose. is preferred.
(Polymer X1) a: 20 to 60% by mass, b: 10 to 50% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
(Polymer X2) a: 20 to 60% by mass, b: 10 to 50% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
(Polymer X3) a: 30 to 65% by mass, b: 1.0 to 20% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
(Polymer X4) a: 1.0 to 20% by mass, b: 20 to 60% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.

The binder polymer may also contain a polymer having a structural unit having a carboxylic anhydride structure (hereinafter also referred to as "polymer X").
The carboxylic anhydride structure may be either a linear carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.
The ring of the cyclic carboxylic anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

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

In Formula P-1, R ^A1a represents a substituent, n ^1a R ^A1a may be the same or different, and Z ^1a is -C(=O)-OC(=O)- and n ^1a represents an integer of 0 or more.

Examples of the substituent represented by ^RA1a include an alkyl group.
Z ^1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms.
^n1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, even more preferably 0.
When ^n1a represents an integer of 2 or more, multiple R ^A1a may be the same or different. In addition, two or more ^RA1a groups may combine with each other to form a ring, but preferably do not combine with each other to form a ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, and an unsaturated aliphatic cyclic carboxylic acid anhydride. Structural units derived from acid anhydride are more preferred, structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.

Specific examples of structural units having a carboxylic anhydride structure are given below, but the structural units having a carboxylic anhydride structure are not limited to these specific examples. In the structural units below, Rx represents a hydrogen atom, a methyl group, a _CH2OH group, or a _CF3 group, and Me represents a methyl group.

The structural unit having a carboxylic anhydride structure in the polymer X may be of one type alone, or may be of two or more types.

The total content of structural units having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, more preferably 10 to 35 mol%, relative to the total structural units of the polymer X. preferable.

The photosensitive layer may contain only one type of polymer X, or may contain two or more types.
When the photosensitive layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, based on the total mass of the photosensitive layer. .5 to 20% by mass is more preferable, and 1 to 20% by mass is even more preferable.

The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

The acid value of the binder polymer is preferably 10-200 mgKOH/g, more preferably 60-200 mgKOH/g, still more preferably 60-150 mgKOH/g, and particularly preferably 70-125 mgKOH/g.
The acid value of the binder polymer is a value measured according to the method described in JIS K0070:1992.
From the viewpoint of developability, the degree of dispersion of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and 1.0 to 3.0. 0.0 is particularly preferred.

The photosensitive layer may contain only one type of binder polymer, or may contain two or more types.
The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, based on the total mass of the photosensitive layer.

-Polymerizable compound-
The photosensitive layer may contain a polymerizable compound.
A polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include radically polymerizable groups and cationic polymerizable groups, with radically polymerizable groups being preferred.

The polymerizable compound preferably contains a radically polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as "ethylenically unsaturated compound").
A (meth)acryloxy group is preferred as the ethylenically unsaturated group.
The ethylenically unsaturated compound in the present specification is a compound other than the above binder polymer, and preferably has a molecular weight of less than 5,000.

One preferred embodiment of the polymerizable compound is a compound represented by the following formula (M) (also simply referred to as "compound M").
Q ² -R ¹ -Q ¹ Formula (M)
In formula (M), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

Q ¹ and Q ² in formula ⁽ M ⁾ are preferably the same group from the viewpoint of ease of synthesis.
Moreover, Q ¹ and Q ² in formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
R ¹ in formula (M) is an alkylene group, an alkyleneoxyalkylene group (-L ¹ -OL ¹ -), or a polyalkyleneoxyalkylene group (-(L ¹ -O) _p -L ¹ -). is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is even more preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred.
The hydrocarbon group may at least partially have a chain structure, and the portion other than the chain structure is not particularly limited. 5 linear alkylene group, arylene group, ether bond, and combinations thereof, preferably an alkylene group or a group in which two or more alkylene groups and one or more arylene groups are combined. , an alkylene group is more preferred, and a linear alkylene group is even more preferred.
Each L ¹ above independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, preferably an integer of 2-10.

Further, the number of atoms in the shortest linking chain linking Q ¹ and Q ² in compound M is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and 8 to Twelve are particularly preferred.
As used herein, “the number of atoms in the shortest linking chain linking ^Q1 and ^Q2 ” refers to the number of atoms in ^R1 linking ^Q1 to the atom in ^{R1 linking Q2 .} It is the shortest number of atoms.

Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydrogenation Di(meth)acrylate of bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate , and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture.
Among the above compounds, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. ) is preferably at least one compound selected from the group consisting of acrylates, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10- More preferably, at least one compound selected from the group consisting of decanediol di(meth)acrylates, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth) More preferably, it is at least one compound selected from the group consisting of acrylates.

Moreover, as one of the preferred embodiments of the polymerizable compound, a bifunctional or higher ethylenically unsaturated compound can be mentioned.
As used herein, the term "bifunctional or higher ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.
A (meth)acryloyl group is preferred as the ethylenically unsaturated group in the ethylenically unsaturated compound.
A (meth)acrylate compound is preferable as the ethylenically unsaturated compound.

The bifunctional ethylenically unsaturated compound can be appropriately selected from known compounds.
Bifunctional ethylenically unsaturated compounds other than compound M include tricyclodecanedimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimenanol dimethacrylate ( Product name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (product name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6 -Hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

The tri- or more functional ethylenically unsaturated compound can be appropriately selected from known compounds.
Examples of tri- or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton can be mentioned.

Here, "(tri/tetra/penta/hexa) (meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. and "(tri/tetra)(meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

Examples of the polymerizable compound include caprolactone-modified compounds of (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.), (meth) ) Alkylene oxide-modified compounds of acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) of Daicel Allnex Co., Ltd. ) 135, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).

The polymerizable compound also includes urethane (meth)acrylate compounds.
Urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates.
Urethane (meth)acrylates also include trifunctional or higher urethane (meth)acrylates. The lower limit of the number of functional groups is more preferably 6 or more, and still more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Trifunctional or higher urethane (meth)acrylates include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd. ), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H , and UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.).

One preferred embodiment of the polymerizable compound is an ethylenically unsaturated compound having an acid group.
Acid groups include phosphate groups, sulfo groups, and carboxy groups.
Among these, a carboxy group is preferable as the acid group.
Examples of the ethylenically unsaturated compound having an acid group include tri- to tetra-functional ethylenically unsaturated compounds having an acid group [pentaerythritol tri- and tetraacrylate (PETA) having a carboxyl group introduced into its skeleton (acid value: 80- 120 mg KOH/g)], 5- to 6-functional ethylenically unsaturated compounds having acid groups (dipentaerythritol penta and hexaacrylate (DPHA) skeletons with carboxy groups introduced [acid value: 25-70 mg KOH/g)] etc.
If necessary, these trifunctional or higher ethylenically unsaturated compounds having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group.

As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of bifunctional or higher ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof is preferable.
When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher ethylenically unsaturated compound having a carboxyl group and its carboxylic acid anhydride, the developability and film strength are improved. increase.
The bifunctional or higher ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
Examples of bifunctional or higher ethylenically unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.) can be mentioned.

The ethylenically unsaturated compound having an acid group is preferably a polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942. incorporated into the specification.

As the polymerizable compound, for example, a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane Urethane monomers such as (meth)acrylate compounds having bonds, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl -o-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate and other phthalic acid compounds, and (meth)acrylic acid alkyl esters.
These are used alone or in combination of two or more.

Compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane , polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups. and polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate , trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) ) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate is mentioned. Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, such as tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or Di(trimethylolpropane)tetraacrylate is more preferred.

Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., 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 compounds of ethylenically unsaturated compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Allnex Co., Ltd. ) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

As the polymerizable compound (particularly, an ethylenically unsaturated compound), those containing an ester bond are also preferable from the viewpoint of excellent developability of the photosensitive layer after transfer.
The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. Saturated compounds are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate are more preferred.
From the viewpoint of imparting reliability, the ethylenically unsaturated compounds include an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms, and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure. It preferably contains a compound and
Ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecanedimethanol di(meth)acrylate. (Meth)acrylates are mentioned.

One preferred embodiment of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
As the polymerizable compound, a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure). Bifunctional ethylenically unsaturated compounds having a ring structure in which two or more aliphatic hydrocarbon rings are condensed are preferred, and tricyclodecanedimethanol di(meth)acrylate is even more preferred.
As the aliphatic hydrocarbon ring structure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoboron structure is preferable.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
Among the polymerizable compounds contained in the photosensitive layer, the content ratio of polymerizable compounds having a molecular weight of 300 or less is preferably 30% by mass or less with respect to the content of all polymerizable compounds contained in the photosensitive layer. , 25% by mass or less, and even more preferably 20% by mass or less.

As one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a bifunctional or higher ethylenically unsaturated compound, and more preferably contains a trifunctional or higher ethylenically unsaturated compound. More preferably, it contains a tetrafunctional ethylenically unsaturated compound.

Further, as one preferred embodiment of the photosensitive layer, the photosensitive layer comprises a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer having a structural unit having an aliphatic hydrocarbon ring. preferably included.

Further, as one preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, and 1,9-nonane More preferably, it contains diol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and 1,9-nonanediol diacrylate and tricyclodecanedimethanol diacrylate. More preferably, it contains an acrylate and a succinic acid modified form of dipentaerythritol pentaacrylate.

Further, as one preferred embodiment of the photosensitive layer, the photosensitive layer contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later. is preferable, and it is more preferable to contain a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

Further, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer is composed of a bifunctional ethylenically unsaturated compound (preferably, a bifunctional (meth) acrylate compound) and a tri- or more functional ethylenically unsaturated compound (preferably a tri- or more functional (meth)acrylate compound).
The content ratio by mass of the difunctional ethylenically unsaturated compound and the trifunctional or higher ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
The content of the bifunctional ethylenically unsaturated compound is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of all ethylenically unsaturated compounds.
The content of the bifunctional ethylenically unsaturated compound in the photosensitive layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.

Further, as one of preferred embodiments of the photosensitive layer, the photosensitive layer preferably contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. .
In addition, as one of the preferred embodiments of the photosensitive layer, the photosensitive layer includes the compound M and an ethylenically unsaturated compound having an acid group, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. It preferably contains a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and more preferably an ethylenically unsaturated compound having an acid group, compound M, an aliphatic hydrocarbon It is more preferable to contain a bifunctional ethylenically unsaturated compound having a ring structure, a trifunctional or higher ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, compound M, an aliphatic hydrocarbon ring structure. It is particularly preferable to include a difunctional ethylenically unsaturated compound having a trifunctional or more functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.
Further, as one preferred embodiment of the photosensitive layer, the photosensitive layer is composed of 1,9-nonanediol diacrylate, 1,9-nonanediol diacrylate, And preferably contains a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group more preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, 1 ,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, ethylenically unsaturated compounds having carboxylic acid groups, and urethane acrylate compounds are particularly preferred.

The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
The content of the bifunctional or higher ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive layer, and 80 ~100% by mass is more preferable, and 90 to 100% by mass is even more preferable.

Polymerizable compounds (especially, ethylenically unsaturated compounds) may be used singly or in combination of two or more.
The content of the polymerizable compound (especially the ethylenically unsaturated compound) in the photosensitive layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, more preferably 5 to 60% by mass, based on the total mass of the photosensitive layer. % by mass is more preferred, and 5 to 50% by mass is particularly preferred.

-Specific dye-
The photosensitive layer contains a specific dye.
The specific dye is a dye that has a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer, and the difference between the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer is 40 nm or more. Say.
The type and properties of the specific dye contained in the photosensitive layer (photosensitive layer B) and the relationship with the maximum sensitivity wavelength of the photosensitive layer are the same as for the photosensitive layer A described above, and the preferred embodiment is also the same. be.

As a preferred embodiment, when the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and the photosensitive layer contains a specific dye having a maximum absorption wavelength of 300 to 395 nm, the maximum absorption wavelength in the photosensitive layer is The content of dyes having a wavelength of more than 395 nm and 500 nm or less (the dyes referred to herein preferably do not include "dyes whose maximum absorption wavelength changes due to acids, bases, or radicals") is the total weight of the photosensitive layer. is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and more preferably 1.0% by mass or less in view of the superior effect of the present invention. It is preferably not more than 0.1% by weight, particularly preferably not more than 0.01% by weight. As a lower limit, it is 0 mass % or more.
As a particularly preferred embodiment, the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and when the photosensitive layer contains a specific dye having a maximum absorption wavelength of 300 to 395 nm, the maximum absorption wavelength in the photosensitive layer is more than 395 nm and 500 nm or less (the dye herein preferably does not include a "dye whose maximum absorption wavelength changes with acid, base or radical").

As a preferred embodiment, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and when the photosensitive layer contains a specific dye having a maximum absorption wavelength of more than 395 nm and 500 nm or less, the maximum absorption wavelength in the photosensitive layer is The content of dyes having a wavelength of 300 to 395 nm (the dyes referred to herein preferably do not include "dyes whose maximum absorption wavelength is changed by acids, bases or radicals") is based on the total weight of the photosensitive layer. On the other hand, it is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and further preferably 1.0% by mass or less from the viewpoint that the effect of the present invention is more excellent. , is particularly preferably 0.1% by weight or less, most preferably 0.01% by weight or less. As a lower limit, it is 0 mass % or more.
As a particularly preferred embodiment, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and when the photosensitive layer contains a specific dye having a maximum absorption wavelength of more than 395 nm and 500 nm or less, the maximum absorption wavelength in the photosensitive layer is 300 to 395 nm (the dye herein preferably does not include a "dye whose maximum absorption wavelength is changed by an acid, a base or a radical").

The content of the specific dye is preferably from 0.01 to 15.0% by mass, more preferably from 0.05 to 10.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint that the effects of the present invention are more excellent. %, more preferably 0.1 to 10.0% by mass, and particularly preferably 1.0 to 10.0% by mass.

-Polymerization initiator-
The photosensitive layer may contain a polymerization initiator.
A photopolymerization initiator is preferable as the polymerization initiator.
The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
As the photopolymerization initiator, a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an “oxime photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α- Also referred to as "aminoalkylphenone-based photopolymerization initiator".), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), an acylphosphine oxide structure A photopolymerization initiator having Also referred to as "agent".) and the like.

The photopolymerization initiator is selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based polymerization initiators, and N-phenylglycine-based photopolymerization initiators. It preferably contains at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators. is more preferable.

Further, as the photopolymerization initiator, for example, paragraphs [0031] to [0042] of JP-A-2011-95716, and paragraphs [0064] to [0081] of JP-A-2015-014783 A polymerization initiator may be used.

Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF Co., Ltd.], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02 , manufactured by BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 -[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad (registered trademark) 379EG, IGM Resins B.V. V company], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad (registered trademark) 907, IGM Resins B.V. V company], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad (registered trademark) 127 , IGM ResinsB. V company], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad (registered trademark) 369, IGM Resins B.V. V company], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad (registered trademark) 1173, IGM Resins B.V. V company], 1-hydroxycyclohexylphenyl ketone [trade name: Omnirad (registered trademark) 184, IGM Resins B.V. V company], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: Omnirad (registered trademark) 651, IGM Resins B.V. V company], etc., oxime ester [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione -2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Power Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2 -furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), 3-cyclohexyl-1-( 6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG- 391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.) and the like. .

A photoinitiator may be used individually by 1 type, and can also use 2 or more types. When two or more are used in combination, an oxime photopolymerization initiator and at least one selected from α-aminoalkylphenone photopolymerization initiators and α-hydroxyalkylphenone polymerization initiators can be used. preferable.
When the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, and 0.5% by mass or more, relative to the total weight of the photosensitive layer. is more preferable, and 1.0% by mass or more is even more preferable. Moreover, the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive composition layer.

-Heterocyclic compound-
The photosensitive layer may contain a heterocyclic compound.
The heterocyclic ring contained in the heterocyclic compound may be either monocyclic or polycyclic heterocyclic ring.
A nitrogen atom, an oxygen atom, and a sulfur atom are mentioned as a heteroatom which a heterocyclic compound has. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.
Among the above, the heterocyclic compound is at least one selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds. are preferred, and at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds is more preferred.

Preferred specific examples of the heterocyclic compound are shown below. Examples of triazole compounds and benzotriazole compounds include the following compounds.

Examples of tetrazole compounds include the following compounds.

Examples of thiadiazole compounds include the following compounds.

Examples of triazine compounds include the following compounds.

Examples of rhodanine compounds include the following compounds.

Examples of thiazole compounds include the following compounds.

Examples of benzothiazole compounds include the following compounds.

Examples of benzimidazole compounds include the following compounds.

Examples of benzoxazole compounds include the following compounds.

A heterocyclic compound may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, preferably 0.10 to 10.0% by mass, based on the total mass of the photosensitive layer. It is more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass.

- Aliphatic thiol compound -
The photosensitive layer may contain an aliphatic thiol compound.
When the photosensitive layer contains an aliphatic thiol compound, the en-thiol reaction between the aliphatic thiol compound and the radically polymerizable compound having an ethylenically unsaturated group suppresses curing shrinkage of the formed film. and stress is relieved.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher aliphatic thiol compound) is preferable.

Among them, polyfunctional aliphatic thiol compounds are preferable as the aliphatic thiol compound from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).

As used herein, a "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

A low-molecular-weight compound having a molecular weight of 100 or more is preferable as the polyfunctional aliphatic thiol compound. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, still more preferably 150 to 1,000.

The number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably 2 to 10 functional, more preferably 2 to 8 functional, and even more preferably 2 to 6 functional, from the viewpoint of adhesion of the pattern to be formed.

Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate ), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate pionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1, 3-propanedithiol, 1,6-hexamethylenedithiol, 2,2′-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

Among the above, polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5- At least one compound selected from the group consisting of tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

The photosensitive layer may contain a single aliphatic thiol compound, or may contain two or more aliphatic thiol compounds.

When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, based on the total mass of the photosensitive layer, 5 to 30% by mass % is more preferred, and 8 to 20% by mass is particularly preferred.

-Thermal crosslinkable compound-
The photosensitive layer preferably contains a thermal crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.
Thermally crosslinkable compounds include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.
Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when at least one of the binder polymer and the radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, The hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to be strengthened.
The blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".

Although the dissociation temperature of the blocked isocyanate compound is not particularly limited, it is preferably 100 to 160°C, more preferably 130 to 150°C.
The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
As the 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 to this.

Blocking agents having a dissociation temperature of 100 to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds ( Formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and compounds having a structure represented by -C(=N-OH)- in the molecule such as cyclohexanone oxime).
Among these, the blocking agent having a dissociation temperature of 100 to 160° C. is preferably at least one selected from oxime compounds from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent tend to have a dissociation temperature within a preferred range and produce less development residue than compounds having no oxime structure. It is preferable because it is easy to

The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and any known polymerizable group can be used, and a radically polymerizable group is preferred.
Polymerizable groups include groups having ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups, and styryl groups, and epoxy groups such as glycidyl groups.
Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and still more preferably an acryloxy group.

A commercial item can be used as a block isocyanate compound.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corp.).

The thermally crosslinkable compounds may be used singly or in combination of two or more.
When the photosensitive layer contains a heat-crosslinkable compound, the content of the heat-crosslinkable compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, based on the total weight of the photosensitive composition layer.

- Hydrogen donating compound -
The photosensitive layer may contain a hydrogen donating compound.
The hydrogen-donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

Hydrogen-donating compounds include, for example, amines and amino acid compounds.

Examples of amines include M.I. R. Sander et al., "Journal of Polymer Society", Vol. JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure 33825. More specifically, 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (alias: leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl dimethylaniline and p-methylthiodimethylaniline.
Among them, at least one selected from the group consisting of 4,4′-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane is used as the amine, since the effects of the present invention are more excellent. preferable.

Amino acid compounds include, for example, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine.
Among them, N-phenylglycine is preferable as the amino acid compound because the effects of the present invention are more excellent.

Further, as the hydrogen-donating compound, for example, an organometallic compound (such as tributyltin acetate) described in JP-B-48-042965, a hydrogen donor described in JP-B-55-034414, and JP-A-6 Also included are sulfur compounds (such as trithiane) described in JP-A-308727.

The hydrogen-donating compounds may be used singly or in combination of two or more.
When the photosensitive layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is 0.00% relative to the total weight of the photosensitive layer, from the viewpoint of improving the curing rate by the balance between the polymerization growth rate and the chain transfer. 01 to 10.0% by mass is preferable, 0.01 to 8.0% by mass is more preferable, and 0.03 to 5.0% by mass is even more preferable.

－Other Additives－
The photosensitive layer may contain additives other than those mentioned above.
The other additives are the same as the other additives contained in the photosensitive layer A described above, and the preferred embodiments are also the same.

-impurities-
The photosensitive layer may contain impurities.
The impurities are the same as those in the photosensitive layer A described above, and the preferred embodiments are also the same.

-Other ingredients-
The photosensitive layer may contain components other than the components described above (hereinafter also referred to as "other components"). Other ingredients include, for example, colorants, antioxidants, and particles (eg, metal oxide particles). Further, as other components, other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can also be mentioned.

-particle-
As the particles, metal oxide particles are preferred.
Metals in metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
The average primary particle size of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of the transparency of the cured film.
The average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.

-coloring agent-
Although the photosensitive layer may contain a slight amount of coloring agent (pigment, dye, etc.), it is preferred that the photosensitive layer does not substantially contain coloring agent, for example, from the viewpoint of transparency.
When the photosensitive layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the photosensitive layer.

-Antioxidant-
Examples of antioxidants include 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine be done.
Among them, 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant, because the effects of the present invention are more excellent.

-Characteristics of photosensitive layer (photosensitive layer B)-
The average thickness of the photosensitive layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, even more preferably 1 to 20 μm. Thereby, the developability of the photosensitive layer can be improved, and the resolution can also be improved.
The average thickness of the photosensitive layer is the average of 10 thicknesses measured by observing a cross section perpendicular to the in-plane direction of the photosensitive layer using a scanning electron microscope (SEM). value.

(middle layer)
In the composition layer, the intermediate layer is present between the thermoplastic resin layer and the photosensitive layer, and can be formed during the coating formation of the thermoplastic resin layer and the photosensitive layer and during storage after coating formation. Mixing of components can be suppressed.
A water-soluble resin layer containing a water-soluble resin can be used as the intermediate layer.
As the intermediate layer, an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-072724, can also be used. It is preferable that the intermediate layer is an oxygen-blocking layer because the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved.
The oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers described in the above publications. Among them, an oxygen-blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred.

Each component that can be included in the water-soluble resin layer (intermediate layer) is described below.

-Water-soluble resin-
The water-soluble resin layer (intermediate layer) contains a resin.
The resin includes a water-soluble resin as part or all of it.
Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Examples include resins such as coalescence.
A (meth)acrylic acid/vinyl compound copolymer or the like can also be used as the water-soluble resin. As the (meth)acrylic acid/vinyl compound copolymer, a (meth)acrylic acid/allyl (meth)acrylate copolymer is preferable, and a methacrylic acid/allyl methacrylate copolymer is more preferable.
When the water-soluble resin is a (meth)acrylic acid/vinyl compound copolymer, the composition ratio (mol%) is preferably 90/10 to 20/80, and preferably 80/20 to 30/70. more preferred.

The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Moreover, the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
The dispersity (Mw/Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.

In order to further improve the ability of the water-soluble resin layer (intermediate layer) to suppress interlayer mixing, the resin in the water-soluble resin layer (intermediate layer) is arranged on one side of the water-soluble resin layer (intermediate layer). It is preferable that the resin contained in the layer on which the second surface is arranged is different from the resin contained in the layer arranged on the other surface side.

The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of further improving the oxygen blocking property and the property of suppressing interlayer mixing.

One type of water-soluble resin may be used alone, or two or more types may be used.
Although the content of the water-soluble resin is not particularly limited, it is preferably 50% by mass or more with respect to the total mass of the water-soluble resin layer (intermediate layer) in order to further improve the oxygen barrier property and the ability to suppress interlayer mixing. , more preferably 70% by mass or more. Although the upper limit is not particularly limited, for example, 99.9% by mass or less is preferable, and 99.8% by mass or less is more preferable.

The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the inter-layer mixing suppression ability is excellent without lowering the oxygen barrier properties. Furthermore, it is possible to suppress the increase in the time required for removing the water-soluble resin layer (intermediate layer) during development.

The thickness of the intermediate layer is preferably 3.0 μm or less, more preferably 2.0 μm or less. The lower limit is preferably 1.0 μm or more.

(Thermoplastic resin layer)
A thermoplastic resin layer is usually arranged between the temporary support and the photosensitive layer. By providing the transfer film with the thermoplastic resin layer, followability to the substrate is improved in the bonding process of the transfer film and the substrate, and entrapment of air bubbles between the substrate and the transfer film can be suppressed. As a result, it is possible to ensure adhesion with a layer (for example, a temporary support) adjacent to the thermoplastic resin layer.
Examples of the thermoplastic resin layer include paragraphs [0189] to [0193] of JP-A-2014-085643, the contents of which are incorporated herein.
Each component that the thermoplastic resin layer may contain will be described below.

-Thermoplastic resin layer-
The thermoplastic resin layer contains a thermoplastic resin.
As the thermoplastic resin, an alkali-soluble resin is preferred.
Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, and polyhydroxystyrene resins. , polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.
As the alkali-soluble resin, the alkali-soluble resin contained in the photosensitive layer described above may be used.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.
Here, the "acrylic resin" is selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. means a resin containing at least one structural unit
In acrylic resins, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides is equal to the total mass of the acrylic resin. On the other hand, 30% by mass or more is preferable, and 50% by mass or more is more preferable. The upper limit is preferably 100% by mass or less with respect to the total mass of the acrylic resin.
Among them, the total content of structural units derived from (meth) acrylic acid and structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, based on the total mass of the acrylic resin, and 50 to 100% by mass is more preferred.

A resin having an acid group is preferable as the alkali-soluble resin.
The acid group includes, for example, a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, with the carboxy group being preferred.
Further, the alkali-soluble resin preferably contains a structural unit having an acid group, and more preferably contains a structural unit having a carboxy group. Acrylic resins having structural units derived from acrylic acid are more preferred.

The acid value of the alkali-soluble resin is preferably 60 mgKOH/g or more from the viewpoint of developability. The upper limit is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Among them, as the alkali-soluble resin, an alkali-soluble resin having an acid value of 60 mgKOH/g or more is preferable, and an acrylic resin having a carboxyl group having an acid value of 60 mgKOH/g or more is more preferable.

As the acrylic resin having a carboxyl group with an acid value of 60 mgKOH/g or more, for example, it can be appropriately selected from known resins and used.
Specifically, paragraph [0025] of JP-A-2011-095716, paragraphs [0033] to [0052] of JP-A-2010-237589 and paragraphs [0053] to [0068 of JP-A-2016-224162 ] is mentioned.

The content of structural units having a carboxy group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

The alkali-soluble resin may have a polymerizable group.
The polymerizable group may be any group as long as it participates in the polymerization reaction, for example, a group having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group; an epoxy group, an oxetane group, and the like. group having a cationic polymerizable group.
Among them, as the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

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

The thermoplastic resin may be used singly or in combination of two or more.
The content of the thermoplastic resin is preferably 10.0 to 99.0% by mass, preferably 20.0 to 90%, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. 0% by mass is more preferable, 40.0 to 90.0% by mass is even more preferable, and 60.0 to 90.0% by mass is particularly preferable.

-Dye B-
The thermoplastic resin layer contains a dye having a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development, and a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter also simply referred to as "dye B"). may contain.
The preferred embodiments of the dye B are the same as those of the above dye N, and the preferred embodiments are also the same, except for the points described later.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoints of visibility in exposed and unexposed areas and resolution. .
From the viewpoint of visibility of exposed and unexposed areas and resolution, the thermoplastic resin layer contains both a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound that generates an acid by light, which will be described later. is preferably included.

You may use the pigment|dye B individually by 1 type or in 2 or more types.
The content of the dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6.0% by mass, based on the total mass of the thermoplastic resin layer in terms of visibility of the exposed and unexposed areas. More preferably, 0.2 to 5.0% by mass is even more preferable.
The “content of dye B” means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example.
A solution of dye B (0.001 g) and a solution of dye B (0.01 g) in 100 mL of methyl ethyl ketone are prepared. A radical photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm, so that all the dyes B are colored. After that, the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
Then, in the same manner as described above, except that the thermoplastic resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dye B, the absorbance of the solution in which all the dyes are developed is measured. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye B contained in the thermoplastic resin layer is calculated based on the calibration curve.

- A compound (compound C) that generates an acid, base or radical upon exposure to light -
The thermoplastic resin layer may contain a compound that generates an acid, base, or radical upon exposure to light (hereinafter also simply referred to as "compound C").
Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.
Examples of the compound C include known photoacid generators, photobase generators and photoradical polymerization initiators (photoradical generators).

..Photo-acid generator The thermoplastic resin layer may contain a photo-acid generator from the viewpoint of resolution.
The photoacid generator includes, for example, a photocationic polymerization initiator that can be contained in the photosensitive layer.

From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. Therefore, it is more preferred to include an oxime sulfonate compound.
As the photoacid generator, a photoacid generator having the following structure is also preferable.

.. Radical photopolymerization initiator The thermoplastic resin layer may contain a radical photopolymerization initiator.
Examples of photoradical polymerization initiators include photoradical polymerization initiators that can be contained in the photosensitive layer, and preferred embodiments are also the same.

..Photobase generator The thermoplastic resin composition may contain a photobase generator.
Examples of the photobase generator include known photobase generators.
Specifically, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2- nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-( 2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3 ,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine. be done.

You may use the compound C individually by 1 type or in 2 or more types.
The content of the compound C is preferably 0.1 to 10.0% by mass relative to the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed and unexposed areas and resolution, and 0 0.5 to 5.0% by mass is more preferable.

-Plasticizer-
The thermoplastic resin layer may contain a plasticizer from the viewpoint of resolution, adhesion to adjacent layers, and developability.
The plasticizer preferably has a smaller molecular weight (weight-average molecular weight if it is an oligomer or polymer and has a molecular weight distribution) than the thermoplastic resin (preferably alkali-soluble resin). Specifically, the molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
The plasticizer is not particularly limited as long as it is a compound compatible with the alkali-soluble resin and exhibits plasticity.
From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
Polyalkylene glycol compounds are preferred as plasticizers.

The plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution and adhesion with adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.
The (meth)acrylate compound includes, for example, a (meth)acrylate compound as a polymerizable compound that can be contained in the photosensitive layer.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, the (meth)acrylate compound may not be polymerized even in the exposed areas after exposure from the viewpoint of adhesion between the thermoplastic resin layer and adjacent layers. preferable.
In addition, the (meth)acrylate compound is a polyfunctional compound having two or more (meth)acryloyl groups in one molecule, from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability. (Meth)acrylate compounds are preferred.
Furthermore, as the (meth)acrylate compound, a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferable.

A preferred embodiment of the plasticizer includes an alkylene oxide-modified tri- or higher ethylenically unsaturated compound, an alkylene glycol di(meth)acrylate, and a di- or higher-functional urethane (meth)acrylate (preferably urethane di(meth) ) acrylates) are also preferred. Preferred examples of these compounds include the same compounds described as the polymerizable compounds that can be contained in the photosensitive layer.

You may use a plasticizer by 1 type individual or in 2 or more types.
The content of the plasticizer is 0.5 to 40.0% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to adjacent layers, and the developability. is preferred, 1.0 to 40.0 mass % is more preferred, and 5.0 to 40.0 mass % is even more preferred.

- Sensitizer -
The thermoplastic resin layer may contain a sensitizer.
Sensitizers include sensitizers that can be included in the photosensitive layer.

A sensitizer may be used singly or in combination of two or more.
The content of the sensitizer is 0.01 to 10.0% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoint of improving sensitivity to light sources and visibility of exposed and unexposed areas. Preferably, 0.05 to 8.0% by mass is more preferable.

-Polymerization inhibitor-
The polymerization inhibitor may contain impurities.
Polymerization inhibitors include, for example, impurities contained in the photosensitive layer.
The content of the polymerization inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 1.0% by mass, with respect to the total mass of the thermoplastic resin layer in that the effect of the present invention is more excellent. is more preferred.

－Other Additives－
The thermoplastic resin layer may contain other additives in addition to the above components.
Other additives include, for example, other additives that can be contained in the photosensitive layer.

-impurities-
The thermoplastic resin layer may contain impurities.
Impurities include, for example, impurities that may be contained in the photosensitive layer.

The average thickness (layer thickness) of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. The upper limit is preferably 20 µm or less, more preferably 10 µm or less, and even more preferably 8 µm or less, from the viewpoint of developability and resolution.
Examples of the method for measuring the average thickness include the method for measuring the average thickness of the photosensitive layer A.

(Other layers)
The composition layer may contain layers other than the photosensitive layer, the intermediate layer, and the thermoplastic resin layer. Other layers include an intermediate layer (hereinafter also referred to as "intermediate layer A") disposed between the temporary support and the photosensitive layer.

-Intermediate layer A-
The intermediate layer A is preferably a layer having a function of improving the peelability of the temporary support and/or having an oxygen barrier function. Further, the intermediate layer A is preferably a layer that is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22° C.).
As the intermediate layer A, a water-soluble resin layer containing a water-soluble resin can be used.

Each component that the water-soluble resin layer (intermediate layer A) may contain will be described below.
The intermediate layer A contains a water-soluble resin.
Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins (e.g., water-soluble cellulose derivatives such as hydroxypropylcellulose and hydroxypropylmethylcellulose), acrylamide-based resins, and polyethers. resins (for example, polyalkylene oxide resins such as polyethylene glycol and polypropylene glycol), gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.
A (meth)acrylic acid/vinyl compound copolymer or the like can also be used as the water-soluble resin. As the (meth)acrylic acid/vinyl compound copolymer, a (meth)acrylic acid/allyl (meth)acrylate copolymer is preferable, and a methacrylic acid/allyl methacrylate copolymer is more preferable. When the water-soluble resin is a (meth)acrylic acid/vinyl compound copolymer, the composition ratio (mol%) is preferably 90/10 to 20/80, and preferably 80/20 to 30/70. more preferred.

The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Moreover, the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
The dispersity (Mw/Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.

The water-soluble resin preferably contains one or more selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone, more preferably polyvinyl alcohol, and still more preferably both polyvinyl alcohol and polyvinylpyrrolidone. The compounding ratio (mass ratio) of polyvinyl alcohol and polyvinylpyrrolidone is preferably 5/95 to 95/5, more preferably 20/80 to 80/20, and even more preferably 25/75 to 70/25. .
Further, as the water-soluble resin, it is preferable to use at least one selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone in combination with at least one of water-soluble cellulose derivatives and polyethers. It is more preferable to use at least one selected from the group consisting of a water-soluble cellulose derivative in combination.
When one or more selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone is used in combination with a water-soluble cellulose derivative as a water-soluble resin, the peelability of the temporary support is further improved and/or the oxygen blocking ability. is more excellent, the content of the water-soluble cellulose derivative is preferably less than 10% by mass relative to the total content of polyvinyl alcohol, polyvinylpyrrolidone, and the water-soluble cellulose derivative, and 5% by mass or less. It is more preferable to have Although the lower limit is not particularly limited, it is preferably 0.1% by mass or more, for example.

Examples of water-soluble cellulose derivatives include, but are not limited to, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and ethyl cellulose.
Polyethers include polyethylene glycol and polypropylene glycol.

One type of water-soluble resin may be used alone, or two or more types may be used.
Although the content of the water-soluble resin is not particularly limited, it is 40% by mass based on the total mass of the intermediate layer A in terms of further improving the peelability of the temporary support and/or more excellent oxygen blocking ability. The above is preferable, and 50% by mass or more is more preferable. Although the upper limit is not particularly limited, it is, for example, 90% by mass or less, preferably 80% by mass or less.

In addition, the intermediate layer A may contain other components than the above water-soluble resin. Examples of other components include polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives, and amide compounds.

[Modification of Transfer Film of First Embodiment]
In the upper part, the transfer film of the first embodiment was mentioned as an example of the transfer film in which the photosensitive layer contains a specific dye, but the transfer film in which the photosensitive layer contains a specific dye is not limited to the above configuration.
Another example of a transfer film in which the photosensitive layer contains a specific dye is a composition layer having a two-layer structure consisting of a temporary support, an intermediate layer A and a photosensitive layer containing a specific dye in order from the temporary support side, and a protective film in this order.
Another example of a transfer film in which a photosensitive layer contains a specific dye is a transfer film having a temporary support, a photosensitive layer containing a specific dye, and a protective film in this order. In addition, in the case of the transfer film of the above aspect, the composition layer has a single-layer configuration of the photosensitive layer.
Furthermore, the transfer film mentioned above as a modified example of the transfer film of the first embodiment may not include a protective film.

[Transfer Film of Second Embodiment]
An example of an embodiment of the transfer film of the second embodiment will be described below.
The transfer film 50 shown in FIG. , in that order. The thermoplastic resin layer 53 contains a specific pigment.
In addition, although the transfer film 50 shown in FIG. 4 has a form in which the protective film 41 is arranged, the protective film 41 may not be arranged.
The photosensitive layer 57 may or may not contain a specific dye.

Each element constituting the transfer film will be described below.
The transfer film of the second embodiment is the same as the transfer film of the first embodiment, except that the thermoplastic resin layer contains the specific dye and the photosensitive layer does not need to contain the specific dye. It has the same configuration as

<Thermoplastic resin layer>
-Specific dye-
The thermoplastic resin layer contains a specific dye.
The specific dye contained in the thermoplastic resin layer has the same meaning as the specific dye contained in the photosensitive layer of the transfer film of the first embodiment described above, and the preferred embodiments are also the same.
As described above, the specific dye preferably does not contain a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (for example, a dye B to be described later).

In the transfer film of the second embodiment, as an example of a preferred embodiment of the combination of the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the specific dye, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and the specific dye has a maximum absorption wavelength of more than 395 nm and 500 nm or less. In the above embodiment, the maximum absorption wavelength of the specific dye is also preferably 410 to 500 nm.
Another preferred embodiment of the combination of the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the specific dye is that the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and the maximum absorption wavelength of the specific dye is is 300 to 395 nm. In the above embodiment, the maximum sensitivity wavelength of the photosensitive layer is preferably from 410 to 500 nm, more preferably from 410 to 450 nm.

As a preferred embodiment of the thermoplastic resin layer, the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and the thermoplastic resin layer contains a specific dye having a maximum absorption wavelength of 300 to 395 nm. A dye having a maximum absorption wavelength in the layer of more than 395 nm and 500 nm or less (the dye referred to here preferably does not include "a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (e.g., dye B)"). The content of is preferably 5.0% by mass or less with respect to the total mass of the thermoplastic resin layer, and more preferably 2.0% by mass or less in terms of more excellent effects of the present invention. It is preferably 1.0% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less. As a lower limit, it is 0 mass % or more.
As a particularly preferred embodiment of the thermoplastic resin layer, the maximum sensitivity wavelength of the photosensitive layer is more than 395 nm and 500 nm or less, and the thermoplastic resin layer has a maximum absorption wavelength of 300 to 395 nm. A dye having a maximum absorption wavelength of more than 395 nm and 500 nm or less in the resin layer (the dye referred to here preferably does not include a “dye whose maximum absorption wavelength changes with acid, base, or radical (for example, dye B)”. ) is not included.

As a preferred embodiment of the thermoplastic resin layer, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and the photosensitive layer contains a specific dye having a maximum absorption wavelength of more than 395 nm and 500 nm or less. containing a dye having a maximum absorption wavelength of 300 to 395 nm in The amount is preferably 5.0% by mass or less with respect to the total mass of the thermoplastic resin layer, and more preferably 2.0% by mass or less from the viewpoint that the effects of the present invention are more excellent. It is more preferably 1.0% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less. As a lower limit, it is 0 mass % or more.
As a particularly preferred embodiment of the thermoplastic resin layer, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and the thermoplastic resin layer has a maximum absorption wavelength of more than 395 nm and 500 nm or less. A dye having a maximum absorption wavelength of 300 to 395 nm in the layer (the dye referred to here preferably does not include a “dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (for example, dye B)”). An aspect that does not include it is exemplified.

The content of the specific dye is preferably 0.01 to 20.0% by mass, more preferably 0.05 to 15.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint that the effects of the present invention are more excellent. % by mass is more preferred, and 1.0 to 10.0% by mass is even more preferred.

-Preferred embodiment of the content of each component in the thermoplastic resin layer-
A suitable example of the content of each of the above components in the thermoplastic resin layer is, for example, 20.0 to 90.0% by mass of the resin and 5.0% of the plasticizer with respect to the total mass of the thermoplastic resin layer. 40.0% by mass, 0 to 10.0% by mass of compound C, and 0.01 to 20.0% by mass of a specific dye.
Further, another preferred example of the content of each of the above components in the thermoplastic resin layer is, for example, 40.0 to 90.0% by mass of the resin and the plasticizer with respect to the total mass of the thermoplastic resin layer. 5.0 to 40.0% by mass, 0 to 10.0% by mass of compound C, and 0.01 to 20.0% by mass of a specific dye.
Further, another preferred example of the content of each of the above components in the thermoplastic resin layer is, for example, 40.0 to 90.0% by mass of the resin and the plasticizer with respect to the total mass of the thermoplastic resin layer. 5.0 to 40.0% by mass, 0 to 10.0% by mass of compound C, and 1.0 to 10.0% by mass of a specific dye.

<Photosensitive layer>
In the transfer film of the second embodiment, the photosensitive layer may or may not contain a specific dye.
The photosensitive layer containing no specific dye is the same as the photosensitive layer of the transfer film of the above-described first embodiment except that the photosensitive layer does not contain the specific dye, and the preferred embodiment is also the same. As the photosensitive layer that does not contain a specific dye, the aforementioned photosensitive layer A that does not contain a specific dye is particularly preferable.
Further, the photosensitive layer containing the specific dye is the same as the photosensitive layer of the transfer film of the above-described first embodiment, and the preferred mode is also the same. Among them, the photosensitive layer A described above is preferable as the photosensitive layer containing the specific dye.

-Preferred embodiment of the content of each component in the photosensitive layer containing no specific dye-
Preferred embodiments of the content of each component in the photosensitive layer containing no specific dye are described below.
The photosensitive layer that does not contain a specific dye preferably contains a resin, a polymerizable compound, and a polymerization initiator, and more preferably contains a resin, a polymerizable compound, a polymerization initiator, and a sensitizer. More preferably, it contains a polymerizable compound, a polymerization initiator, a sensitizer, and a polymerization inhibitor.
Moreover, it is also preferable that the resin includes an alkali-soluble resin.
A suitable example of the content of each of the above components in the photosensitive layer is, for example, 10.0 to 90.0% by weight of the resin and 5.0 to 5.0% of the polymerizable compound with respect to the total weight of the photosensitive layer. 70.0% by mass, and an embodiment containing 0.01 to 15.0% by mass of a polymerization initiator.
Further, another preferred example of the content of each of the components in the photosensitive layer is, for example, 10.0 to 90.0% by weight of the resin and the polymerizable compound with respect to the total weight of the photosensitive layer. Examples include an embodiment containing 5.0 to 70.0% by mass, 0.01 to 10.0% by mass of a polymerization initiator, and 0.01 to 5.0% by mass of a sensitizer.
Further, another preferred example of the content of each of the components in the photosensitive layer is, for example, 10.0 to 90.0% by weight of the resin and the polymerizable compound with respect to the total weight of the photosensitive layer. 5.0 to 70.0% by mass, 0.01 to 10.0% by mass of a polymerization initiator, 0.01 to 5.0% by mass of a sensitizer, and 0.001 to 0.001% by mass of a polymerization inhibitor. An aspect containing 5% by mass is mentioned.

[Modification of Transfer Film of Second Embodiment]
In the upper part, the transfer film of the second embodiment was mentioned as an example of the transfer film in which the thermoplastic resin layer contains a specific dye, but the transfer film in which the photosensitive layer contains a specific dye is not limited to the above configuration.
Another example of a transfer film in which a thermoplastic resin layer contains a specific dye includes a temporary support, a thermoplastic resin layer containing a specific dye in order from the temporary support side, an intermediate layer, and a photosensitive layer containing a specific dye. and a protective film in this order. As the photosensitive layer containing the specific dye, the photosensitive layer in the transfer film of the first embodiment can be applied.
Furthermore, the transfer film mentioned above as a modified example of the transfer film of the second embodiment may not include a protective film.

In addition to the modes described in the first and second embodiments, the intermediate layer in the composition layer may contain a specific dye.

[Manufacturing method of transfer film]
The method of manufacturing the transfer film of the first embodiment and the second embodiment (hereinafter also referred to as "method of manufacturing the transfer film") is not particularly limited, and known methods can be used.
For example, the method for producing the transfer film 30 shown in FIG. 3 and the transfer film 40 shown in FIG. A step of drying to form a thermoplastic resin layer, a step of applying a water-soluble resin composition to the surface of the thermoplastic resin layer to form a coating film, and further drying this coating film to form an intermediate layer and a step of applying a composition for forming a photosensitive layer to the surface of the intermediate layer to form a coating film, and further drying the coating film to form a photosensitive layer.

The transfer film 30 shown in FIG. 3 and the transfer film 40 shown in FIG. 4 are produced by pressing a protective film onto the photosensitive layer of the laminate produced by the above-described production method.
Further, the transfer film 30 shown in FIG. 3 and the transfer film 40 shown in FIG. 4 may be wound up after being manufactured and stored as a roll-shaped transfer film. The transfer film in roll form can be provided as it is in the step of laminating with a substrate in a roll-to-roll system, which will be described later.

3 and the transfer film 40 shown in FIG. 4, after forming a photosensitive layer and an intermediate layer on a protective film, a thermoplastic resin layer is formed on the surface of the intermediate layer. It may be a manufacturing method of forming.

<Method for Forming Thermoplastic Resin Composition and Thermoplastic Resin Layer>
The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and known methods can be used. For example, it can be formed by applying a thermoplastic resin composition onto a temporary support and drying it if necessary.
The thermoplastic resin composition preferably contains the above-described various components forming the thermoplastic resin layer and a solvent. In addition, in the thermoplastic resin composition, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the thermoplastic resin layer described above.
The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Examples of the solvent include those similar to the solvent contained in the photosensitive composition described later, and the preferred embodiments are also the same.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. For example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) mentioned.

<Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)>
The method for forming the intermediate layer on the thermoplastic resin layer is not particularly limited, and known methods can be used. For example, it can be formed by applying a water-soluble resin composition onto the thermoplastic resin layer and drying it as necessary.
The water-soluble resin composition preferably contains various components and a solvent for forming the intermediate layer (water-soluble resin layer) described above. In the water-soluble resin composition, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the water-soluble resin layer described above.
The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, preferably at least one selected from the group consisting of water and water-miscible organic solvents, water or water and water-miscible organic solvents A mixed solvent with a solvent is more preferable.
Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
A solvent may be used individually by 1 type, and may be used 2 or more types.
The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. For example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) mentioned.

<Composition for forming photosensitive layer and method for forming photosensitive layer>
The method for forming the photosensitive layer on the intermediate layer is not particularly limited, and known methods can be used. For example, the photosensitive layer can be formed by applying a composition for forming a photosensitive layer onto the intermediate layer and drying it as necessary.
The photosensitive layer-forming composition preferably contains the above-described various components for forming the photosensitive layer and a solvent. In addition, in the photosensitive layer-forming composition, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the photosensitive layer described above.
The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar Solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these can be mentioned.

The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable. A mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferable.

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ethers.
Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
As the solvent, the solvent described in paragraphs [0092] to [0094] of WO 2018/179640, and the solvent described in paragraph [0014] of JP-A-2018-177889 may be used. the contents of which are incorporated herein.
A solvent may be used individually by 1 type, and may be used 2 or more types.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

Examples of the method of applying the composition for forming a photosensitive layer include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method). be done.

Heat drying and reduced pressure drying are preferable as a method for drying the coating film of the composition for forming a photosensitive layer.

Furthermore, the transfer film of the first embodiment and the second embodiment can be produced by laminating the protective film to the photosensitive layer.
A method for bonding the protective film to the photosensitive layer is not particularly limited, and known methods can be used.
Apparatuses for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an autocut laminator.
Preferably, the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.

In the method for producing a transfer film, when the intermediate layer A is provided between the temporary support and the photosensitive layer, the method for forming the intermediate layer A may be the above-described <water-soluble resin composition and intermediate layer (water-soluble resin layer ) method>.

[Use of transfer film]
The transfer film of the present invention is applied to a substrate with a transparent conductive layer (substrate with a transparent conductive layer) having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate.
The substrate with a transparent conductive layer will be described below.

<Transparent substrate>
A base material with a transparent conductive layer has a transparent base material.
Materials for the transparent substrate include, for example, resin materials and inorganic materials.
Examples of resin materials include polyester (eg, polyethylene terephthalate and polyethylene naphthalate), polyetheretherketone, acrylic resin, cycloolefin polymer, and polycarbonate.
Examples of inorganic materials include glass and quartz.

The transparent substrate is preferably a resin film, preferably a polyethylene terephthalate film, a polyethylene naphthalate film, or a cycloolefin polymer film.

The thickness of the transparent substrate is not particularly limited. The average thickness of the transparent substrate is preferably from 10 to 100 μm, more preferably from 10 to 60 μm, from the viewpoints of transportability, electrical properties, and film-forming properties. The average thickness of the transparent substrate is the average of 10 thicknesses measured by observing a cross section perpendicular to the in-plane direction of the transparent substrate using a scanning electron microscope (SEM). value.

<Transparent conductive layer>
The substrate with a transparent conductive layer has transparent conductive layers arranged on both sides of the transparent substrate. That is, the substrate with a transparent conductive layer has a first transparent conductive layer and a second transparent conductive layer on two opposing surfaces of the transparent substrate, as shown in FIG.

The volume resistivity of the transparent conductive layer is preferably less than 1×10 ⁶ Ωcm, more preferably less than 1×10 ⁴ Ωcm. Note that the lower limit is 1 Ωcm or more. The volume resistivity is measured using a known resistivity meter (eg EC-80P, manufactured by Napson Co., Ltd.).

The transparent conductive layer preferably contains at least one selected from the group consisting of metal nanowires and metal nanoparticles.
Examples of metal nanoparticles include metal nanoparticles such as silver nanoparticles, copper nanoparticles, gold nanoparticles, and platinum nanoparticles. Examples of metal nanowires include silver nanowires, copper nanowires, gold nanowires, platinum nanowires, and the like, and silver nanoparticles or silver nanowires are preferable because of their superior transparency.

The thickness of the transparent conductive layer is not particularly limited. The average thickness of the transparent conductive layer is preferably 0.001 to 1,000 μm, more preferably 0.005 to 15 μm, more preferably 0.01 to 10 μm is even more preferred. The average thickness of the transparent conductive layer is measured by a method according to the method for measuring the average thickness of the transparent substrate.

The transparent conductive layer may be arranged on the entire transparent substrate, or may be arranged on a part of the transparent substrate.

In addition, the substrate with a transparent conductive layer is used for the purpose of, for example, protecting the transparent conductive layer, controlling electrical properties, and controlling the adhesion between the transparent conductive layer and the transfer film after bonding the transfer film to the transparent conductive layer. , the surface of the transparent conductive layer opposite to the transparent base material side may further have another layer.
The other layers are not particularly limited. The other layer may be a layer composed of an organic substance, a layer composed of an inorganic substance, a layer in which an inorganic substance is dispersed in an organic matrix, a layer in which an organic substance is dispersed in an inorganic matrix, or the like. .

(Method for forming base material with transparent conductive layer)
The method for forming the substrate with the transparent conductive layer is not particularly limited, and known methods can be used.
Examples of the method of forming the base material with a transparent conductive layer include a method of forming a transparent conductive layer on a transparent base material by coating, vacuum deposition, sputtering, plating, or the like.
When the base material with the transparent conductive layer has another layer on the surface opposite to the transparent base material side of the first transparent conductive layer, methods for forming the other layer include, for example, coating, vacuum deposition, sputtering, and known methods such as lamination.

[Laminate]
The laminate of the present invention comprises a substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate; and a film.
The base material with the transparent conductive layer of the laminate has the same meaning as the base material with the transparent conductive layer described above, and the preferred embodiments are also the same.
Moreover, the transfer film of the present invention described above corresponds to the transfer film of the laminate.

The laminate is formed by bonding the transfer film of the present invention to the base material with the transparent conductive layer. At the time of bonding, it is preferable to bond the surface exposed by peeling the protective film and the transparent conductive layer of the substrate with the transparent conductive layer after peeling off the protective film in the transfer film. Moreover, after bonding, the temporary support in the transfer film may be peeled off. In other words, the laminate may or may not have a temporary support.

A specific example of the laminate is the laminate 20 shown in FIGS. 1 and 2 .

In one transfer film in the laminate, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, the maximum absorption wavelength of the specific dye is more than 395 nm and 500 nm or less, and the other transfer film has the maximum sensitivity wavelength of the photosensitive layer. is more than 395 nm and 500 nm or less, the maximum absorption wavelength of the specific dye is preferably 300 to 395 nm, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395 nm, and the maximum absorption wavelength of the specific dye is 410 to 500 nm. More preferably, in the other transfer film, the maximum sensitivity wavelength of the photosensitive layer is 410 to 500 nm, and the maximum absorption wavelength of the specific dye is 300 to 395 nm.

[Pattern formation method]
The pattern forming method of the present invention comprises
A method for forming a pattern by exposing and developing the transfer film in the laminate of the present invention,
A first exposure step of exposing the photosensitive layer (hereinafter also referred to as "first photosensitive layer") in one transfer film in the laminate;
A second exposure step of exposing the photosensitive layer (hereinafter also referred to as “second photosensitive layer”) in the other transfer film in the laminate;
A first development step of developing the first photosensitive layer exposed through the first exposure step to form a resin pattern;
and a second developing step of developing the second photosensitive layer exposed through the second exposure step to form a resin pattern.

In the pattern forming method of the present invention, among others, the dominant wavelength λ ₁ of the exposure wavelength in the first exposure step is different from the dominant wavelength λ ₂ of the exposure wavelength in the second exposure step (in other words, λ ₁ ≠ λ ₂ ).

Each step of the pattern forming method of the present invention will be specifically described below.
In addition, in the pattern forming method of the present invention, the laminate of the present invention and its preferred embodiment are as described above.

[First exposure step]
In the first photosensitive layer exposed in the first exposure step, the solubility in the developer changes between the exposed area and the unexposed area. For example, when the first photosensitive layer is a positive photosensitive layer, the exposed portion of the first photosensitive layer is more soluble in a developer than the unexposed portion. On the other hand, for example, when the first photosensitive layer is a negative photosensitive layer, the exposed portion of the first photosensitive layer is less soluble in a developer than the unexposed portion.

Examples of the method of exposing the first photosensitive layer include a method using a photomask. For example, by placing a photomask between the first photosensitive layer and the light source, the first photosensitive layer can be exposed in a pattern through the photomask. By subjecting the first photosensitive layer to pattern exposure, an exposed portion and an unexposed portion can be formed in the first photosensitive layer.

In the first exposure step, the first photosensitive layer and the photomask are preferably brought into contact with each other for exposure. The resolution can be improved by a method in which the first photosensitive layer and the photomask are brought into contact with each other for exposure (referred to as "contact exposure").

In the first exposure step, in addition to the contact exposure described above, a proximity exposure method, a lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser or the like may be appropriately selected and used. . In the case of a lens-based projection exposure system, an exposure machine with an appropriate lens numerical aperture (NA) can be used according to the required resolution and depth of focus. In the case of the direct exposure method, drawing may be performed directly on the photosensitive layer, or reduction projection exposure may be performed on the photosensitive layer via a lens. Moreover, the exposure may be performed not only in the air but also in a reduced pressure or a vacuum, and the exposure may be performed by interposing a liquid such as water between the light source and the photosensitive layer.

When a temporary support is arranged on the first photosensitive layer, the first photosensitive layer may be exposed through the temporary support, and the first photosensitive layer may be exposed after removing the temporary support from the first photosensitive layer. One photosensitive layer may be exposed. When exposing the first photosensitive layer by contact exposure, it is preferable to expose the first photosensitive layer through a temporary support from the viewpoint of avoiding contamination of the photomask and the influence of foreign matter adhering to the photomask on the exposure. preferable. When the first photosensitive layer is exposed through a temporary support, it is preferable to perform the first development step described below after removing the temporary support.

The temporary support used when exposing the first photosensitive layer through the temporary support is preferably a film capable of transmitting light irradiated during exposure.

The light source for exposure is not limited as long as it can emit light in a wavelength range (for example, 365 nm or 436 nm) that can change the solubility of the first photosensitive layer in the developer. Light sources for exposure include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light emitting diodes (LEDs).

The dominant wavelength λ ₁ of the exposure wavelength in the first exposure step may be the same as or different from the dominant wavelength λ ₂ of the exposure wavelength in the second exposure step, but is preferably different.
The dominant wavelength λ ₁ of the exposure wavelength in the first exposure step may be determined in the wavelength range of 10 to 450 nm, for example. The dominant wavelength λ ₁ is, for example, preferably within the range of 300-400 nm or 370-450 nm, more preferably within the range of 300-380 nm or 390-450 nm.

The exposure wavelength in the first exposure step preferably does not include the wavelength of 365 nm. In the present specification, the phrase “not including a wavelength of 365 nm” means that the intensity at a wavelength of 365 nm is 30% or less when the maximum value of intensity in the entire exposure wavelength range (that is, the intensity of the dominant wavelength; the same shall apply hereinafter) is 100%. means that When the maximum value of the intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 365 nm is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. 3% or less is particularly preferred, and 1% or less is most preferred. The lower limit of the intensity at a wavelength of 365 nm is not particularly limited. When the maximum value of intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 365 nm is, for example, 0% or more.

When the exposure wavelength in the first exposure step does not include a wavelength of 365 nm, the exposure wavelength in the first exposure step includes a dominant wavelength in the wavelength range of 370 to 450 nm, and the intensity of the dominant wavelength is 100%, The intensity at a wavelength of 365 nm is preferably 30% or less, and when the wavelength range of 390 to 450 nm includes the dominant wavelength and the intensity at the dominant wavelength is 100%, the intensity at a wavelength of 365 nm is 30% or less. is more preferable, and when the wavelength range of 420 to 450 nm includes a dominant wavelength and the intensity of the dominant wavelength is 100%, it is particularly preferable that the intensity at a wavelength of 365 nm is 30% or less. When the intensity of the dominant wavelength is 100%, the intensity at a wavelength of 365 nm is preferably 20% or less, more preferably 10% or less, even more preferably 5% or less, and 3% or less. It is particularly preferred to have some, and most preferably not more than 1%. The lower limit of the intensity at a wavelength of 365 nm is not particularly limited. When the intensity of the dominant wavelength is 100%, the intensity of the wavelength of 365 nm is, for example, 0% or more.

It is also preferable that the exposure wavelength in the first exposure step does not include the wavelength of 436 nm.
In the present specification, "not including a wavelength of 436 nm" means that the intensity at a wavelength of 436 nm is 30% or less when the maximum value of intensity in the entire exposure wavelength range is 100%. When the maximum value of the intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 436 nm is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. 3% or less is particularly preferred, and 1% or less is most preferred. The lower limit of the intensity at a wavelength of 436 nm is not particularly limited. When the maximum value of the intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 436 nm is, for example, 0% or more.

When the exposure wavelength in the first exposure step does not include a wavelength of 436 nm, the exposure wavelength in the first exposure step includes a dominant wavelength in the wavelength range of 300 to 400 nm, and the intensity of the dominant wavelength is 100%, The intensity at a wavelength of 436 nm is preferably 30% or less, and when the dominant wavelength is included in the wavelength range of 300 to 380 nm and the intensity of the dominant wavelength is 100%, the intensity at a wavelength of 436 nm is 30% or less. is more preferable, and when the wavelength range of 350 to 380 nm includes the dominant wavelength and the intensity of the dominant wavelength is 100%, it is particularly preferable that the intensity at the wavelength of 436 nm is 30% or less. When the intensity of the dominant wavelength is 100%, the intensity at a wavelength of 436 nm is preferably 20% or less, more preferably 10% or less, even more preferably 5% or less, and 3% or less. It is particularly preferred to have some, and most preferably not more than 1%. The lower limit of the intensity at a wavelength of 436 nm is not particularly limited. When the intensity of the dominant wavelength is 100%, the intensity of the wavelength of 436 nm is, for example, 0% or more.

As an embodiment of the exposure wavelength in the first exposure step, the intensity of the wavelength 365 nm is greater than the intensity of the wavelength 436 nm (hereinafter referred to as "condition (1-1)" in this paragraph), or the intensity of the wavelength 436 nm is an exposure wavelength (hereinafter referred to as “condition (1-2)” in this paragraph) that is greater than the intensity of a wavelength of 365 nm. When the intensity at a wavelength of 365 nm is 100% in condition (1-1), the intensity at a wavelength of 436 nm is preferably 80% or less, more preferably 50% or less, and preferably 20% or less. More preferably, it is particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the intensity at a wavelength of 436 nm in condition (1-1) is not particularly limited. When the intensity at a wavelength of 365 nm is 100% in condition (1-1), the intensity at a wavelength of 436 nm is, for example, 0% or more. On the other hand, when the intensity at a wavelength of 436 nm is 100% under condition (1-2), the intensity at a wavelength of 365 nm is preferably 80% or less, more preferably 50% or less, and 20% or less. is more preferred, 10% or less is particularly preferred, and 5% or less is most preferred. The lower limit of the intensity at a wavelength of 365 nm in condition (1-2) is not particularly limited. Assuming that the intensity at a wavelength of 436 nm is 100% in condition (1-2), the intensity at a wavelength of 365 nm is, for example, 0% or more.

Methods for adjusting the exposure wavelength in the first exposure step include, for example, a method using a filter having wavelength selectivity and a method using a light source capable of irradiating light having a specific wavelength. For example, by exposing the first photosensitive layer through a filter having wavelength selectivity, the wavelength of light reaching the first photosensitive layer can be adjusted within a specific range.

The exposure dose is preferably 5 to 1,000 mJ/cm ² , more preferably 10 to 500 mJ/cm ² and even more preferably 10 to 200 mJ/cm ² . The amount of exposure is determined based on the illuminance of the light source and the exposure time. Alternatively, the exposure amount may be measured using a photometer.

In the first exposure step, the first photosensitive layer may be exposed without using a photomask. When exposing the first photosensitive layer without using a photomask (hereinafter sometimes referred to as "maskless exposure"), for example, the first photosensitive layer can be exposed using a direct drawing device.
A direct drawing device can draw an image directly using an active energy ray. Light sources for maskless exposure include, for example, lasers (e.g., semiconductor lasers, gas lasers, solid-state lasers, etc.), mercury short arc lamps (e.g., ultra-high pressure mercury lamps), etc., capable of irradiating light with a wavelength of 350 to 410 nm. is mentioned. The dominant wavelength λ ₁ of the exposure wavelength in the maskless exposure may be the same as or different from the dominant wavelength λ ₂ of the exposure wavelength in the second exposure step, but is preferably different.
The preferred range of exposure wavelength is as described above. The amount of exposure is determined based on the illuminance of the light source and the moving speed of the laminate. The drawing pattern can be controlled by a computer.

[Second exposure step]
In the second photosensitive layer exposed in the second exposure step, the solubility in the developer changes between the exposed area and the unexposed area. For example, when the second photosensitive layer is a positive photosensitive layer, the exposed portion of the second photosensitive layer is more soluble in a developer than the unexposed portion. On the other hand, for example, when the second photosensitive layer is a negative photosensitive layer, the exposed portion of the second photosensitive layer is less soluble in a developer than the unexposed portion.

Examples of the method of exposing the second photosensitive layer include a method using a photomask. For example, by placing a photomask between the second photosensitive layer and the light source, the second photosensitive layer can be patternwise exposed through the photomask. By subjecting the second photosensitive layer to pattern exposure, an exposed portion and an unexposed portion can be formed in the second photosensitive layer.

In the second exposure step, it is preferable to expose the layered product and the photomask while they are in contact with each other. The resolution can be improved by a method of exposing by bringing the laminate and the photomask into contact (also referred to as “contact exposure”).

When a temporary support is disposed on the second photosensitive layer, the second photosensitive layer may be exposed through the temporary support, and the second photosensitive layer may be exposed after removing the temporary support from the second photosensitive layer. Two photosensitive layers may be exposed. When exposing the second photosensitive layer by contact exposure, it is preferable to expose the second photosensitive layer through a temporary support from the viewpoint of avoiding contamination of the photomask and the influence of foreign matter adhering to the photomask on the exposure. preferable. When the second photosensitive layer is exposed through a temporary support, it is preferable to perform the second development step described below after removing the temporary support.

The temporary support used when exposing the second photosensitive layer through the temporary support is preferably a film capable of transmitting light irradiated during exposure.

The light source for exposure is not limited as long as it can emit light in a wavelength range (for example, 365 nm or 436 nm) that can change the solubility of the second photosensitive layer in the developer. Light sources for exposure include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light emitting diodes (LEDs).

The dominant wavelength λ ₂ of the exposure wavelength in the second exposure step may be the same as or different from the dominant wavelength λ ₁ of the exposure wavelength in the first exposure step, as described above, but they are different. is preferred. The dominant wavelength λ ₂ of the exposure wavelength in the second exposure step may be determined in the wavelength range of 10 to 410 nm, for example. The dominant wavelength λ ₂ is, for example, preferably within the range of 300-400 nm or 370-450 nm, more preferably within the range of 300-380 nm or 390-450 nm. For example, when the dominant wavelength λ ₁ in the first exposure step is in the range of 300 to 400 nm (preferably 300 to 380 nm), the dominant wavelength λ ₂ in the second exposure step is 370 to 450 nm (preferably 390 to 450 nm). preferably within the range. For example, when the dominant wavelength λ ₁ in the first exposure step is in the range of 370 to 450 nm (preferably 390 to 450 nm), the dominant wavelength λ ₂ in the second exposure step is 300 to 400 nm (preferably 300 to 380 nm). preferably within the range.

If the exposure wavelength in the first exposure step does not include the wavelength of 365 nm, the exposure wavelength in the second exposure step preferably does not include the wavelength of 436 nm. By adopting the above exposure wavelengths in the first exposure step and the second exposure step, each photosensitive layer can be more selectively exposed. When the maximum value of the intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 436 nm is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. 3% or less is particularly preferred, and 1% or less is most preferred. The lower limit of the intensity at a wavelength of 436 nm is not particularly limited. When the maximum value of the intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 436 nm is, for example, 0% or more.

When the exposure wavelength in the second exposure step does not include a wavelength of 436 nm, the exposure wavelength in the second exposure step includes a dominant wavelength in the wavelength range of 300 to 400 nm, and the intensity of the dominant wavelength is 100%, The intensity at a wavelength of 436 nm is preferably 30% or less, and when the dominant wavelength is included in the wavelength range of 300 to 380 nm and the intensity of the dominant wavelength is 100%, the intensity at a wavelength of 436 nm is 30% or less. is more preferable, and when the wavelength range of 350 to 380 nm includes the dominant wavelength and the intensity of the dominant wavelength is 100%, it is particularly preferable that the intensity at the wavelength of 436 nm is 30% or less. When the intensity of the dominant wavelength is 100%, the intensity at a wavelength of 436 nm is preferably 20% or less, more preferably 10% or less, even more preferably 5% or less, and 3% or less. It is particularly preferred to have some, and most preferably not more than 1%. The lower limit of the intensity at a wavelength of 436 nm is not particularly limited. When the intensity of the dominant wavelength is 100%, the intensity of the wavelength of 436 nm is, for example, 0% or more.

If the exposure wavelength in the first exposure step does not include the wavelength of 436 nm, the exposure wavelength in the second exposure step preferably does not include the wavelength of 365 nm. By adopting the above exposure wavelengths in the first exposure step and the second exposure step, the photosensitive layer can be more selectively exposed. When the maximum value of the intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 365 nm is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. 3% or less is particularly preferred, and 1% or less is most preferred. The lower limit of the intensity at a wavelength of 365 nm is not particularly limited. When the maximum value of intensity in the entire exposure wavelength range is 100%, the intensity at a wavelength of 365 nm is, for example, 0% or more.

When the exposure wavelength in the second exposure step does not include a wavelength of 365 nm, the exposure wavelength in the second exposure step includes a dominant wavelength in the wavelength range of 370 to 450 nm, and the intensity of the dominant wavelength is 100%, The intensity at a wavelength of 365 nm is preferably 30% or less, and when the wavelength range of 390 to 450 nm includes the dominant wavelength and the intensity at the dominant wavelength is 100%, the intensity at a wavelength of 365 nm is 30% or less. More preferably, the wavelength range of 420 to 450 nm includes a dominant wavelength, and when the intensity of the dominant wavelength is 100%, the intensity at a wavelength of 365 nm is more preferably 30% or less. When the intensity at the dominant wavelength is 100%, the intensity at a wavelength of 365 nm is preferably 20% or less, more preferably 10% or less, even more preferably 5% or less, and 3% or less. It is particularly preferred to have some, and most preferably not more than 1%. The lower limit of the intensity at a wavelength of 365 nm is not particularly limited. When the intensity of the dominant wavelength is 100%, the intensity of the wavelength of 365 nm is, for example, 0% or more.

When the exposure wavelength in the first exposure step is "an exposure wavelength where the intensity at a wavelength of 365 nm is greater than the intensity at a wavelength of 436 nm", the exposure wavelength in the second exposure step is an exposure where the intensity at a wavelength of 436 nm is greater than the intensity at a wavelength of 365 nm. It is preferably a wavelength (hereinafter referred to as “condition (2-1)” in this paragraph). Preferred aspects of the condition (2-1) are the same as the preferred aspects of the condition (1-2) described in the section "First exposure step" above. On the other hand, when the exposure wavelength in the first exposure step is "an exposure wavelength in which the intensity at a wavelength of 436 nm is greater than the intensity at a wavelength of 365 nm", the exposure wavelength in the second exposure step is such that the intensity at a wavelength of 365 nm is higher than the intensity at a wavelength of 436 nm. A large exposure wavelength (hereinafter referred to as “condition (2-2)” in this paragraph) is preferred. A preferred embodiment of the condition (2-2) is the same as the preferred embodiment of the condition (1-1) described in the section "First exposure step" above.

Methods for adjusting the exposure wavelength in the second exposure step include, for example, a method using a filter having wavelength selectivity and a method using a light source capable of irradiating light having a specific wavelength. For example, by exposing the second photosensitive layer through a filter having wavelength selectivity, the wavelength of light reaching the second photosensitive layer can be adjusted within a specific range.

The exposure dose is preferably 5 to 1,000 mJ/cm ² , more preferably 10 to 500 mJ/cm ² and even more preferably 10 to 200 mJ/cm ² . The amount of exposure is determined based on the illuminance of the light source and the exposure time. Alternatively, the exposure amount may be measured using a photometer.

Above all, it is preferable that the dominant wavelength λ ₁ and the dominant wavelength λ ₂ are as follows.
The dominant wavelength λ ₁ is preferably in the range of 250 nm or more and 395 nm or less, and more preferably in the range of 335 nm or more and 395 nm or less, from the viewpoint of suppressing exposure fogging.
The dominant wavelength _λ2 is preferably in the range of more than 395 nm and 500 nm or less, more preferably in the range of 396 nm or more and 456 nm or less, from the viewpoint of suppressing exposure fogging.
Further, from the viewpoint of suppressing exposure fogging, it is more preferable that the dominant wavelength λ ₁ is in the range of 250 nm or more and 395 nm or less, and the dominant wavelength λ ₂ is in the range of more than 395 nm and 500 nm or less. It is particularly preferable that λ ₁ is in the range of 335 nm or more and 395 nm or less, and the dominant wavelength λ ₂ is in the range of 396 nm or more and 456 nm or less.

In the pattern forming method of the present invention, the exposure dose in the first exposure step and the exposure dose in the second exposure step may be the same or different.

In the second exposure step, the second photosensitive layer may be exposed without using a photomask. When the first photosensitive layer is exposed without using a photomask (hereinafter sometimes referred to as "maskless exposure"), for example, the first photosensitive layer can be exposed using a direct drawing device. A direct drawing device can draw an image directly using an active energy ray. Light sources for maskless exposure include, for example, lasers (e.g., semiconductor lasers, gas lasers, and solid-state lasers) and mercury short arc lamps (e.g., ultra-high pressure mercury lamps) capable of emitting light having a wavelength of 350 to 410 nm. be done. The dominant wavelength _λ2 of the exposure wavelength in the maskless exposure is not limited as long as it is different from the dominant wavelength _λ2 of the exposure wavelength in the first exposure step. A preferred range of exposure wavelengths is as described above. The amount of exposure is determined based on the illuminance of the light source and the moving speed of the laminate. The drawing pattern can be controlled by a computer.

In the pattern forming method of the present invention, the first exposure step and the second exposure step may be performed simultaneously or sequentially. The order of performing the first exposure process and the second exposure process may be performed in the order of the first exposure process→the second exposure process, or may be performed in the order of the second exposure process→the first exposure process. The first exposure step and the second exposure step are preferably performed at the same time from the viewpoint of further improving productivity.

In the present specification, "the first exposure step and the second exposure step are performed simultaneously" is not limited to the case where the exposure of the first photosensitive layer and the exposure of the second photosensitive layer are performed completely simultaneously. , including the case where the period for exposing the first photosensitive layer and the period for exposing the second photosensitive layer overlap.

Further, "the first exposure step and the second exposure step are sequentially performed" means that the period for exposing the first photosensitive layer and the period for exposing the second photosensitive layer do not overlap. It means exposing the photosensitive layer and the second photosensitive layer respectively.

[First development step]
The pattern forming method of the present invention includes a step of developing the exposed first photosensitive layer to form a first resin pattern (first developing step). In the first development step, for example, the first resin pattern can be formed by removing a portion of the exposed first photosensitive layer that has relatively high solubility in the developer.

The developing method is not particularly limited, and known methods can be used. For example, a developer can be used to develop the first photosensitive layer.
The developer is not particularly limited, and known developers can be used. Examples of the developer include the developer described in JP-A-5-072724. Preferred developers include, for example, those described in paragraph 0194 of WO2015/093271.
The developer is preferably an alkaline aqueous solution type developer containing a compound having a pKa of 7 to 13. In the alkaline aqueous developer, the concentration of the compound having a pKa of 7 to 13 is preferably 0.05 to 5 mol/L.
The developer may contain, as components other than those described above, for example, an organic solvent miscible with water and a surfactant.
The temperature of the developer is preferably 20-40°C.
The developing method is not particularly limited, and known methods can be used. Development methods include, for example, puddle development, shower development, shower and spin development, and dip development.

The first development step may include a step of heat-treating the first resin pattern (also referred to as “post-baking”).
The heat treatment is preferably performed in an environment of 8.1 to 121.6 kPa, more preferably in an environment of 8.1 to 114.6 kPa, and more preferably in an environment of 8.1 to 101.3 kPa. is more preferred.
The temperature of the heat treatment is preferably 20 to 250°C, more preferably 30 to 170°C, even more preferably 50 to 150°C.
The heat treatment time is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, even more preferably 2 to 4 minutes.
The heat treatment may be performed in an air environment or in a nitrogen-substituted environment.

[Second development step]
The pattern forming method of the present invention includes a step of developing the exposed second photosensitive layer to form a second resin pattern (second developing step). In the second development step, for example, the second resin pattern can be formed by removing a portion of the exposed second photosensitive layer that has relatively high solubility in the developer.
The specific embodiment of the second developing step is the same as the first developing step described above, and the preferred mode is also the same.

In the pattern forming method of the present invention, the first development step and the second development step may be performed simultaneously or sequentially. As for the order of implementation of the first development process and the second development process, the first development process→the second development process may be performed, or the second development process→the first development process may be performed. The first development step and the second development step are preferably performed at the same time from the viewpoint of further improving productivity.

In the present specification, "the first development step and the second development step are performed simultaneously" is not limited to the case where the development of the first photosensitive layer and the development of the second photosensitive layer are performed completely simultaneously. , including the case where the period for developing the first photosensitive layer and the period for developing the second photosensitive layer overlap.

Further, "the first developing step and the second developing step are sequentially performed" means that the period for developing the first photosensitive layer and the period for developing the second photosensitive layer do not overlap. It means exposing the photosensitive layer and the second photosensitive layer respectively.

A preferred embodiment of the pattern forming method includes an embodiment in which the first exposure step and the second exposure step are performed simultaneously, and the first development step and the second development step are performed simultaneously. According to the above embodiment, the time and environment from the exposure to the start of development can be made the same, so it is easy to stabilize the product quality, the process length can be shortened, and the process cost can be reduced.
In another preferred embodiment of the pattern forming method, the first exposure step and the second exposure step are performed sequentially, or the first development step and the second development step are preferably performed sequentially. For example, if the reaction progress rate after exposure is significantly different for the first photosensitive layer and the second photosensitive layer, or if it is necessary to place different exposure light sources away from the photosensitive layer, the first exposure step and Preferably, the second exposure steps are performed sequentially. Further, for example, when the developer used for developing the first photosensitive layer and the developer used for developing the second photosensitive layer are different, the first developing step and the second developing step are performed sequentially. preferably done.

[Etching process]
It is also preferable that the pattern forming method has an etching step after the developing step.
The etching step is a step of performing at least one of a step of etching the first transparent conductive layer using the first resin pattern as a mask and a step of etching the second transparent conductive layer using the second resin pattern as a mask. .
Through the etching process, the pattern of the first transparent conductive layer and/or the pattern of the second transparent conductive layer can be formed on the transparent substrate.

Etching includes, for example, dry etching and wet etching. Etching is preferably wet etching because it does not require a vacuum process and the process is simple. Examples of etching include the methods described in paragraphs 0048 to 0054 of JP-A-2010-152155.

The etchant used in wet etching includes, for example, an acid-type etchant and an alkaline-type etchant.

Examples of acidic etching solutions include aqueous solutions containing acidic components (eg, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and phosphoric acid), and acidic components and salts (eg, ferric chloride, ammonium fluoride, iron nitrate, and potassium permanganate).
The acidic type etchant may contain one type of acidic component alone, or may contain two or more types. Moreover, the acidic type etching solution may contain one kind of salt alone or two or more kinds thereof.

Alkaline etching solutions include, for example, aqueous solutions containing alkali components [e.g., sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide]), and alkali components and and an aqueous solution containing a salt (eg, potassium permanganate).
The alkaline type etchant may contain one kind of alkali component alone or two or more kinds thereof. Moreover, the alkaline type etchant may contain one kind of salt alone or two or more kinds thereof.

The etchant may contain an antirust agent from the viewpoint of etching rate control. Rust preventives include, for example, nitrogen-containing compounds (eg, triazole compounds, imidazole compounds, tetrazole compounds, etc.).
The temperature of the etchant is preferably 45° C. or less.

In the pattern forming method of the present invention, the first resin pattern used as a mask and the second resin pattern used as a mask preferably have excellent resistance to an etchant at 60° C. or less in terms of better etching resistance. .

In the etching step, etching of the first transparent conductive layer and the second transparent conductive layer may be performed simultaneously or sequentially. The first exposure step and the second exposure step are preferably performed at the same time from the viewpoint of further improving productivity.

[Washing process and drying process]
From the viewpoint of preventing contamination of the process line, the pattern forming method of the present invention may include a washing step and a drying step after the etching step, if necessary.

A specific example of the washing process includes a method of washing the laminate using pure water at room temperature (eg, 25° C.). The cleaning time can be appropriately set, for example, within the range of 10 to 300 seconds.
A specific example of the drying process includes a method of drying the laminate using an air blow. The air blow pressure is preferably 0.1-5 kg/cm ² .

[Overall exposure process]
The pattern forming method of the present invention may include a step of exposing at least one of the first resin pattern and the second resin pattern to light (hereinafter also referred to as “whole surface exposure step”). The entire surface exposure step is preferably performed before the removal step, which will be described later. By including the entire surface exposure step in the pattern forming method of the present invention, the reactivity of the pattern remaining after development can be further improved, and/or the removability of the resin pattern in the removal step described later can be improved.
For example, a resin pattern formed of a positive photosensitive layer is further improved in removability in the removal step described later by the entire surface exposure step. On the other hand, the resin pattern formed by the negative photosensitive layer is further cured by the entire surface exposure process, and the resistance of the resin pattern to the process is improved.
It should be noted that "overall exposure" intends to expose the region where the first resin pattern and the second resin pattern are arranged on the base material with the transparent conductive layer. A region where the first resin pattern is not arranged on the base material with the transparent conductive layer and a region where the second resin pattern is not arranged on the base material with the transparent conductive layer may be exposed or exposed. It doesn't have to be. It is preferable that the entire surface of the base material with the transparent conductive layer is exposed from the viewpoint of convenience.

A light source for exposure is not particularly limited, and a known light source can be used. Light sources for exposure include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and light emitting diodes (LEDs).
The exposure wavelength preferably includes a wavelength of 365 nm or a wavelength of 436 nm from the viewpoint of removability.
From the viewpoint of removability, the exposure dose is preferably 5 to 1,000 mJ/cm ² , more preferably 10 to 800 mJ/cm ² , even more preferably 100 to 500 mJ/cm ² .
From the viewpoint of removability, the exposure amount is preferably equal to or greater than the exposure amount in at least one of the first exposure step and the second exposure step, and the exposure in at least one step of the first exposure step and the second exposure step More preferably, it is greater than the amount.
The exposure illuminance is preferably 5 to 25,000 mW/cm ² , more preferably 20 to 20,000 mW/cm ² , even more preferably 30 to 15,000 mW/cm ² . By increasing the illuminance, the time required to expose the entire surface is shortened.

[Heating process]
In the pattern forming method of the present invention, at least one of the first resin pattern and the second resin pattern is heated during the overall exposure step, before the overall exposure step, and/or before the removal step described below. A step (hereinafter also referred to as a “heating step”) may be included.
Since the pattern forming method of the present invention includes the heating step, the first resin pattern and the second resin pattern can be easily removed. For example, in a resin pattern formed of a positive photosensitive layer, the reaction speed of the photoacid generator and the reaction speed of the generated acid and the positive photosensitive composition can be improved, thereby improving the removal performance.

The heating device is not particularly limited, and a known heating device can be used. Heating devices include, for example, infrared heaters, hot blowers, and convection ovens.
The heating temperature is preferably 30 to 100°C, more preferably 30 to 80°C, and particularly preferably 30 to 60°C, from the viewpoint of removability.
From the viewpoint of removability, the heating time is preferably 1 to 600 seconds, more preferably 1 to 120 seconds, particularly preferably 5 to 60 seconds. Here, the "heating time" means the time calculated from the time when the surface of the substrate with the transparent conductive layer reaches the set temperature, and does not include the time during temperature rise.
The heating atmosphere is preferably air (relative humidity: 10 to 90% RH). The heating atmosphere may be an inert gas (eg, nitrogen and argon).
The pressure is preferably normal pressure.

If a large amount of water adheres to the base material with the transparent conductive layer, at least one of before and during the heating process, from the viewpoint of increasing the heating efficiency, a step of blowing off excess water with an air knife or the like. may be combined.

[Removal process]
The pattern forming method of the present invention may include a step of removing at least one of the first resin pattern and the second resin pattern (hereinafter also referred to as "removing step"). Note that, hereinafter, the first resin pattern and the second resin pattern may be collectively referred to as "resin pattern".

As a method for removing the resin pattern, for example, a method using a chemical such as a remover is exemplified, and a specific example is a method of immersing the laminate in the remover.
As the removing liquid, a liquid capable of dissolving or dispersing the resin pattern is preferable.
The temperature of the removing liquid is preferably 30 to 80°C, more preferably 50 to 80°C.
The immersion time in the removing liquid is preferably 1 to 30 minutes.

The removal liquid preferably contains water in terms of further improving the removability.
The content of water in the removing liquid is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

The removing liquid preferably contains an inorganic alkaline component or an organic alkaline component.
Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkali components include primary to tertiary amine compounds and quaternary ammonium salt compounds.
Among them, the removing liquid more preferably contains an organic alkaline component in terms of further improving the removability. The content of the organic alkaline component in the remover is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the remover, in terms of better removability. is more preferable.

From the viewpoint of removability, the removal liquid preferably contains a surfactant. The surfactant is not particularly limited, and known surfactants can be used.
From the viewpoint of removability, the content of the surfactant is preferably 0.1 to 10% by mass with respect to the total mass of the removing liquid.

The removing liquid preferably contains a water-soluble organic solvent. Water-soluble organic solvents include, for example, dimethylsulfoxide, lower alcohols, glycol ethers, and N-methylpyrrolidone.

Methods of contacting the removing liquid and the resin pattern in the removing step include, for example, a spray method, a shower method, and a paddle method.

As the removal liquid, JP-A-11-021483, JP-A-2002-129067, JP-A-07-028254, JP-A-2001-188363, JP-A-04-048633, and Japanese Patent No. 5318773 Stripping solutions described in publications can also be applied.

The removal of the first resin pattern and the removal of the second resin pattern may be performed simultaneously or sequentially. The removal of the first resin pattern and the removal of the second resin pattern are preferably performed simultaneously from the viewpoint of productivity.

[Roll-to-roll method]
The pattern forming method of the present invention is preferably carried out by a roll-to-roll method.
The roll-to-roll method is not particularly limited, and a known roll-to-roll method can be used. For example, in the pattern forming method of the present invention, by providing at least a step of unwinding the laminate and at least a step of winding the laminate before and after at least one step, the laminate can be processed while being transported.

[Other processes]
The pattern forming method of the present invention may include steps other than those described above. Examples of steps other than the above include the following steps.

(Step of reducing visible light reflectance)
The pattern forming method of the present invention may include a step of treating part or all of the first transparent conductive layer and the second transparent conductive layer to reduce the visible light reflectance.

The treatment for reducing the visible light reflectance includes, for example, oxidation treatment. For example, when the first transparent conductive layer and the second transparent conductive layer contain copper, the visible light reflectance of the first transparent conductive layer and the second transparent conductive layer is reduced by oxidizing the copper to form copper oxide. can be made

Preferred aspects of the treatment for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315. , the contents of which are incorporated herein by reference.

[Method for manufacturing circuit board]
A circuit board manufacturing method of the present invention includes the pattern forming method of the present invention.
The pattern forming method of the present invention is as described above.
Examples of circuit boards include printed wiring boards and touch panel sensors.

The present invention will be described in further detail based on examples below. The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

[Abbreviation]
The following abbreviations represent the following compounds, respectively.
(binder)
"AA-1": Propylene glycol monomethyl ether acetate solution of copolymer of styrene/methacrylic acid/methyl methacrylate (solid concentration: 30.0% by mass, ratio of each monomer: 52% by mass/29% by mass/19 % by mass, Mw: 70,000)
"AA-3": Propylene glycol monomethyl ether acetate solution of copolymer of benzyl methacrylate, methacrylic acid, and acrylic acid (solid concentration: 40.0% by mass, Mw: 13,000, ratio of each monomer: 78 mass %/14.5% by mass/7.5% by mass acid value: 153 mgKOH/g)

(Polymerizable compound/plasticizer)
"AB-1": BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
"AB-3": NK Ester A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
"AB-4": 8UX-015A (polyfunctional urethane (meth) acrylate, manufactured by Taisei Fine Chemical Co., Ltd.)
"AB-5": Aronix TO-2349 (a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate with a succinic acid derivative, manufactured by Toagosei Co., Ltd.)
"AB-7": NK ester A-HD-N (1,6-hexanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
"AB-8": NK ester HD-N (1,6-hexanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

(initiator/photoacid generator)
"AC-1": B-CIM (polymerization initiator, manufactured by Kurogane Kasei Co., Ltd.)
"AC-11": a compound having the structure shown below (a photoacid generator, a compound synthesized according to the method described in paragraph 0227 of JP-A-2013-047765)

(sensitizer)
"AC-5": Coumarin 7 (manufactured by Tokyo Chemical Industry Co., Ltd.)
"AC-6": 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)
"AC-10": 3-acetyl-7-(diethylamino) coumarin (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

(Polymerization inhibitor)
"AD-1": TDP-G (manufactured by Kawaguchi Chemical Industry Co., Ltd.)
"AD-2": 1-phenyl-3-pyrazolidone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
"AD-3": N-nitroso-N-phenylhydroxylamine aluminum (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

(Dyes (excluding dyes whose maximum absorption wavelength changes with acids, bases, or radicals))
"AE-3": Solvent Yellow 56 (manufactured by Tokyo Chemical Industry Co., Ltd., a substance that absorbs light of 436 nm)
"AE-8": Diethylamino-phenylsulfonyl UV absorber (manufactured by Daito Chemical Co., Ltd., a substance that absorbs light of 365 nm)
"AE-15": Bonasorb UA3911 (manufactured by Orient Chemical Co., a substance that absorbs light of 405 nm)
"AE-16": Bonasorb UA3912 (manufactured by Orient Chemical Co., a substance that absorbs light of 405 nm)
"AE-17": FDB-009 (manufactured by Yamada Chemical Industry Co., Ltd., a substance that absorbs light of 405 nm)
"AE-18": a compound represented by the following structural formula (a substance that absorbs light at 405 nm)

"AE-19": a compound represented by the following structural formula (a substance that absorbs light of 405 nm)

"AE-20": a compound represented by the following structural formula (a substance that absorbs light of 405 nm)

"AE-21": a compound represented by the following structural formula (a substance that absorbs light at 405 nm)

"AE-22": a compound represented by the following structural formula (a substance that absorbs light at 405 nm)

"AE-23": a compound represented by the following structural formula (a substance that absorbs light at 405 nm)

(Other additives)
"AE-1": Leuco Crystal Violet (manufactured by Tokyo Chemical Industry Co., Ltd.)
"AE-2": N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
"AE-12": CBT-1 (carboxybenzotriazoles, Johoku Chemical Industry Co., Ltd.)
"AE-13": F-552 (surfactant, manufactured by DIC Corporation)
"AE-24": isonicotinamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
"AE-25": 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
"AE-26": 1,1-oxalyldiimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
"AE-27": a compound with the structure shown below (a dye that develops color with an acid)

(solvent)
"AF-1": methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
"AF-2": propylene glycol monomethyl ether acetate (manufactured by Showa Denko K.K.)
"AF-3": Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.)

[Examples 1 to 6 and Comparative Examples 1 to 3]
Resin patterns were formed on both sides of the transparent substrate by the following method.

[Preparation of transfer film]
Based on the formulations shown in Table 2, each transfer film for transferring a photosensitive layer to two opposing surfaces (A surface and B surface) of a transparent substrate was produced. Each of the A-side and B-side transfer films has a structure in which a temporary support, a photosensitive layer disposed on the temporary support, and a protective film are provided in this order. For example, in the case of Example 1, the A-side transfer film includes a temporary support and a photosensitive layer formed on the temporary support using the composition for forming a photosensitive layer of prescription a-1. and a protective film. In addition, the transfer film for B side includes a temporary support, a photosensitive layer formed on the temporary support using the photosensitive layer forming composition of prescription b-1, and a protective film. have. Table 1 shows the formulation of each composition for forming a photosensitive layer. Also, the transfer films used in Examples 2 to 6 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that each recipe number of the composition for forming a photosensitive layer was changed according to Table 2. made.

Specifically, each transfer film for the A side and the B side was produced by the following method.
On a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%), using a slit nozzle, the coating width is 1.0 m, and the layer thickness after drying is 3.0 μm. A composition for forming a photosensitive layer having the prescription number shown in Table 2 was applied as follows. The photosensitive layer-forming composition on the temporary support was dried in a convection oven at 100° C. for 2 minutes to form a photosensitive layer. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was laminated on the photosensitive layer to prepare a transfer film. For example, in the case of Example 1, the A-side transfer film includes a temporary support, a photosensitive layer formed from the composition for forming a photosensitive layer of prescription a-1, and a protective film in this order. was made. Also, as a transfer film for side B, a transfer film having a temporary support, a photosensitive layer formed from the composition for forming a photosensitive layer of formulation b-1, and a protective film in this order was produced.

[Production of laminate]
After cutting the transfer film selected according to Table 2 into 50 cm squares, the protective film was peeled off from the transfer film. Next, under lamination conditions of a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m/min, the transfer film was placed on two opposing surfaces (surface A) of a transparent substrate (polyethylene terephthalate film, thickness: 40 μm). and B side). A laminate was produced by the above procedure.
In the following, the photosensitive layer in the transfer film laminated on the A side of the transparent substrate is referred to as the "first photosensitive layer", and the photosensitive layer in the transfer film laminated on the B side of the transparent substrate. is sometimes referred to as "second photosensitive layer". The laminate has a structure of temporary support/first photosensitive layer/transparent substrate/second photosensitive layer/temporary support.

[Pattern formation]
Without peeling off the temporary support, a glass mask (Duty ratio 1:1) having a line and space pattern with a line width of 3 to 40 μm is adhered to both sides of the laminate (the surface of the temporary support, which is the outermost layer of the laminate). let me At this time, the glass masks were arranged on both sides of the laminate so that the line patterns of the glass masks were orthogonal to each other when viewed from above. The first photosensitive layer and the second photosensitive layer were then exposed simultaneously. When exposing the first photosensitive layer and the second photosensitive layer at the same time, the first photosensitive layer is exposed from the side where the first photosensitive layer is arranged (side A) with respect to the transparent substrate, and , the second photosensitive layer was exposed from the side on which the second photosensitive layer was arranged (side B) with respect to the transparent substrate.
Exposure conditions were determined as follows.
First photosensitive layer: The first photosensitive layer is exposed through the glass mask using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.), left for 1 hour after exposure, and developed. The amount of exposure was adjusted so that the remaining pattern width would be in the range of 49.0 microns to 51.0 microns in the pattern area of 50 microns line/50 microns space.
Second photosensitive layer: The second photosensitive layer is exposed through the glass mask using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.), left for 1 hour after exposure, and developed. The amount of exposure was adjusted so that the remaining pattern width would be in the range of 49.0 microns to 51.0 microns in the pattern area of 50 microns line/50 microns space.

In the table, the following terms and symbols described in the "exposure conditions" column have the following meanings.
"Not including 365 nm": Using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.), exposure was performed through a short wavelength cut filter (model number: LU0422, cutoff wavelength: 422 nm, manufactured by Asahi Spectrosco Co., Ltd.) . The dominant wavelength is 436 nm. When the intensity at the dominant wavelength is 100%, the intensity at the wavelength of 365 nm is 0.5% or less.
"Does not contain 436 nm": Using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.), exposure is performed through a mercury exposure bandpass filter (model number: HB0365, center wavelength: 365 nm, manufactured by Asahi Spectrosco Co., Ltd.). did. The dominant wavelength is 365 nm. When the intensity of the dominant wavelength is 100%, the intensity of the wavelength of 436 nm is 0.5% or less.
"-": Exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.) without using a wavelength-selective filter.

After leaving for 1 hour after exposure, the temporary support was peeled off, and then a resin pattern was formed by development. Development was performed by shower development for 30 seconds using a 1.0% potassium carbonate aqueous solution (developer) at 28°C. Development was carried out simultaneously for the first photosensitive layer and the second photosensitive layer.
By the above procedure, the transparent substrate, the first resin pattern formed from the first photosensitive layer on one of the two opposing surfaces of the transparent substrate (A surface), and the second resin pattern on the other surface (B surface) A transparent base material (hereinafter also referred to as "base material with resin pattern") having a second resin pattern formed from a photosensitive layer was formed.

〔evaluation〕
Using the resin patterned substrates produced in Examples 1 to 6 and Comparative Examples 1 to 3, resolution and exposure fogging were evaluated. Table 2 shows the evaluation results.

<Resolution>
Among the resin patterns, the line width of the pattern with the highest resolution was defined as the final resolution. Based on the reached resolution, the resolution was evaluated according to the following criteria. E was assigned when the side wall of the pattern was greatly roughened, or when footing was conspicuous and connected to the adjacent line pattern. As an evaluation, D is preferable, C is more preferable, B is still more preferable, and A is particularly preferable.
(Evaluation criteria)
A: 10 μm or less B: More than 10 μm, 18 μm or less C: More than 18 μm, 20 μm or less D: More than 20 μm, 30 μm or less E: More than 30 μm, or not resolved

<Exposure fog>
The non-exposed area (limited to the exposed area on the surface of the transparent substrate opposite to the non-exposed area; hereinafter the same applies in this paragraph) of the surface of the substrate with the resin pattern was observed, and the exposure fogging was determined according to the following criteria. evaluated. When exposure fogging occurs, residues derived from the photosensitive layer are observed in the non-exposed areas.

(Evaluation criteria)
A: When observed with an optical microscope with a magnification of 50 times, the side where the first photosensitive layer was arranged with reference to the transparent substrate and the side where the second photosensitive layer was arranged with reference to the transparent substrate. No residue is observed on either side.
B: When observed with an optical microscope with a magnification of 50 times, the side where the first photosensitive layer was arranged with reference to the transparent substrate and the side where the second photosensitive layer was arranged with reference to the transparent substrate. Residue is observed on at least one of the sides that were

Tables 1 and 2 are shown below.
In addition, the unit of the amount (addition amount) of each component described in Table 1 is parts by mass.
Further, "maximum sensitivity wavelength" in Table 2 represents the maximum sensitivity wavelength of the photosensitive layer. The method for measuring the maximum sensitivity wavelength of the photosensitive layer is as described above.
In addition, "dye maximum absorption wavelength" represents the maximum absorption wavelength of a dye (unit: nm). The method for measuring the maximum absorption wavelength of the dye is as described above.
In each item of the photosensitive layer and the thermoplastic resin layer, "dye 1" and "dye 2" indicate dyes having a maximum absorption wavelength in the wavelength region of 300 to 500 nm contained in the layer.
Further, in Table 2, "the absorbance of the dye at the maximum sensitivity wavelength of the photosensitive layer" means that when the dye contained in the photosensitive layer is one, the absorbance of the dye is measured by the method described above. represents the measured value. When two or more types of dyes are contained in the photosensitive layer, the above two or more types of dyes are mixed so as to have a compounding ratio (mass ratio) in the layer, and the absorbance in this mixed state is measured as described above. It represents the value measured by the measurement method.

It is clear that the resin patterned substrates of Examples are excellent in the resolution of the resin pattern, and that exposure fogging is suppressed. Therefore, according to the transfer film and the laminate of the present invention, it is clear that a resin pattern having excellent resolution can be formed, and exposure fogging is suppressed.

For example, taking Example 1 using a filter having wavelength selectivity as an example, the exposure light for the A side is reflected by the filter having wavelength selectivity used for selecting the wavelength of the exposure light for the B side. However, even if this reflected light occurs, the reflected light is a dye that can absorb light of a wavelength that is the same as or close to the maximum sensitivity wavelength of the A-side photosensitive layer in the B-side photosensitive layer. can be absorbed into As a result, it is possible to suppress deterioration in resolution on the A surface due to reflected light. Further, on the B side, the exposure fog caused by the exposure light on the A side is suppressed.
In addition, the exposure light on the B side can be reflected by a filter having wavelength selectivity used for selecting the wavelength of the exposure light on the A side. can be absorbed by a dye in the sensitive layer capable of absorbing light at a wavelength that is the same as or close to the wavelength of maximum sensitivity of the B-side photosensitive layer. As a result, it is possible to suppress deterioration in resolution on the B surface due to reflected light. Further, on the A side, the exposure fog caused by the exposure light on the B side is suppressed.

Further, for example, taking Example 3 in which a filter having wavelength selectivity is not used, even if the exposure light on side A passes through the transparent base material and enters the photosensitive layer on side B, The light having a wavelength that is the same as or close to the maximum sensitivity wavelength of the B-side photosensitive layer is reduced in intensity per unit area by the action of the dye contained in the A-side photosensitive layer. there is As a result, exposure fogging on the B side can be suppressed.
In addition, even if the exposure light on side B passes through the transparent base material and enters the photosensitive layer on side A, the light that has entered is affected by the action of the dye contained in the photosensitive layer on side B. The intensity per unit area of light having a wavelength that is the same as or close to the maximum sensitivity wavelength of the side photosensitive layer is reduced. As a result, exposure fogging on the A side can be suppressed.
In both the A side and the B side, the maximum absorption wavelength of the dye to be introduced differs from the maximum sensitivity wavelength of the photosensitive layer by 40 nm or more, so that the resolution of the resin pattern is excellent.

From the comparison of Examples 1 to 6, it was confirmed that when the maximum sensitivity wavelength of side B is 450 nm or less, a resin pattern with better resolution can be formed.
From the comparison of the examples, it was confirmed that a resin pattern with better resolution can be formed when the photosensitive layer does not contain a dye that is the same as or similar to the maximum sensitivity wavelength of the photosensitive layer (Examples 1 and 2 and Example 5 and 6).

[Examples 11 to 31, Comparative Examples 4 to 6]
[Preparation of transfer film]
Based on the formulations shown in Table 4, each transfer film for transferring a photosensitive layer to two opposing surfaces (A surface and B surface) of a transparent substrate was produced. Each of the transfer films for A-side and B-side has a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive layer, and a protective film in this order. For example, in the case of Example 11, the A-side transfer film includes a temporary support, a thermoplastic resin layer formed from the thermoplastic resin composition of prescription A-1, and an intermediate layer-forming composition described later ( It has an intermediate layer formed by M-1), a photosensitive layer formed by the composition for forming a photosensitive layer of formulation a-4, and a protective film. Further, the transfer film for side B is formed of a temporary support, a thermoplastic resin layer formed from the thermoplastic resin composition of prescription B-1, and an intermediate layer forming composition (M-1) described later. and a photosensitive layer formed from the composition for forming a photosensitive layer of formulation b-6, and a protective film.
The formulation of each photosensitive layer-forming composition is as shown in Table 1, and the formulation of each thermoplastic resin composition is as shown in Table 3.
Specifically, each transfer film for the A side and the B side was produced by the following method.

On a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%), using a slit nozzle, the coating width is 1.0 m and the layer thickness after drying is 3.0 μm. The thermoplastic resin composition having the recipe number listed in Table 4 was applied so as to obtain After that, the coating film of the obtained thermoplastic resin composition was dried at 80° C. for 40 seconds to form a thermoplastic resin layer.
Next, an intermediate layer-forming composition was applied onto the obtained thermoplastic resin layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 1.2 μm. (M-1) was applied. Thereafter, the obtained coating film of the intermediate layer forming composition (M-1) was dried at 80° C. for 40 seconds to form an intermediate layer.
Next, a composition for forming a photosensitive layer was applied onto the obtained intermediate layer using a slit-shaped nozzle so that the coating width was 1.0 m and the layer thickness after drying was 3.0 μm. was coated and dried in a convection oven at 100°C for 2 minutes to form a photosensitive layer. Then, a protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was pasted on the photosensitive layer to prepare each transfer film.
For example, in the case of Example 11, as a transfer film for A side, a temporary support, a thermoplastic resin layer formed from a thermoplastic resin composition of prescription A-1, an intermediate layer, and a photosensitive of prescription a-4 A transfer film having a photosensitive layer formed from the composition for forming a protective layer and a protective film in this order was produced. Further, as a transfer film for B side, a temporary support, a thermoplastic resin layer formed from the thermoplastic resin composition of prescription B-1, an intermediate layer, and a composition for forming a photosensitive layer of prescription b-6 and a protective film in this order.

[Preparation of intermediate layer forming composition (M-1)]
A composition for forming an intermediate layer was prepared by mixing the following components.
・Kuraray Poval PVA-4-88LA (manufactured by Kuraray): 3.22 parts by mass ・Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai): 1.49 parts by mass ・Megafac F-444 (manufactured by DIC): 0.0015 mass Parts Ion-exchanged water: 38.12 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical): 57.17 parts by mass

[Production of laminate]
After cutting the transfer film selected according to Table 4 into 50 cm squares, the protective film was peeled off from the transfer film. Next, under lamination conditions of a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m/min, the transfer film was placed on two opposing surfaces (surface A) of a transparent substrate (polyethylene terephthalate film, thickness: 40 μm). and B side). A laminate was produced by the above procedure.
The laminate has a structure of temporary support/thermoplastic resin layer/intermediate layer/first photosensitive layer/transparent substrate/second photosensitive layer/intermediate layer/thermoplastic resin layer/temporary support.

Using the produced laminates, substrates with resin patterns of Examples 11 to 31 and Comparative Examples 4 to 6 were produced according to the method described in the section "Pattern Formation" above. Using the obtained substrate with a resin pattern, the resolution and exposure fog described in the above section "Evaluation" were evaluated. Table 4 shows the evaluation results.

Tables 3 and 4 are shown below.
In addition, the unit of the amount (addition amount) of each component described in Table 3 is parts by mass.
Further, "maximum sensitivity wavelength" in Table 4 represents the maximum sensitivity wavelength of the photosensitive layer. The method for measuring the maximum sensitivity wavelength of the photosensitive layer is as described above.
In addition, "dye maximum absorption wavelength" represents the maximum absorption wavelength of a dye (unit: nm). The method for measuring the maximum absorption wavelength of the dye is as described above.
In each item of the photosensitive layer and the thermoplastic resin layer, "dye 1" and "dye 2" indicate dyes having a maximum absorption wavelength in the wavelength region of 300 to 500 nm contained in the layer.
Further, in Table 4, "the absorbance of the dye at the maximum sensitivity wavelength of the photosensitive layer" is the absorbance of the dye when the type of dye used in the photosensitive layer and the thermoplastic resin layer is one. represents the value measured by the measurement method described above. When two or more types of dyes are used in the photosensitive layer and the thermoplastic resin layer, the above two or more types of dyes are mixed so as to have a compounding ratio (mass ratio) in the layer. , represents the value obtained by measuring the absorbance in this mixed state by the measurement method described above.

It is clear that the resin patterned substrates of Examples are excellent in the resolution of the resin pattern, and that exposure fogging is suppressed. Therefore, according to the transfer film and the laminate of the present invention, it is clear that a resin pattern having excellent resolution can be formed, and exposure fogging is suppressed.

For example, taking Example 11 using a filter having wavelength selectivity as an example, the exposure light for the A side is reflected by the filter having wavelength selectivity used for selecting the wavelength of the exposure light for the B side. However, even if this reflected light occurs, the reflected light can absorb light of a wavelength that is the same as or similar to the maximum sensitivity wavelength of the photosensitive layer on the A side in the thermoplastic resin layer on the B side. It can be absorbed by pigments. As a result, it is possible to suppress deterioration in resolution on the A surface due to reflected light. Further, on the B side, the exposure fog caused by the exposure light on the A side is suppressed.
In addition, the exposure light on the B side can be reflected by a wavelength-selective filter used for selecting the wavelength of the exposure light on the A side. It can be absorbed by a dye in the plastic layer that is capable of absorbing light of a wavelength that is the same as or close to the wavelength of maximum sensitivity of the B-side photosensitive layer. As a result, it is possible to suppress exposure fogging and deterioration of resolution on the B side due to reflected light. Further, on the A side, the exposure fog caused by the exposure light on the B side is suppressed.

Further, for example, taking Example 17 in which a filter having wavelength selectivity is not used, even if the exposure light on the A side passes through the transparent base material and enters the photosensitive layer on the B side, The intensity per unit area of the light having a wavelength that is the same as or similar to the maximum sensitivity wavelength of the photosensitive layer on the B side is reduced by the action of the dye contained in the thermoplastic resin layer on the A side. ing. As a result, exposure fogging on the B side can be suppressed.
Further, even if the exposure light on the B side passes through the transparent base material and enters the photosensitive layer on the A side, the light that has entered is affected by the action of the dye contained in the thermoplastic resin layer on the B side. The intensity per unit area of light having a wavelength that is the same as or close to the maximum sensitivity wavelength of the photosensitive layer on the face side is reduced. As a result, exposure fogging on the A side can be suppressed.
In both the A side and the B side, the maximum absorption wavelength of the dye to be introduced differs from the maximum sensitivity wavelength of the photosensitive layer by 40 nm or more, so that the resolution of the resin pattern is excellent.

From comparison with Examples, it was confirmed that when the specific dye was a non-sensitizing dye, a resin pattern with better resolution could be formed (results of Examples 16 and 17).
From the comparison of the examples, it was found that when the composition layer consists of a photosensitive layer, an intermediate layer and a thermoplastic resin layer, and when the thermoplastic resin layer contains a specific dye, a resin pattern with better resolution can be formed. It was confirmed (contrast Examples 11-14).
From the comparison of the examples, it was confirmed that a resin pattern with better resolution can be formed when the photosensitive layer does not contain a dye that is the same as or similar to the maximum sensitivity wavelength of the photosensitive layer (Examples 14 and 15). result).
Further, from the results of Example 16, it was confirmed that the sensitizing dye can function as the specific dye in the thermoplastic resin layer containing no initiator.

In the production of each laminate of Examples 1 to 6 and Examples 11 to 18, the transparent substrate was changed to a substrate with a transparent conductive layer having a transparent substrate and AgNW layers with a thickness of 50 nm on both sides of the transparent substrate. Laminates (Examples 1A to 6A and Examples 11A to 18A) were produced in the same manner except that they were evaluated, and similar results were obtained.

Further, in Examples 19 and 21 to 24, since the i-line absorption ability of the dye on the B side is slightly inferior, some of the exposure light from the B side is transmitted to the A side, resulting in slightly inferior resolution. result.

20 Laminate 5A First transfer film 11 Base material with transparent conductive layer 5B Second transfer film 3A First photosensitive layer 3B Second photosensitive layer 1A First temporary support 1B Second temporary support 9 Transparent base material 7A, 7B transparent conductive layer 12 mask 13, 15 filter having wavelength selectivity white arrow, black arrow exposure light L11, L12, L21, L22 part of exposure light 30, 50 transfer film 31 temporary support 33, 53 thermoplastic resin layer 35, 55 intermediate layer 37, 57 photosensitive layer 39, 59 composition layer 41 protective film

Claims (18)

A transfer film applied to a substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate,
Having a temporary support and a composition layer containing at least a photosensitive layer,
The composition layer contains a dye having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer,
The transfer film, wherein the difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40 nm or more. The transfer film according to claim 1, wherein the transparent conductive layer contains at least one selected from the group consisting of metal nanowires and metal nanoparticles. 3. The transfer film according to claim 1, wherein the photosensitive layer has a maximum sensitivity wavelength of 300 to 395 nm, and the dye has a maximum absorption wavelength of more than 395 nm and 500 nm or less. 3. The transfer film according to claim 1, wherein the photosensitive layer has a maximum sensitivity wavelength of more than 395 nm and 500 nm or less, and the dye has a maximum absorption wavelength of 300 to 395 nm. The transfer film of any one of claims 1-4, wherein the dye is not sensitized. 6. The transfer film according to any one of claims 1 to 5, wherein the dye has an absorbance of 1 or less at the maximum sensitivity wavelength of the photosensitive layer. The composition layer contains a sensitizer,
The sensitizer is at least one selected from the group consisting of benzophenone compounds, thioxanthone compounds, cyanine compounds, coumarin compounds, and merocyanine compounds, according to any one of claims 1 to 6. Transfer film as described. The transfer film according to any one of claims 1 to 7, wherein the photosensitive layer contains the dye. The transfer film according to any one of claims 1 to 8, wherein the composition layer further has a thermoplastic resin layer closer to the temporary support than the photosensitive layer. The transfer film according to claim 9, wherein the thermoplastic resin layer contains the dye. The photosensitive layer further contains a polymerization inhibitor,
The transfer film according to any one of claims 1 to 10, wherein the polymerization inhibitor is at least one selected from the group consisting of phenothiazine compounds, hindered phenol compounds, and phenoxazine compounds. 12. A base material with a transparent conductive layer having a transparent base material and transparent conductive layers disposed on both sides of the transparent base material, and a base material with a transparent conductive layer laminated on both sides of the base material with the transparent conductive layer. A laminate comprising the transfer film according to item 1. In one transfer film in the laminate, the photosensitive layer has a maximum sensitivity wavelength of 300 to 395 nm, and the dye has a maximum absorption wavelength of more than 395 nm and 500 nm or less,
13. The laminate according to claim 12, wherein in the other transfer film, the photosensitive layer has a maximum sensitivity wavelength of more than 395 nm and 500 nm or less, and the dye has a maximum absorption wavelength of 300 to 395 nm. A method of forming a pattern by exposing and developing the transfer film in the laminate according to claim 12 or 13,
a first exposure step of exposing the photosensitive layer in one transfer film in the laminate;
a second exposure step of exposing the photosensitive layer in the other transfer film in the laminate;
a first development step of developing the photosensitive layer exposed through the first exposure step to form a resin pattern;
and a second developing step of developing the photosensitive layer exposed through the second exposing step to form a resin pattern. 15. The pattern forming method according to claim 14, wherein said first exposure step and said second exposure step are performed simultaneously or sequentially. 16. The pattern forming method according to claim 14, wherein said first developing step and said second developing step are performed simultaneously or sequentially. using the resin pattern formed through the first developing step as a mask to etch the transparent conductive layer disposed between the transparent substrate and the resin pattern formed through the first developing step; 1 etching step;
using the resin pattern formed through the second developing step as a mask to etch the transparent conductive layer disposed between the transparent substrate and the resin pattern formed through the second developing step; 2. The pattern forming method according to any one of claims 14 to 16, comprising: 2 etching steps. A method for manufacturing a circuit board, comprising the pattern forming method according to any one of claims 14 to 17.

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