CN115480446A

CN115480446A - Transfer film, laminate, pattern forming method, and method for manufacturing circuit board

Info

Publication number: CN115480446A
Application number: CN202210557670.8A
Authority: CN
Inventors: 两角一真; 片山晃男; 佐藤守正; 有富隆志; 佐佐木大辅; 东笃志
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-05-31
Filing date: 2022-05-19
Publication date: 2022-12-16

Abstract

The present invention provides a transfer film which is suitable for both surfaces of a substrate with transparent conductive layers, the substrate having a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate, wherein when exposure is performed from both sides of a laminate in which the transfer film is disposed on both surfaces of the substrate with transparent conductive layers, exposure fogging can be suppressed and the resolution of a formed resin pattern is also excellent. Also, a laminate, a pattern forming method, and a method of manufacturing a circuit board are provided. The present invention also provides a transfer film suitable for a substrate with a transparent conductive layer, which has a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate, the transfer film comprising a temporary support and a composition layer containing at least a photosensitive layer, wherein the composition layer contains 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 sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40nm or more.

Description

Transfer film, laminate, pattern forming method, and method for manufacturing circuit board

Technical Field

The invention relates to a transfer film, a laminate, a pattern forming method, and a method for manufacturing a circuit board.

Background

Since the number of steps for obtaining a predetermined pattern is small, the following methods are widely used: 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 the photosensitive layer (see patent document 1).

Patent document 1: japanese patent laid-open No. 2020-086238

The present inventors have studied a method of forming patterned conductive layers on both surfaces of a transparent substrate by a double-sided photolithography process using a transfer film, and as a result, they have found that, for example, when a laminate having a conductive layer and a photosensitive layer on 2 opposing surfaces of a transparent substrate in this order from the transparent substrate side is subjected to double-sided exposure, a phenomenon (hereinafter, also referred to as "exposure fogging") may occur in which the photosensitive layer on the other side is also exposed to exposure light when the photosensitive layer on one side is exposed to exposure light. If exposure fogging occurs, the desired shape of the photosensitive layer may not be formed.

Further, the present inventors have further studied a method of forming patterned conductive layers on both surfaces of a transparent base material by a double-sided photolithography process, and have found that the resolution of a resin pattern formed by each photosensitive layer by exposure/development treatment is sometimes poor.

Disclosure of Invention

Accordingly, an object of the present invention is to provide a transfer film which is suitable for both surfaces of a substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate, and which can suppress exposure fogging and can form a resin pattern having excellent resolution when exposure (double-sided exposure) is performed from both sides of a laminate in which transfer films are disposed on both surfaces of the substrate with the transparent conductive layer.

Another object of the present invention is to provide a laminate, a pattern forming method, and a method for manufacturing a circuit board.

The present inventors have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by the following configuration.

[ 1 ] A transfer film which is suitable for a substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate,

the transfer film has a temporary support and a composition layer containing at least a photosensitive layer,

the composition layer contains a coloring matter having a maximum absorption wavelength at a wavelength different 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 40nm or more.

[ 2 ] the transfer film according to [ 1 ], wherein,

the transparent conductive layer includes at least 1 selected from metal nanowires and metal nanoparticles.

[ 3 ] the transfer film according to [ 1 ] or [ 2 ], wherein,

the maximum sensitivity wavelength of the photosensitive layer is 300 to 395nm, and the maximum absorption wavelength of the dye is over 395nm and is less than 500 nm.

[ 4 ] the transfer film according to [ 1 ] or [ 2 ], wherein,

the maximum sensitivity wavelength of the photosensitive layer is over 395nm and below 500nm, and the maximum absorption wavelength of the pigment is 300-395 nm.

[ 5 ] the transfer film according to any one of [ 1 ] to [ 4 ], wherein,

the pigment is non-sensitizing pigment.

[ 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 transfer film according to any one of [ 1 ] to [ 6 ], wherein,

the above-mentioned composition layer contains a sensitizer,

the sensitizer is at least 1 selected from benzophenone compound, thioxanthone compound, cyanine compound, coumarine compound and merocyanine compound.

[ 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 includes a thermoplastic resin layer at a position closer to the temporary support than the photosensitive layer.

[ 10 ] the transfer film according to [ 9 ], wherein,

the thermoplastic resin layer contains the coloring matter.

[ 11 ] the transfer film according to any one of [ 1 ] to [ 10 ], wherein,

the photosensitive layer further contains a polymerization inhibitor,

the polymerization inhibitor is at least 1 selected from phenothiazine compounds, hindered phenol compounds and phenoxazine compounds.

[ 12 ] A laminate comprising:

a substrate with a transparent conductive layer, which has a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate; and

the transfer film according to any one of [ 1 ] to [ 11 ] which is bonded to both surfaces of the substrate with a transparent conductive layer.

[ 13 ] the laminate according to [ 12 ], wherein,

in one transfer film of the laminate, the maximum sensitivity wavelength of the photosensitive layer is 300 to 395nm, the maximum absorption wavelength of the dye exceeds 395nm and is 500nm or less,

In the transfer film on the other side, the maximum sensitivity wavelength of the photosensitive layer is more than 395nm and 500nm or less, and the maximum absorption wavelength of the dye is 300 to 395nm.

[ 14 ] A method for forming a pattern by subjecting a transfer film in the laminate according to [ 12 ] or [ 13 ] to exposure treatment and development treatment,

the pattern forming method includes:

a first exposure step of exposing the photosensitive layer in one transfer film of the laminate;

a second exposure step of exposing the photosensitive layer in the transfer film on the other side of the laminate;

a 1 st developing step of developing the photosensitive layer exposed in the 1 st exposure step to form a resin pattern; and

and a 2 nd developing step of developing the photosensitive layer exposed in the 2 nd exposure step to form a resin pattern.

[ 15 ] the pattern forming method according to [ 14 ], wherein,

the 1 st exposure step and the 2 nd exposure step are performed simultaneously or sequentially.

[ 16 ] the pattern forming method according to [ 14 ] or [ 15 ], wherein,

the 1 st developing step and the 2 nd developing step are performed simultaneously or sequentially.

[ 17 ] the pattern forming method according to any one of [ 14 ] to [ 16 ], comprising:

a 1 st etching step of etching the transparent conductive layer disposed between the transparent base material and the resin pattern formed in the 1 st developing step, using the resin pattern formed in the 1 st developing step as a mask; and

and a 2 nd etching step of etching the transparent conductive layer disposed between the transparent base material and the resin pattern formed in the 2 nd developing step, using the resin pattern formed in the 2 nd developing step as a mask.

A method for manufacturing a circuit board, comprising the pattern forming method of any one of [ 14 ] to [ 17 ].

Effects of the invention

According to the present invention, there is provided a transfer film which is applied to both surfaces of a substrate with a transparent conductive layer having a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate, and which can suppress exposure fogging and can form a resin pattern having excellent resolution when exposure (double-sided exposure) is performed from both sides of a laminate in which the transfer film is disposed on both surfaces of the substrate with the transparent conductive layer.

Further, according to the present invention, a laminate, a pattern forming method, and a method for manufacturing a circuit board can be provided.

Drawings

Fig. 1 is a schematic diagram for explaining the mechanism of action of the transfer film of the present invention when double-sided exposure is performed on a laminate in which the transfer film of the present invention is disposed on both sides of a substrate with transparent conductive layers.

Fig. 2 is a schematic diagram for explaining the mechanism of action of the transfer film of the present invention when double-sided exposure is performed on a laminate in which the transfer film of the present invention is disposed on both sides of a substrate having transparent conductive layers.

Fig. 3 is a schematic diagram for explaining embodiment 1 of the transfer film.

Fig. 4 is a schematic diagram for explaining embodiment 2 of the transfer film.

Detailed Description

The present invention will be described in detail below.

In the present specification, the numerical range expressed by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the present specification, in the numerical ranges recited in the stepwise manner, the upper limit value or the lower limit value recited in a certain numerical range may be replaced with the upper limit value or the lower limit value recited in another stepwise manner. In the numerical ranges described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.

In the present specification, the term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when the step is not clearly distinguished from other steps.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of polystyrene as a standard substance measured as follows: TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) was used as a column, THF (tetrahydrofuran) was used as an eluent, a differential refractometer was used as a detector, polystyrene was used as a standard substance, and the measurement was performed by a Gel Permeation Chromatography (GPC) analyzer.

In the present specification, the molecular weight of the compound having a molecular weight distribution is a weight average molecular weight (Mw) unless otherwise specified.

In the present specification, the ratio of the structural units of the polymer is a mass ratio unless otherwise specified.

In the present specification, unless otherwise specified, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP) spectroscopic analyzer.

In this specification, unless otherwise specified, the refractive index is a value measured with an ellipsometer at a wavelength of 550 nm.

In the present specification, unless otherwise specified, the hue is a value measured by a color difference meter (CR-221, minolta Co., ltd).

In the present invention, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, "(meth) acryloyloxy" is a concept including both acryloyloxy and methacryloyloxy, and "(meth) acrylate" is a concept including both acrylate and methacrylate.

In the present specification, "alkali-soluble" means that the solubility in 100g of a 1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more.

In the present specification, "water-soluble" means that the solubility in 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the solubility conditions described above.

In the present specification, "solid component" of the composition means a component for forming a composition layer formed using the composition, and when the composition contains a solvent (an organic solvent, water, or the like), all components except the solvent are referred to. In addition, if the component is a component forming the composition layer, even a liquid component is considered as a solid component.

In the present specification, when the "maximum sensitivity wavelength" is referred to for the photosensitive layer, the "maximum sensitivity wavelength" refers to a wavelength at which the minimum exposure amount is the smallest when the minimum exposure amount at which the photosensitive layer reacts at each wavelength of light is determined as the spectral sensitivity.

The "maximum sensitivity wavelength" can be determined by the following method, for example. When light of a specific wavelength is irradiated to the photosensitive layer through a step-edge lobe (Stouffer 4105) in a range of 250 to 500nm, the minimum exposure amount at which the photosensitive material in the photosensitive layer reacts is designated as Emin. By varying the wavelength of the illumination, a spectral sensitivity curve can be obtained. Since Emin differs for each wavelength, the wavelength of the minimum value becomes the "maximum sensitivity wavelength".

In the negative photosensitive layer, the minimum exposure amount of the remaining exposed portion can be designated as Emin. On the other hand, in the positive photosensitive layer, the minimum exposure amount at which the exposed portion is removed can be regarded as Emin.

In the present specification, the "exposure wavelength" refers to the wavelength of light irradiated when the photosensitive layer is exposed, and refers to the wavelength of light reaching the photosensitive layer. For example, when a photosensitive layer is exposed through a filter having wavelength selectivity, the wavelength of light before passing through the filter does not match the exposure wavelength. Here, "wavelength selectivity" refers to a property of transmitting light in a specific wavelength range. In the present specification, the wavelength of Light and the intensity of Light are measured by a known spectroscope (for example, RPS900-R, manufactured by International Light Technologies).

In the present specification, the term "dominant wavelength" refers to the wavelength of light having the strongest intensity among the wavelengths of light reaching the photosensitive layer (i.e., the exposure wavelength). For example, the light reaching the photosensitive layer has a wavelength of 365nm and a wavelength of 436nm, and in the case of exposure light having an intensity of 365nm which is greater than an intensity of 436nm, the dominant wavelength of the exposure light is 365nm. In the present specification, "exposure light" refers to light for exposing the photosensitive layer.

In the present invention, "transparent" means that the transmittance at the main wavelength in the exposure wavelength is 30% or more. The transmittance is preferably 50% or more, more preferably 60% or more, further 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 was measured by a known transmittance measuring instrument (for example, V-700 series manufactured by JASCO Corporation).

[ transfer film ]

The transfer film of the present invention is suitable for 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 surfaces of the transparent substrate,

The composition layer contains a dye having a maximum absorption wavelength at a wavelength different from the wavelength of maximum sensitivity of the photosensitive layer,

Hereinafter, a dye having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer and a difference between the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer of 40nm or more will also be referred to as a "specific dye".

The specific dye preferably has a maximum absorption wavelength in any wavelength band in the ultraviolet to visible region, more preferably a maximum absorption wavelength in a wavelength band of 300 to 780nm, and still more preferably a maximum absorption wavelength in a wavelength band of 300 to 500 nm.

According to the transfer film of the present invention having the above configuration, exposure fogging can be suppressed when exposure (double-sided exposure) is performed from both sides of a laminate in which the transfer film of the present invention is disposed on both sides of a substrate having a transparent conductive layer. That is, when the photosensitive layer of one transfer film is exposed, the photosensitive layer of the other transfer film is less likely to be exposed by the exposure light.

Further, the resolution of the resin pattern formed by the transfer film of the present invention is also excellent.

The details thereof are not clear, but the inventors of the present invention presume as follows. Hereinafter, the structure and the operation mechanism of the transfer film of the present invention will be described in more detail 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 pigment will be described.

Fig. 1 is a view showing an embodiment of a laminate in which the transfer film of the present invention is disposed on both surfaces of a substrate having a transparent conductive layer.

The laminate 20 shown in fig. 1 and 2 includes the 1 st transfer film 5A, the substrate 11 with the transparent conductive layer, and the 2 nd transfer film 5B in this order. The 1 st transfer film 5A includes a 1 st photosensitive layer 3A and a 1 st temporary support 1A in this order from the substrate 11 side with the transparent conductive layer. The 2 nd transfer film 5B includes a 2 nd photosensitive layer 3B and a 2 nd temporary support 1B in this order from the substrate 11 side with the transparent conductive layer. The substrate 11 with a transparent conductive layer includes a transparent substrate 9, a transparent conductive layer 7A disposed on a surface of the transparent substrate 9 on the side contacting the 1 st transfer film, and a transparent conductive layer 7B disposed on a surface of the transparent substrate 9 on the side contacting the 2 nd transfer film.

Here, the maximum sensitivity wavelength of the 1 st photosensitive layer 3A is in the range of 300 to 395 nm. The 1 st photosensitive layer 3A contains a dye, the maximum absorption wavelength of the dye is in a range of 395nm to 500nm inclusive, and the difference between the maximum sensitivity wavelength of the 1 st photosensitive layer 3A and the maximum absorption wavelength of the dye is 40nm or more. The maximum sensitivity wavelength of the 2 nd photosensitive layer 3B is in the range of 395nm to 500nm inclusive. The 2 nd photosensitive layer 3B contains a coloring matter, the maximum absorption wavelength of the coloring matter is in the range of 300 to 395nm, and the difference between the maximum sensitivity wavelength of the 2 nd photosensitive layer 3B and the maximum absorption wavelength of the coloring matter is 40nm or more.

(mechanism of action for suppressing fogging upon exposure and exhibiting excellent resolution)

Hereinafter, the 1 st mechanism of action which can suppress exposure fogging and exhibit excellent resolution will be described with reference to fig. 1.

For example, when the 1 st photosensitive layer 3A of the laminate 20 is exposed using light source light having discrete (e.g., g-ray, h-ray, i-ray) light intensity distribution such as a high-pressure mercury lamp, a part of the exposure light incident on the mask opening portion from the white arrow direction in fig. 1 is absorbed by the dye in the 1 st photosensitive layer 3A and is suppressed from entering the 2 nd photosensitive layer 3B (L12 in the figure). The maximum absorption wavelength of the dye is the same as or close to the maximum sensitivity wavelength of the 2 nd photosensitive layer 3B. That is, by the presence of the coloring matter in the 1 st photosensitive layer 3A, the intensity per unit area of light having a wavelength equal to or close to the maximum sensitivity wavelength of the 2 nd photosensitive layer 3B is reduced in the exposure light reaching the 2 nd photosensitive layer 3B. As a result, various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) by exposure of the 2 nd photosensitive layer 3B can be suppressed, and thus exposure fogging can be suppressed. On the other hand, even if light (L21 in fig. 1) having a wavelength equal to or similar to the maximum sensitivity wavelength of the 1 st photosensitive layer 3A enters the 2 nd photosensitive layer 3B, it does not generally contribute to various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) by exposure of the 2 nd photosensitive layer 3B.

When the 2 nd photosensitive layer 3B of the laminated body 20 is exposed using light source light having a discrete light amount distribution (e.g., g-ray, h-ray, i-ray) such as a high-pressure mercury lamp, for example, part of the exposure light incident on the mask opening portion from the direction of the black arrow in fig. 1 is absorbed by the dye in the 2 nd photosensitive layer 3B and is suppressed from entering the 1 st photosensitive layer 3A (L22 in the figure). The maximum absorption wavelength of the dye is the same as or similar to the maximum sensitivity wavelength of the 1 st photosensitive layer 3A. That is, by the presence of the coloring matter in the 2 nd photosensitive layer 3B, the intensity per unit area of light having a wavelength equal to or close to the maximum sensitivity wavelength of the 1 st photosensitive layer 3A is reduced in the exposure light reaching the 1 st photosensitive layer 3A. As a result, various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) by exposure of the 1 st photosensitive layer 3A can be suppressed, and thus exposure fogging can be suppressed. On the other hand, even if light (L22 in fig. 1) having a wavelength equal to or close to the maximum sensitivity wavelength of the 2 nd photosensitive layer 3B enters the 1 st photosensitive layer 3A, it does not generally contribute to various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) by exposure of the 1 st photosensitive layer 3A.

Further, since the difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40nm or more, the amount of exposure required for various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) by exposure of the photosensitive layer can be suppressed from being absorbed by the dye and reduced. In other words, the dye can suppress a decrease in sensitivity of the photosensitive layer. As a result, the resolution of the resin pattern formed by the transfer film of the present invention is also excellent.

Next, referring to fig. 2, a 2 nd mechanism of action that can suppress exposure fogging and exhibit excellent resolution will be described.

For example, when the 1 st photosensitive layer 3A of the laminate 20 is exposed by using light source light having discrete (e.g., g-ray, h-ray, i-ray) light quantity distribution such as a high pressure mercury lamp and performing wavelength control using a filter or the like so that only a wavelength that is the same as or close to the maximum sensitivity wavelength of the 1 st photosensitive layer 3A is used as exposure light, a part of the exposure light incident on the mask opening portion from the white arrow direction in fig. 2 may enter the 2 nd photosensitive layer 3B and be reflected by the filter 15 or the like having wavelength selectivity. Since the reflected light has the same or similar maximum absorption wavelength as that of the dye in the 2 nd photosensitive layer 3B, the reflected light is absorbed by the dye in the 2 nd photosensitive layer 3B, and re-entry into the 1 st photosensitive layer 3A can be suppressed (L21 in fig. 2). As a result, the resolution of the resin pattern can be prevented from being lowered by the reflected light. In addition, even if light (L21 in fig. 2) having a wavelength equal to or similar to the maximum sensitivity wavelength of the 1 st photosensitive layer 3A enters the 2 nd photosensitive layer 3B, it does not generally contribute to various reactions (for example, a polymerization reaction in the case of a negative photosensitive layer) by exposure of the 2 nd photosensitive layer 3B. Therefore, exposure fogging can also be suppressed.

When the 2 nd photosensitive layer 3B of the laminate 20 is exposed by using light source light having discrete (e.g., g-ray, h-ray, i-ray) light quantity distribution such as a high pressure mercury lamp and performing wavelength control using a filter or the like so as to use only a wavelength that is the same as or close to the maximum sensitivity wavelength of the 2 nd photosensitive layer 3B as exposure light, a part of the exposure light incident on the mask opening portion from the black arrow direction in fig. 2 may enter the 1 st photosensitive layer 3A and be reflected by the filter 13 or the like having wavelength selectivity. Since the reflected light has the same or similar maximum absorption wavelength as that of the dye in the 1 st photosensitive layer 3A, the reflected light is absorbed by the dye in the 1 st photosensitive layer 3A, and re-entry into the 2 nd photosensitive layer 3B can be suppressed (L11 in fig. 2). As a result, the resolution of the resin pattern can be prevented from being lowered by the reflected light. In addition, even if light (L11 in fig. 2) having a wavelength equal to or similar to the maximum sensitivity wavelength of the 2 nd photosensitive layer 3B enters the 1 st photosensitive layer 3A, it does not generally contribute to various reactions (for example, a polymerization reaction in the case of a negative photosensitive layer) by exposure of the 1 st photosensitive layer 3A. Therefore, exposure fogging can also be suppressed.

Further, since the difference between the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the dye is 40nm or more, the amount of exposure light required for various reactions (for example, polymerization reaction in the case of a negative photosensitive layer) by exposure of the photosensitive layer can be suppressed from being absorbed by the dye and reduced. In other words, the dye can suppress a decrease in sensitivity of the photosensitive layer. This is also presumed to contribute to the development of excellent resolution of the resin pattern formed by the transfer film of the present invention.

Hereinafter, the fact that the transfer film is more excellent in exposure fogging and/or the resolution of the resin pattern formed by the transfer film is more excellent may be also referred to as "the effect of the present invention is more excellent".

The transfer film of the present invention will be described below.

The transfer film of the present invention has a temporary support and a composition layer including at least a photosensitive layer.

The composition layer may have a single-layer structure or 2 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.

The composition layer contains a dye (specific dye) having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer and having a difference of 40nm or more between the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer. The layer containing a specific pigment is not limited, and examples thereof include a photosensitive layer and a thermoplastic resin layer.

The specific pigment may be contained in any 1 or more layers of the composition layer, or may be contained in a plurality of 2 or more layers.

The composition layer may contain only the photosensitive layer, or may contain the photosensitive layer and other layers. When the composition layer is composed of only a photosensitive layer, the photosensitive layer contains a specific pigment.

The transfer film may have a structure in which a protective film (hereinafter, also referred to as a "cover film") is provided on the composition layer.

An example of the transfer film of the present invention will be described below, but the present invention is 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 each of the above structures, the photosensitive layer is preferably a negative photosensitive layer. The photosensitive layer is also preferably a colored resin layer.

The transfer film of the present invention will be described below by taking an example of a specific embodiment.

[ transfer film of embodiment 1 ]

An example of an embodiment of the transfer film according to embodiment 1 will be described below.

The transfer film 30 shown in fig. 3 includes a temporary support 31, a composition layer 39, and a protective film 41 in this order, and the composition layer 39 includes a thermoplastic resin layer 33, an intermediate layer 35, and a photosensitive layer 37 in this order from the temporary support 31 side. The photosensitive layer 37 contains a specific pigment.

The transfer film 30 shown in fig. 3 is a system in which the protective film 41 is disposed, but the protective film 41 may not be disposed. The transfer film 30 shown in fig. 3 is a system in which the thermoplastic resin layer 33 and the intermediate layer 35 are disposed, but the thermoplastic resin layer 33 and the intermediate layer 35 may not be disposed. In other words, the composition layer 39 may be constituted only by the photosensitive layer 37.

Hereinafter, each element constituting the transfer film will be described.

< temporary support >

The transfer film has a temporary support.

Examples of the temporary support include a glass substrate, a resin film, and paper. The temporary support is preferably a resin film from the viewpoint of strength and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. The temporary support is preferably a polyethylene terephthalate film, more preferably a biaxially stretched polyethylene terephthalate film.

As the temporary support, a film which has flexibility and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat can be used. Examples of such a film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable as the temporary support. Further, the film used as the temporary support is preferably free from deformation such as wrinkles and scratches.

From the viewpoint of enabling pattern exposure through the temporary support, the temporary support preferably has high transparency. The transmittance of the temporary support at the dominant wavelength in the exposure wavelength is preferably 60% or more, and more preferably 70% or more.

The temporary support is preferably low in haze from the viewpoints of pattern formability in pattern exposure through the temporary support and transparency of the temporary support. Specifically, the haze defined in JIS-K-7136 of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

From the viewpoint of pattern formability in pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of particles, foreign matters and defects having a diameter of 1 μm or more is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, the number of cells is more preferably 3/10 mm ² The average particle size is preferably 0 piece/10 mm ² 。

The thickness of the temporary support is not particularly limited, but is preferably 5 to 200. Mu.m, more preferably 10 to 150. Mu.m, and still more preferably 10 to 50 μm, from the viewpoint of easy handling and versatility.

Preferable examples of the temporary support are described in paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-085643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-027363, paragraphs 0041 to 0057 of International publication No. 2012/081680, and paragraphs 0029 to 0040 of International publication No. 2018/179370, the contents of which are incorporated in the present specification.

< 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, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

As the protective film, a resin film made of the same material as the temporary support can be used.

Among these, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is further preferable.

The thickness of the protective film is preferably 1 to 100. Mu.m, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and 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 relative inexpensiveness.

In the protective film, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 fish eyes/m ² The following.

The term "fish eye" refers to a defect in which foreign matter, undissolved matter, oxidized and degraded matter of a material are introduced into a film when the material is thermally melted and the film is formed by a method such as kneading, extrusion, biaxial stretching, or casting.

The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² Hereinafter, more preferably 10 pieces/mm ² Hereinafter, it is more preferably 5/mm ² The following.

This can suppress defects caused by transfer of the unevenness due to the particles contained in the protective film to the photosensitive layer or the conductive layer.

From the viewpoint of imparting windup properties, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the surface contacting the composition layer 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 smaller than 0.50. Mu.m, more preferably 0.40 μm or smaller, and still more preferably 0.30 μm or smaller.

The surface roughness Ra of the surface of the protective film in contact with the composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more, from the viewpoint of suppressing defects at the time of transfer. On the other hand, it is preferably smaller than 0.50. Mu.m, more preferably 0.40 μm or smaller, and still more preferably 0.30 μm or smaller.

< composition layer >

The transfer film includes a composition layer on a temporary support. The composition layer at least comprises a photosensitive layer. The transfer film according to embodiment 1 has a structure having 1 photosensitive layer as a composition layer. Hereinafter, the photosensitive layer will be described first.

When the transfer film is used as a resist as the photosensitive layer, the photosensitive layer (photosensitive layer a) of the following embodiment 1 is preferable, and when the transfer film is used as a wiring protective film, the photosensitive layer (photosensitive layer B) of the following embodiment 2 is preferable.

Among them, the photosensitive layer a is preferable as the photosensitive layer of the transfer film according to embodiment 1.

(photosensitive layer A) of embodiment 1)

The photosensitive layer a will be described below.

The photosensitive layer preferably contains a resin, a polymerizable compound, a polymerization initiator, and a specific pigment, more preferably contains a resin, a polymerizable compound, a polymerization initiator, a sensitizer, and a specific pigment, and further preferably contains a resin, a polymerizable compound, a polymerization initiator, a sensitizer, a polymerization inhibitor, and a specific pigment.

Also, the above resin preferably includes an alkali-soluble resin.

As a preferred example of the content of each component in the photosensitive layer, there is a mode in which the resin is contained in an amount of 10.0 to 90.0 mass%, the polymerizable compound is contained in an amount of 5.0 to 70.0 mass%, the polymerization initiator is contained in an amount of 0.01 to 15.0 mass%, and the specific pigment is contained in an amount of 0.01 to 15.0 mass%, with respect to the total mass of the photosensitive layer.

As another preferred example of the content of each component in the photosensitive layer, there can be mentioned, for example, a system including 10.0 to 90.0 mass% of a resin, 5.0 to 70.0 mass% of a polymerizable compound, 0.01 to 10.0 mass% of a polymerization initiator, 0.01 to 5.0 mass% of a sensitizer, and 0.01 to 15.0 mass% of a specific pigment, based on the total mass of the photosensitive layer.

Further, another preferable example of the content of each component in the photosensitive layer includes, for example, a mode including 10.0 to 90.0 mass% of a resin, 5.0 to 70.0 mass% of a polymerizable compound, 0.01 to 10.0 mass% of a polymerization initiator, 0.01 to 5.0 mass% of a sensitizer, 0.001 to 0.5 mass% of a polymerization inhibitor, and 0.01 to 15.0 mass% of a specific pigment, with respect to the total mass of the photosensitive layer.

Hereinafter, each component that the photosensitive layer may contain will be described.

-resins-

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 a thermoplastic resin layer described later can be used.

The resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing thickening of line width and deterioration of resolution when a focus position is shifted during exposure.

Examples of the aromatic hydrocarbon group include a phenyl group which may have a substituent and an aralkyl group which may have a substituent.

The content of the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, and further preferably 30.0% by mass or more, based on the total mass of the resin. The upper limit is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and further preferably 55.0% by mass or less, based on the total mass of the resin. When the photosensitive layer contains a plurality of resins, the mass average value of the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like), a monomer having an aralkyl group or styrene is preferable, and styrene is more preferable.

When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 10.0 to 80.0% by mass, more preferably 20.0 to 60.0% by mass, and still more preferably 30.0 to 55.0% by mass, based on the total mass of the resin. When the photosensitive layer contains a plurality of resins, the mass average value of the content of the structural unit having an aromatic hydrocarbon group is preferably within the above range.

Examples of the aralkyl group include a phenylalkyl group which may have a substituent (excluding a benzyl group) and a benzyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.

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

Examples of the monomer having a benzyl group include (meth) acrylates having a benzyl group such as benzyl (meth) acrylate and benzyl chloride (meth) acrylate; the vinyl monomer having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol is preferably a (meth) acrylate having a benzyl group, and more preferably benzyl (meth) acrylate.

When the monomer having an aromatic hydrocarbon group is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 85.0% by mass, and further preferably 30.0 to 85.0% by mass, based on the total mass of the resin.

The resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group, at least 1 kind of the following 1 st monomer and/or at least 1 kind of the following 2 nd monomer.

The resin not containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least 1 later-described 1 st monomer, and more preferably by polymerizing at least 1 st monomer with at least 1 later-described 2 nd monomer.

The 1 st monomer is a monomer having a carboxyl group in the molecule.

Examples of the 1 st monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half-ester, and (meth) acrylic acid is preferable.

The content of the structural unit derived from the 1 st monomer is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, and still more preferably 10.0 to 30.0% by mass, based on the total mass of the resin.

When the content is 5.0 mass% or more, excellent developability, control of edge meltability, and the like can be achieved. When the content is 50.0 mass% or less, high resolution of the resist pattern, control of the Tailing (Tailing) shape, and high chemical resistance of the resist pattern can be achieved.

The 2 nd monomer is a monomer which is not acidic (has no acidic group) and has a polymerizable group in the molecule.

The polymerizable group has the same meaning as a polymerizable group of a polymerizable compound described later, and the preferable embodiment is also the same.

Examples of the 2 nd monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; (meth) acrylonitrile.

Among them, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.

The content of the structural unit derived from the 2 nd monomer is preferably 1.0 to 80.0% by mass, more preferably 1.0 to 60.0% by mass, and still more preferably 10.0 to 50.0% by mass, based on the total mass of the resin.

The resin may have any 1 of a linear structure, a branched structure, and an alicyclic structure in a side chain.

By using a monomer containing a group having a branched structure in a side chain or a monomer containing a group having an alicyclic structure in a side chain, a branched structure or an alicyclic structure can be introduced into a side chain of a resin. The group having an alicyclic structure may be any 1 of monocyclic and polycyclic groups.

"side chain" refers to a group of atoms branching from the main chain. The "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin.

Examples of the monomer containing a group having a branched structure in a 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-octyl (meth) acrylate. Among them, isopropyl (meth) acrylate, isobutyl (meth) acrylate, or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.

Examples of the monomer containing a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms is exemplified.

Specific examples thereof include (bicyclo [ 2.2.1 ] heptyl-2) - (meth) acrylate, 1-adamantyl- (meth) acrylate, 2-adamantyl- (meth) acrylate, 3-methyl-1-adamantyl- (meth) acrylate, 3, 5-dimethyl-1-adamantyl- (meth) acrylate, 3-ethyladamantyl- (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl- (meth) acrylate, 3,5, 8-triethyl-1-adamantyl- (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl- (meth) acrylate, 2-methyl-2-adamantyl- (meth) acrylate, 2-ethyl-2-adamantyl- (meth) acrylate, 3-hydroxy-1-adamantyl- (meth) acrylate, octahydro-4, 7-menthoide-5-yl- (meth) acrylate, octahydro-4, 7-menthoide-1-ylmethyl- (meth) acrylate, 1-menthyl- (meth) acrylate, tris (6-hydroxy-1-menthyl) acrylate, 3, 6-trimethylheptyl- (meth) acrylate, 3-trimethyl-1-menthyl) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl- (meth) acrylate, (norbornyl) acrylate, (isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Among them, cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 1-adamantyl- (meth) acrylate, 2-adamantyl- (meth) acrylate, (fenchyl (meth) acrylate), 1-menthyl- (meth) acrylate, or tricyclodecyl (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 2-adamantyl- (meth) acrylate, or tricyclodecyl (meth) acrylate is more preferable.

From the viewpoint of further improving the effect of the present invention, the resin preferably has a polymerizable group, more preferably contains a structural unit having a polymerizable group, and still more preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

The polymerizable group includes polymerizable groups of polymerizable compounds described later, preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

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 1 st monomer with the 3 rd monomer.

The 3 rd monomer is a monomer having 2 or more polymerizable groups in the molecule, and preferably a monomer having 2 polymerizable groups in the molecule.

Examples of the polymerizable group include polymerizable groups of polymerizable compounds described below. Among these, the 3 rd monomer preferably has 2 polymerizable groups, more preferably has an ethylenically unsaturated group and a cationically polymerizable group, and further preferably has an acryloyl group or a methacryloyl group and an epoxy group.

Examples of the 3 rd 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, more preferably 10.0 to 50.0% by mass, still more preferably 15.0 to 40.0% by mass, and particularly preferably 20.0 to 40.0% by mass, based on the total mass of the resin.

Examples of the method for introducing a polymerizable group into a resin include a method in which an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride are reacted with a group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group of the resin.

Preferred examples of the method for introducing a polymerizable group into a resin include the following methods: after the 1 st monomer is synthesized by polymerization, a part of the carboxyl group derived from the structural unit of the 1 st monomer of the obtained resin is subjected to a polymer reaction with the 3 rd monomer (preferably glycidyl (meth) acrylate), thereby introducing a polymerizable group (preferably a (meth) acryloyloxy group) into the resin. The reaction temperature of the polymer reaction is preferably 80 to 110 ℃. The polymerization reaction preferably uses a catalyst, and more preferably uses an ammonium salt (tetraethylammonium bromide).

The reaction temperature in the above polymerization reaction is preferably 70 to 100 ℃ and more preferably 80 to 90 ℃. In the above polymerization reaction, a polymerization initiator is preferably used, and as the polymerization initiator, an azo-based initiator is more preferably used, and as the polymerization initiator, V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) or V-65 (manufactured by FUJIFILM Wako Pure Chemical Corporation) is further preferably used.

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 resin containing a structural unit derived from methacrylic acid and a structural unit derived from styrene are preferable, and a resin further containing a structural unit having a polymerizable group is more preferable.

In the above, it is also preferable to set the content of each constituent unit to the above-described preferable embodiments.

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

The acid value of the resin is preferably 220mgKOH/g or less, more preferably 200mgKOH/g or less, and still more preferably 170mgKOH/g or less. The lower limit is preferably not less than 10mgKOH/g, more preferably not less than 50mgKOH/g, and still more preferably not less than 70mgKOH/g.

The "acid value (mgKOH/g)" means the mass (mg) of potassium hydroxide required for neutralizing 1g of a sample. For example, the acid value can be determined in accordance with JIS K0070: 1992.

The acid value of the resin can be adjusted by the kind of the 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, the resolution and developability can be improved. When the weight average molecular weight is 5,000 or more, the properties of the developed aggregates and the properties of the unexposed film such as the edge meltability and the chipping property of the transfer film can be controlled. The term "edge-meltability" refers to the degree to which the photosensitive layer easily protrudes from the end face of a roll when the transfer film is wound into a roll. The "swarf property" means a degree of easy scattering of swarf when an unexposed film is cut with a knife. If the chips adhere to the upper surface of the transfer film, the chips are transferred to a mask in a subsequent exposure process or the like, resulting in a defective product.

The dispersity (Mw/Mn) of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0.

The photosensitive layer may contain other resins in addition to the above-mentioned resin.

Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.

The resin may be used alone in 1 or 2 or more.

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

Examples of a method for synthesizing a resin include a method in which an appropriate 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 isopropyl alcohol, and the mixture is heated and stirred. The synthesis may be performed while dropping a part of the mixture in the reaction solution. After the reaction is completed, a solvent may be further added to adjust the concentration to a desired concentration.

Examples of the method for synthesizing the resin include bulk polymerization, suspension polymerization, and emulsion polymerization, in addition to the above.

Polymerizable compound-

The photosensitive layer preferably contains a polymerizable compound.

The polymerizable compound is a compound having 1 or more polymerizable groups and polymerizable by the action of a polymerization initiator described later. The polymerizable compound is a compound different from the resin.

The polymerizable group of the polymerizable compound may be a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; a group having a cationically polymerizable group such as an epoxy group or an oxetanyl group.

The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups (hereinafter, also referred to as "ethylenically unsaturated compound"), and more preferably a compound having 2 or more ethylenically unsaturated groups in the molecule (hereinafter, also referred to as "polyfunctional ethylenically unsaturated compound"), from the viewpoint of more excellent photosensitivity of the photosensitive layer.

In addition, the number of ethylenically unsaturated groups in the molecule of the ethylenically unsaturated compound is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2 to 3, from the viewpoint of further improving resolution and peelability.

The polymerizable compound may have an alkyleneoxy group.

The alkylene group is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group, from the viewpoint of further improving the effects of the present invention. The number of addition of alkyleneoxy groups to the polymerizable compound is preferably 2 to 30, more preferably 2 to 20 per molecule.

From the viewpoint that the balance between the photosensitivity of the photosensitive layer and the resolution and peelability is more excellent, the polymerizable compound preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in the molecule.

The content of the 2-functional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably more than 40.0% by mass, and still more preferably 55.0% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less. That is, all of the polymerizable compounds contained in the photosensitive layer may be 2-functional ethylenically unsaturated compounds.

The content of the 3-functional ethylenically unsaturated compound is preferably 10.0% by mass or more, and more preferably 20.0% by mass or more, based on 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 further preferably 50.0% by mass or less. That is, all of the polymerizable compounds contained in the photosensitive layer may be 3-functional ethylenically unsaturated compounds.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group.

Polymerizable compound B1-

The photosensitive layer preferably further contains a polymerizable compound B1 having an aromatic ring and 2 ethylenically unsaturated groups.

Among the polymerizable compounds, the polymerizable compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in the molecule.

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

The polymerizable compound B1 may have 1 or 2 or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure in order to improve the resolution by suppressing swelling of the photosensitive layer by the developer.

Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and the bisphenol a structure is preferred.

Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.

The bisphenol structure may have 2 polymerizable groups directly bonded to both ends thereof or may have 1 or more alkyleneoxy groups bonded to both ends thereof. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and 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 Japanese patent application laid-open No. 2016-224162, which are incorporated herein by reference.

The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloyloxyalkyloxy) phenyl) propane.

Examples of the 2, 2-bis (4- ((meth) acryloyloxyalkyl polyalkoxy) phenyl) propane include ethoxylated bisphenol a dimethacrylate (BPE series, SHIN-NAKAMURA CHEMICAL Co., ltd. System), such as 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324m, showa Denko Materials Co., ltd. System), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane and 2, 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (fan-NAKAMURA CHEMICAL Co., ltd. System), 2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200my, showa Denko Materials Co., ltd. System), and ethoxylated (10) bisphenol a diacrylate (esnk ter a-BPE-10, SHIN-nakai, nakai Co., ltd. System).

As the polymerizable compound B1, a compound represented by the formula (B1) is also preferable.

[ chemical formula 1]

In the formula (B1), R ₁ And R ₂ Each independently represents a hydrogen atom or a methyl group. A represents a vinyl group. B represents a propenyl group. n1 and n3 each independently represent an integer of 1 to 39. n1+ n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29. n2+ n4 represents an integer of 0 to 30.

The arrangement of the structural units- (A-O) -and- (B-O) -may be either random or block 1. In the case of a block, any 1 of- (A-O) -and- (B-O) -may be on the bisphenyl side.

N1+ n2+ n3+ n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. N2+ n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, particularly preferably 0.

The content of the polymerizable compound B1 is preferably 10.0 mass% or more, more preferably 20.0 mass% or more, and further preferably 25.0 mass% or more with respect to the total mass of the photosensitive layer, from the viewpoint of further improving the resolution. The upper limit is preferably 70.0 mass% or less, more preferably 60.0 mass% or less, from the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive composition bleeds out from the end 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, and further preferably 55.0% by mass or more, based on the total mass of the polymerizable compounds, from the viewpoint of further improving the resolution. From the viewpoint of peelability, the upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, and further preferably 95.0% by mass or less, based on the total mass of the polymerizable compound.

Other polymerizable compounds

In addition to the above, the photosensitive layer preferably contains another polymerizable compound.

Examples of the other polymerizable compound include known polymerizable compounds.

Specifically, there may be mentioned a compound having 1 ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.

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

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), 1, 6-hexanediol diacrylate (A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), ethylene glycol dimethacrylate, 1, 10-decanediol diacrylate and di (meth) acrylate.

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

Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Further, commercially available urethane di (meth) acrylate includes, 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.).

Examples of the ethylenically unsaturated compound having 3 or more functions 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. Also, "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functional groups include caprolactone-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., manufactured by Ltd., kayarad (registered trademark) DPCA-20 and SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd., A-9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., manufactured by Ltd., karad (registered trademark) RP-1040, SHIN-NAKAMURA CHEMICAL Co., ATM-35E and A-9300, DAICEL-ALLNEX LTD, manufactured by EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol esters (e.g., SHIN-NAKAMURA CHEMICAL Co., ltd., A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (TOAGOSCO., manufactured by TOAGOSCO., ARIN-520, AROX-NAKAMURA CHEMICAL Co., manufactured by Ltd., LTEI).

The polymerizable compound may be a polymerizable compound having an acid group (e.g., a carboxyl group). The acid groups may form anhydride groups.

Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) (e.g., TO-2349, M-520, and M-510, manufactured by LTD., 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 Japanese patent application laid-open No. 2004-239942.

The molecular weight of the polymerizable compound is preferably 200 to 3000, more preferably 280 to 2200, and still more preferably 300 to 2200.

The viscosity of the polymerizable compound at 25 ℃ is preferably 1 to 10000 mPas, more preferably 5 to 3000 mPas, and still more preferably 10 to 1500 mPas.

The polymerizable compound may be used alone in 1 kind or 2 or more kinds.

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 still more preferably 30.0 to 70.0% by mass, based on the total mass of the photosensitive layer.

Polymerization initiators

The photosensitive layer preferably contains a polymerization initiator.

Examples of the polymerization initiator include known polymerization initiators depending on the form of the polymerization reaction. Specifically, a thermal polymerization initiator and a photopolymerization initiator are mentioned.

The polymerization initiator may be any 1 of a radical polymerization initiator and a cationic polymerization initiator.

The photosensitive layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that starts polymerization of the polymerizable compound upon receiving active light such as ultraviolet light, visible light, and X-ray.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

Examples of the photo radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylphenone structure, a photopolymerization initiator having an α -hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

The photo radical polymerization initiator preferably contains at least 1 selected from 2,4, 5-triarylimidazole dimers and derivatives thereof, from the viewpoint of photosensitivity, visibility of exposed portions and unexposed portions, and resolution. In addition, 2,4, 5-triarylimidazole dimers and 2,4, 5-triarylimidazole structures in the derivatives thereof may be the same or different.

Examples of the derivatives of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

Examples of the photo-radical polymerization initiator include those described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-095716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783.

Examples of the photo radical polymerization initiator include ethyl Dimethylaminobenzoate (DBE), benzoin methyl ether, anisole (p, p' -dimethoxybenzyl), TAZ-110 (Midori Kagaku Co., ltd., manufactured by Ltd.), TAZ-111 (Midori Kagaku Co., ltd., ltd.), 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-morpholino) phenyl ] -1-butanone (Omnirad 379EG, manufactured by IGM Resins B.V), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Omni 907, IGM Resins B.V), 2-hydroxy-1- {4- (2-hydroxypropionyl) 2-morpholinopropan-1-one (Omni 907, IGM Resins B.V), 2-hydroxy-1- {4- (2-hydroxy-2-methylpropionyl) 127- (2-methylbenzoyl } -1-one (Omni), IGM Resins B.V., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins B.V.), 2-dimethoxy-1, 2-diphenylethan-1-one (Omnirad 651, manufactured by IGM Resins B.V.), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins B.V.), photopolymerization initiator (Mannar 6, manufactured by SH), bis (2 ' -chlorophenyl) -4,4' -bis (DK), 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, changzhou Tronly New Electronic Materials Co.), ltd.), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furancarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (TR-PBG-326, changzzhou Tronly New Electronic Materials Co., ltd.)) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (TR-PBG-391, changzzhou Tronly New Electronic Materials Co., ltd.).

The photo cation polymerization initiator (photoacid generator) is a compound that receives active light to generate an acid.

Examples of the photo cation polymerization initiator include an ionic photo cation polymerization initiator and a nonionic photo cation polymerization initiator.

Examples of the ionic photo cation polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Examples of the ionic photo-cationic polymerization initiator include the ionic photo-cationic polymerization initiators described in paragraphs [0114] to [0133] of Japanese patent application laid-open Nos. 2014-085643.

Examples of the nonionic photocationic polymerization initiator include diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.

Examples of the diazomethane compound and the imide sulfonate compound include compounds described in paragraphs [0083] to [0088] of Japanese patent application laid-open No. 2011-221494.

Examples of the oxime sulfonate compound include compounds described in paragraphs [0084] to [0088] of International publication Nos. 2018/179640.

The polymerization initiator may be used singly in 1 kind or 2 or more kinds.

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 still more preferably 0.5% by mass or more, based on the total mass of the photosensitive layer. The upper limit is preferably 20.0 mass% or less, more preferably 15.0 mass% or less, and further preferably 10.0 mass% or less, with respect to the total mass of the photosensitive layer.

Polymerization inhibitors

The photosensitive layer also preferably contains a polymerization inhibitor (preferably a radical polymerization inhibitor).

The polymerization inhibitor refers to a compound having an effect of delaying or inhibiting the polymerization reaction.

When the photosensitive layer contains a polymerization inhibitor, the effect of the present invention can be further improved.

As the polymerization inhibitor, for example, a known polymerization inhibitor can be used. Specific examples of the polymerization inhibitor include phenothiazine-based compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, and 3, 7-dioctylphenothiazine; hindered phenol compounds such as bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid ] [ vinylbis (oxyethylene) ], 2, 4-bis [ (laurylthio) methyl ] -o-cresol, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl), 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl), 2, 4-bis- (n-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylanilino) -1,3, 5-triazine and pentaerythrityl tetrakis 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; phenoxazine-based compounds such as phenoxazine; nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine and N-nitrosophenylhydroxylamine, or salts thereof; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and tert-butylcatechol; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate.

Among them, from the viewpoint of further improving the effects of the present invention, at least 1 kind selected from phenothiazine-based compounds, hindered phenol-based compounds, and phenoxazine-based compounds is preferable as the polymerization inhibitor.

The polymerization inhibitor may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, even more preferably 0.02 to 2.0% by mass, particularly preferably 0.01 to 1.0% by mass, and most preferably 0.01 to 0.5% by mass, based on the total mass of the photosensitive layer. 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 still more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

Sensitizers

The photosensitive layer preferably contains a sensitizer.

Examples of the sensitizer include known sensitizers, dyes, and pigments.

Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, thiophene compounds, naphthylimine compounds, triarylamine compounds, and aminoacridine compounds.

The content of the sensitizer is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 1.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of enhancing the curing rate by enhancing the sensitivity to a light source and balancing the polymerization rate and the chain transfer.

Examples of the sensitizer include benzophenone compounds (preferably, dialkylaminobenzophenone compounds), thioxanthone compounds, cyanine compounds, coumarin compounds, merocyanine compounds, pyrazoline compounds, anthracene compounds, xanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthylimine compounds, triarylamine compounds, and aminoacridine compounds.

Among them, from the viewpoint of further improving the effects of the present invention, at least 1 selected from the group consisting of benzophenone-based compounds, thioxanthone-based compounds, cyanine-based compounds, coumarin-based compounds and merocyanine-based compounds is preferable.

As the dye-based sensitizer, a color-developing dye can also be used. The color-developing dye is a compound having a function of developing color by light irradiation. Examples of the color-developing dye include a leuco dye and a fluoran dye.

Specific examples of the sensitizer include fuchsin, phthalocyanine Green, coumarin 6, coumarin 7, coumarin 102, 3-acetyl-7- (diethylamino) coumarin, 4' -bis (diethylamino) benzophenone, potassium DOC iodide, indocyanine sodium, auramine base, chalcoxide Green S, coupled magenta, crystal violet, methyl orange, nile blue 2B, victoria blue, MALACHITE Green (Hodogaya Chemical co., ltd., aizen (registered trademark) malachigreen), basic blue 20, and DIAMOND Green (Hodogaya Chemical co., ltd., aizen (registered trademark) DIAMOND Green GH).

The photosensitive layer may contain 1 sensitizer alone or 2 or more sensitizers.

From the viewpoint of further improving the effect of the present invention, the content of the sensitizer is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 1.0% by mass, based on the total mass of the photosensitive layer.

Specific pigments

The photosensitive layer contains a specific pigment.

The specific 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 40nm or more. When the specific dye has a plurality of maximum absorption wavelengths, the difference between all the maximum absorption wavelengths and the maximum sensitivity wavelength is 40nm or more. The difference is obtained by subtracting a small value from a large 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 have the same value, the difference is 0.

The maximum absorption wavelength of a specific dye can be measured as follows: in an atmospheric environment, using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION) measures the transmission spectrum of a solution (liquid temperature 25 ℃) containing a specific dye in the range of 300 to 780nm, and detects a wavelength (maximum absorption wavelength) at which the light intensity is extremely small.

The method of measuring the maximum sensitivity wavelength of the photosensitive layer is as described above.

The specific pigment preferably does not include a pigment whose maximum absorption wavelength is changed by an acid, a base, or a radical. For example, a dye whose maximum absorption wavelength is changed by an acid, an alkali, or a radical corresponds to a dye N described below.

The specific dye may be a sensitizing dye or a non-sensitizing dye, but from the viewpoint of further improving the effect of the present invention, a non-sensitizing dye is preferable. In other words, the specific dye is preferably a non-sensitizing dye.

Further, as the non-sensitizing dye, there is a compound which does not rapidly bring a polymerization initiator into an excited state by energy transfer or electron transfer after changing from a ground state to a singlet excited state by light absorption; and a compound which does not rapidly bring the polymerization initiator into an excited state by energy transfer or electron transfer after the light absorption from the ground state to the singlet excited state in a wavelength range of 300 to 500nm, but rapidly brings the polymerization initiator into an excited state by energy transfer or electron transfer after the light absorption from the ground state to the singlet excited state in a wavelength range other than the above wavelength range.

Among the sensitizers described in the above paragraph, a sensitizer corresponding to a dye having a maximum absorption wavelength at a wavelength different from the maximum sensitivity wavelength of the photosensitive layer and a difference between the maximum absorption wavelength and the maximum sensitivity wavelength of the photosensitive layer of 40nm or more can be used as the specific dye.

The difference between the maximum absorption wavelength of the specific dye and the maximum sensitivity wavelength of the photosensitive layer is preferably 50nm or more, and more preferably 60nm or more. The upper limit is not particularly limited, but is preferably 150nm or less, for example.

The value of the maximum absorption wavelength of the specific dye and the value of the maximum sensitivity wavelength of the photosensitive layer may be larger, and the value of the maximum absorption wavelength of the specific dye may be larger than the value of the maximum sensitivity wavelength of the photosensitive layer, or the value of the maximum sensitivity wavelength of the photosensitive layer may be larger than the value of the maximum absorption wavelength of the specific dye.

The maximum absorption wavelength of the specific dye is preferably a wavelength range of over 395nm and 500nm or less, or a wavelength range of 300 to 395nm, and more preferably a wavelength range of 410 to 500nm or a wavelength range of 300 to 395 nm.

As an example of a preferable mode of combination of the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the specific dye, a mode in which the maximum sensitivity wavelength of the photosensitive layer is 300 to 395nm and the maximum absorption wavelength of the specific dye exceeds 395nm and is 500nm or less is given. In the above embodiment, the maximum absorption wavelength of the specific dye is preferably 410 to 500nm.

Further, another preferable embodiment of the combination of the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the specific dye includes an embodiment in which the maximum sensitivity wavelength of the photosensitive layer exceeds 395nm and is 500nm or less, and the maximum absorption wavelength of the specific dye is 300 to 395 nm. In the above embodiment, the maximum sensitivity wavelength of the photosensitive layer is preferably 410 to 500nm, and more preferably 410 to 450nm.

As the dye, a dye having an appropriate wavelength condition can be appropriately used from known dyes.

The coloring matter is not particularly limited, and examples thereof include a dye (including a metal complex-based coloring matter) and a pigment, and preferably a dye.

Examples of the dye having a maximum absorption wavelength of more than 395nm and 500nm or less include azo dyes, quinoline dyes, nitro dyes, methine dyes, indole dyes, metal complex dyes, and the like.

Examples of the azo dyes include c.i. acid yellow 11, c.i. acid orange 7, c.i. direct yellow 12, c.i. direct orange 26, c.i. reactive yellow 2, c.i. disperse orange 5, c.i. acid intermediate (Mordant) yellow 5, c.i. solvent yellow 16, and c.i. solvent yellow 56.

Examples of quinoline dyes include c.i. solvent yellow 33, c.i. acid yellow 3, and c.i. disperse yellow 64.

Examples of the nitro dyes include c.i. acid yellow 1, c.i. acid orange 3, and c.i. disperse yellow 42.

Examples of the methine dyes include c.i. disperse yellow 201. Further, examples of the methine dyes include compounds having the following structures.

[ chemical formula 2]

Examples of the indole-based dye include Bonasorb UA3912 and UA3912 (ORIENT CHEMICAL INDUSTRIES co., LTD).

Examples of the metal complex dye include a cobalt complex dye and a zinc complex dye.

Examples of the cobalt complex-based coloring matter include c.i. solvent yellow 89.

Examples of the zinc complex-based coloring matter include compounds having the following structures.

[ chemical formula 3]

Examples of the pigment having a maximum absorption wavelength of more than 395nm and 500nm or less include c.i. (pigment 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; c.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.

As the dye having a maximum absorption wavelength of 300 to 395nm, a known ultraviolet absorber can be used. Examples of the ultraviolet absorber having a maximum absorption wavelength of 300 to 395nm include benzotriazole compounds, benzophenone compounds, triazine compounds, salicylate compounds, cyanoacrylate compounds, and the like.

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, the following advantages are present: when the photosensitive layer is exposed, sensitivity reduction due to inhibition of a dye is less likely to occur. The absorbance of the specific dye at the maximum sensitivity wavelength of the photosensitive layer is more preferably 0.5 or less, and still more preferably 0.2 or less, from the viewpoint of further improving the effect of the present invention. The lower limit is not particularly limited, and is, for example, 0 or more.

As the absorbance of the specific dye, a spectrophotometer can be used: UV3100 (manufactured by SHIMADZU CORPORATION) and a transmission spectrum of a solution (liquid temperature 25 ℃) containing a specific dye at a concentration of 0.01 mass% in a range of 300 to 780nm were measured with a quartz cuvette having an optical path length of 1 mm.

When the photosensitive layer contains only 1 type of 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 2 or more kinds of specific dyes, it is preferable that the absorbance of the mixture of the 2 or more kinds of dyes in a state where the mixture ratio (mass ratio) in the layer is within the above numerical range.

In the transfer film according to embodiment 2 described later, when the thermoplastic resin layer contains only 1 type of specific coloring matter, the absorbance of the specific coloring matter at the maximum sensitivity wavelength of the photosensitive layer is preferably within the above numerical range. When the thermoplastic resin layer contains 2 or more kinds of specific coloring matters, the 2 or more kinds of coloring matters are preferably mixed so that the absorbance in a state where the mixing ratio (mass ratio) in the layer is within the above numerical range.

From the viewpoint of further improving the effect of the present invention, the content of the specific dye is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, even more preferably 0.1 to 10.0% by mass, and particularly preferably 1.0 to 10.0% by mass, based on the total mass of the photosensitive layer.

In a preferred embodiment, when the maximum sensitivity wavelength of the photosensitive layer exceeds 395nm and is 500nm or less and the photosensitive layer contains a specific dye having a maximum absorption wavelength of 300 to 395nm, the content of the dye having a maximum absorption wavelength of 395nm and is 500nm or less (the dye mentioned here preferably does not include a "dye (e.g., dye N) whose maximum absorption wavelength changes by an acid, an alkali, or a radical)" in the photosensitive layer is preferably 2.0 mass% or less, more preferably 1.5 mass% or less, and further preferably 1.0 mass% or less, particularly preferably 0.1 mass% or less, most preferably 0.01 mass% or less, based on the total mass of the photosensitive layer, from the viewpoint of further excellent effects of the present invention. The lower limit is 0 mass% or more.

Particularly preferred embodiments include the following: when the maximum sensitivity wavelength of the photosensitive layer exceeds 395nm and is 500nm or less and the photosensitive layer contains a specific dye having a maximum absorption wavelength of 300 to 395nm, the dye having a maximum absorption wavelength exceeding 395nm and being 500nm or less is not contained (the dye is preferably not a "dye whose maximum absorption wavelength is changed by an acid, an alkali, or a radical" (e.g., dye N) ") in the photosensitive layer.

In a preferred embodiment, when the photosensitive layer has a maximum sensitivity wavelength of 300 to 395nm and the photosensitive layer contains a specific coloring matter having a maximum absorption wavelength of more than 395nm and 500nm or less, the content of the coloring matter having a maximum absorption wavelength of 300 to 395nm (the coloring matter mentioned here preferably does not include "a coloring matter having a maximum absorption wavelength that changes by an acid, an alkali, or a radical (e.g., coloring matter N)") in the photosensitive layer 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, particularly preferably 0.1% by mass or less, and most preferably 0.01% by mass or less, based on the total mass of the photosensitive layer, from the viewpoint of further excellent effects of the present invention. The lower limit is 0 mass% or more.

Particularly preferred embodiments include the following: when the photosensitive layer has a maximum sensitivity wavelength of 300 to 395nm and contains a specific dye having a maximum absorption wavelength of over 395nm and 500nm or less, the dye having a maximum absorption wavelength of 300 to 395nm in the photosensitive layer is not contained (the dye preferably does not include a "dye whose maximum absorption wavelength is changed by an acid, an alkali, or a radical" (e.g., dye N)).

Pigment N-

The photosensitive layer may contain a dye (hereinafter, also referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical, in view of visibility of an exposed portion and a non-exposed portion and visibility and resolution of a pattern after development.

Although the detailed mechanism is not clear, when the dye N is contained, the adhesion with an adjacent layer (for example, an intermediate layer or the like) is improved and the resolution is more excellent.

The "dye" changes in the maximum absorption wavelength by an acid, an alkali, or a radical "may mean any of a method in which a dye in a colored state is decolorized by an acid, an alkali, or a radical, a method in which a dye in a decolorized state is colored by an acid, an alkali, or a radical, and a method in which a dye in a colored state is changed to a colored state of another color.

Specifically, the dye N may be any 1 of a compound that develops color by changing from a decolored state by exposure and a compound that develops color by changing from a colored state by exposure. In the above case, the dye may be one that changes the state of color development or decoloration by generating an acid, a base, or a radical in the photosensitive layer by exposure and acting, or may be one that changes the state of color development or decoloration by changing the state (for example, pH or the like) in the photosensitive layer by an acid, a base, or a radical. Further, the dye may be a dye which changes the state of color development or decoloration by being directly stimulated by an acid, an alkali, or a radical without exposure.

Among them, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

In view of the visibility and resolution of the exposed portion and the unexposed portion, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength as the dye N is changed by a radical and a photo radical polymerization initiator. The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, in view of the visibility of the exposed portion and the unexposed portion.

As a color developing mechanism of the pigment N, for example, there is a system in which a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator) or a photo base generator is added to a photosensitive layer, and after exposure, a radical reactive pigment, an acid reactive pigment or a base reactive pigment (for example, leuco pigment) is developed by a radical, an acid or a base generated from the photo radical polymerization initiator, the photo cation polymerization initiator or the photo base generator.

The maximum absorption wavelength in the wavelength range of 400 to 780nm in the color development of the dye N is preferably 550nm or more, more preferably 550 to 700nm, and still more preferably 550 to 650nm, from the viewpoint of the visibility of the exposed portion and the unexposed portion.

The dye N may have 1 or 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm in the case of color development. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm during color development, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the dye N can be measured as follows: under atmospheric conditions, using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION) measures the transmission spectrum of a solution containing dye N (liquid temperature 25 ℃) in the range of 400 to 780nm, and detects a wavelength at which the light intensity becomes extremely small (maximum absorption wavelength).

Examples of the coloring matter which develops color or discolors by exposure include colorless compounds.

Examples of the coloring matter decolorized by exposure to light include a leuco compound, a diarylmethane-based coloring matter, an oxazine-based coloring matter, a xanthene-based coloring matter, an imidonaphthoquinone-based coloring matter, an azomethine-based coloring matter, and an anthraquinone-based coloring matter.

The dye N is preferably a colorless compound in view of visibility of an exposed portion and a non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), a leuco compound having a fluoran skeleton (fluoran-based dye), a leuco compound having a diarylmethane skeleton (diarylmethane-based dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide-based dye), and a leuco compound having a leucoauramine skeleton (leucoauramine-based dye).

Among them, triarylmethane-based dyes and fluorane-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) and fluorane-based dyes are more preferable.

The colorless compound preferably has a lactone ring, a sudane (sulfene) ring, or a sultone ring in view of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sudantin ring or sultone ring of the colorless compound can be reacted with a radical generated from the photo radical polymerization initiator or an acid generated from the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolor it, or the colorless compound can be changed into an open ring state and develop color. As the colorless compound, a compound having a lactone ring, a sudantin ring, or a sultone ring and developing a color by a radical or acid ring opening is preferable, and a compound having a lactone ring and developing a color by a radical or acid ring opening is more preferable.

Examples of the pigment N include dyes and leuco compounds.

Examples of the dye include brilliant GREEN, ethyl violet, methyl GREEN, crystal violet, basic magenta, methyl violet 2B, quinaldine RED, rose bengal, m-aniline yellow, thymol BLUE, xylenol BLUE, methyl orange, p-methyl RED, congo RED, benzo RED violet 4B, α -naphthyl RED, nile BLUE 2B, nile BLUE a, methyl violet, malachite GREEN, coupled magenta, victoria pure BLUE-naphthalene sulfonate, victoria pure BLUE BOH (manufactured by Hodogaya Chemical co., LTD.), OIL BLUE #603 (manufactured by orlent Chemical INDUSTRIES co., LTD.), OIL PINK #312 (ORIENT Chemical INDUSTRIES, inc., LTD, manufactured by LTD), OIL RED5B (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL SCARLET #308 (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL RED OG (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL RED RR (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL GREEN #502 (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), spilon BEH special (Hodgaya Chemical Co., manufactured by Ltd), m-cresol purple, cresol RED, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenylimido-naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylnaphthoquinone, 2-carboxy-p-stearylamido-4-p-stearylaminophenylnaphthoquinone, n-bis (hydroxyethyl) amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazoline, and 1-beta-naphthalene-4-p-binaphthyl diethylaminophenylimino-5-pyrazoline.

Examples of the colorless compound include p, p' -hexamethyltriaminotriphenylmethane (colorless crystal violet), pergascript Blue SRB (manufactured by Ciba-Geigy AG), crystal violet lactone, malachite green lactone, benzoyl leuco methylene Blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidine) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-xylenefluoran, 3- (N, N-diethylamino) -6-methyl-7-chlorofluoran, 3- (N, N-diethylamino) -6-methoxy-7-aminofluoran, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluoran, 3- (N, n-diethylamino-7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-xylanilinofluoran, 3-piperidine-6-methyl-7-anilinofluoran, 3-pyrrolidine-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-phenyl) -7-benzylaminofluorane, and 3- (1' -diethylamino) -6-methyl-7-anilinofluoran, 9' - [9H ] xanthen-3-one.

The dye N is preferably a dye whose maximum absorption wavelength changes by a radical, and more preferably a dye whose color is developed by a radical, because the dye N is excellent in visibility of an exposed portion and a non-exposed portion, visibility of a pattern after development, and resolution.

As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate is preferable.

The pigment N may be used alone in 1 or 2 or more.

The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass, based on the total mass of the 1 st photosensitive layer or the 2 nd photosensitive layer, from the viewpoint of excellent visibility of the exposed portion and the unexposed portion, and visibility of the pattern after development and resolution.

The content of the pigment N is a content of the pigment when all the pigment N included in the total mass of the photosensitive layer is in a colored state. Hereinafter, a method for quantifying the content of pigment N will be described by taking a pigment that develops color by a radical as an example.

A solution prepared by dissolving pigment N (0.001 g) in 100mL of methyl ethyl ketone and a solution prepared by dissolving pigment N (0.01 g) in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, a photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan ltd.) was added and 365nm light was irradiated, thereby generating radicals and bringing all the dye N into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured by a spectrophotometer (UV 3100, manufactured by SHIMADZU CORPORATION) under an atmospheric environment to prepare a calibration curve.

Next, the absorbance of the solution in which all the dyes were developed was measured in the same manner as described above except that the 1 st photosensitive layer or the 2 nd photosensitive layer (3 g) was dissolved in methyl ethyl ketone instead of the dye N. From the obtained absorbance of the solution containing the photosensitive layer, the content of the pigment N contained in the photosensitive layer was calculated from the calibration curve.

Other additives

The photosensitive layer may contain other additives as needed in addition to the above components.

Examples of the other additives include benzotriazoles, carboxybenzotriazoles, surfactants, plasticizers, heterocyclic compounds (e.g., triazole, imidazole, etc.), pyridines (e.g., isonicotinamide, etc.), and purine bases (e.g., adenine, etc.).

Examples of the other additives include metal oxide particles, a chain transfer agent, an antioxidant, a dispersant, an acid amplifier, a development accelerator, conductive fibers, a thickener, a crosslinking agent, an organic or inorganic anti-settling agent, and paragraphs [0165] to [0184] of jp 2014-085643 a, which are incorporated herein.

The other additives may be used alone in 1 or 2 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-methylbenzotriazole and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

-carboxybenzotriazoles-

Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminovinyl carboxybenzotriazole.

Specific examples of carboxybenzotriazoles include CBT-1 (JOOOKU CHEMICAL CO., LTD).

The total content of the benzotriazole and carboxybenzotriazole is preferably 0.01 to 3% by mass, and 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 sensitivity is maintained and the dye discoloration is suppressed more excellently.

Surfactants-

Examples of the surfactant include surfactants described in paragraphs [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application laid-open No. 2009-237362.

The surfactant is preferably a nonionic surfactant, a fluorine surfactant, or a silicone surfactant.

Examples of the fluorine-based surfactant include MEGAFACE 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-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94 and DS-21 (manufactured by Corporation); fluorad FC430, FC431 and FC171 (manufactured by Sumitomo 3M Limited); 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 Inc.); polyFox PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc.); ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by Neos Corporation).

Further, as the fluorine-based surfactant, the following acrylic compounds can also be preferably used: having a molecular structure containing a functional group containing a fluorine atom, a part of the functional group containing a fluorine atom is cleaved upon heating to volatilize the fluorine atom.

Examples of such fluorine-containing surfactants include MEGAFACE DS series (The Chemical Daily Co., ltd. (2016: 2/22 days) and NIKKEI BUSINESS DAILY (2016: 2/23 days))

Further, as the fluorine-based surfactant, 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 is preferably used.

As the fluorine-based surfactant, a block polymer can also be used.

The fluorine-containing surfactant is preferably a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).

Further, examples of the fluorine-based surfactant include fluoropolymers having an ethylenically unsaturated group in a side chain, such as MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (see above, DIC Corporation).

As the fluorine-based surfactant, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferable from the viewpoint of improving environmental compatibility.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, ethoxylates and propoxylates thereof (e.g., glycerin propoxylate and glycerin ethoxylate), 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 corporation); TETRONIC 304, 701, 704, 901, 904 and 150R1 (BASF, supra); solsperse 20000 (made by The Lubrizol Corporation); NCW-101, NCW-1001, and NCW-1002 (both of which are manufactured by FUJIFILM Wako Pure Chemical Corporation); PIONI D-6112, D-6112-W and D-6315 (above, TAKEMOTO OIL & FAT Co., manufactured by Ltd.); OLFINE E1010, surfynol 104, 400 and 440 (above, made by Nissin Chemical Industry co., ltd.).

Examples of the silicone surfactant include linear polymers composed of siloxane bonds, and modified siloxane polymers having organic groups introduced into side chains and/or terminals thereof.

Examples of the silicone surfactant include DOWNSIL 8032ADDITIVE, TORAY SILICON DC3PA, TORAY SILICON SH7PA, TORAY SILICON DC11PA, TORAY SILICON SH21PA, TORAY SILICON SH28PA, TORAY SILICON SH29PA, TORAY SILICON SH30PA, and TORAY SILICON SH8400 (Dow Corning Toray Co., ltd., above); x-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (Shin-Etsu Silicone Co., ltd.); f-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive performance materials Inc.); BYK307, BYK323, and BYK330 (manufactured by BYK-Chemie GmbH).

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

Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of International publication No. 2018/179640.

Impurities-

The photosensitive layer may contain impurities.

Examples of the impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.

Metal impurities and halide ions-

Examples of the metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, ions thereof, and halide ions.

Among them, sodium ions, potassium ions, and halide ions are preferably contained in the following amounts from the viewpoint of easy mixing.

The metal impurities are compounds different from the particles (for example, metal oxide particles) that can be contained in the transfer film.

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

Examples of the method of adjusting the content of the impurity include a method of selecting a raw material having a small content of the impurity as a raw material of the photosensitive layer; a method of preventing impurities from being mixed in when forming a photosensitive layer; and a method of cleaning and removing.

For example, the content of impurities can be determined by a known method such as ICP emission spectrometry, atomic absorption spectrometry, or ion chromatography.

Residual organic solvent-

Examples of the residual organic solvent include benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane.

The content of the residual organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less, based on the total mass of the photosensitive layer. The lower limit is preferably 10 mass ppb or more, and more preferably 100 mass ppb or more, with respect to the total mass of the photosensitive layer.

As a method for adjusting the content of the residual organic solvent, a method for adjusting drying conditions in a method for producing a transfer film to be described later can be mentioned. The content of the residual organic solvent can be quantified by a known method such as gas chromatography.

Residual monomers-

The photosensitive layer may contain a residual monomer of each structural unit of the resin.

The content of the residual monomer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and still more preferably 500 mass ppm or less, based on the total mass of the resin, from the viewpoint of pattern formability and reliability. The lower limit is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, with respect to the total mass of the resin.

In view of pattern formability and reliability, the residual monomer in each structural unit of the alkali-soluble resin is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, with respect to the total mass of the photosensitive layer. The lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, with respect to the total mass of the photosensitive layer.

The residual amount of the monomer in synthesizing the alkali-soluble resin by the high molecular reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.

Examples of the method for adjusting the content of the residual monomer include the above-mentioned methods for adjusting the content of impurities.

The content of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

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

Characteristics of the photosensitive layer (photosensitive layer A)

The average thickness of the photosensitive layer is usually 0.1 to 300. Mu.m, preferably 0.2 to 100. Mu.m, more preferably 0.5 to 50 μm, and still more preferably 1 to 20 μm. This can improve the developability of the photosensitive layer and also improve the resolution.

The average thickness of the photosensitive layer was determined as an average value of the thickness at 10 points measured by observing a cross section perpendicular to the in-plane direction of the photosensitive layer with a Scanning Electron Microscope (SEM).

(photosensitive layer B) of embodiment 2)

The components that can be contained in the photosensitive layer B will be described below.

Adhesive polymers

The photosensitive layer may include a binder polymer.

Examples of the binder polymer include (meth) acrylic resins, styrene resins, epoxy resins, polyamide epoxy resins, alkyd resins, phenol resins, polyester resins, urethane resins, epoxy acrylate resins obtained by reaction of an epoxy resin with (meth) acrylic acid, and acid-modified epoxy acrylate resins obtained by reaction of an epoxy acrylate resin with an acid anhydride.

As one of preferable embodiments of the binder polymer, a (meth) acrylic resin is mentioned in view of excellent alkali developability and film forming property.

In the present specification, the (meth) acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, relative to all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin may be composed of only a structural unit derived from a (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than a (meth) acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100 mass% or less with respect to all the structural units of the (meth) acrylic resin.

Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylonitriles.

Examples of the (meth) acrylic acid ester include alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-trifluoroethyl (meth) acrylate, and 2, 3-tetrafluoropropyl (meth) acrylate, and alkyl (meth) acrylate is preferable.

Examples of the (meth) acrylamide include acrylamides such as diacetone acrylamide.

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

The (meth) acrylic acid ester is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and more preferably methyl (meth) acrylate or ethyl (meth) acrylate.

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 acid compound copolymerizable with the (meth) acrylic acid compound, and examples thereof include styrene compounds which may have a substituent at the α -position or at the aromatic ring, such as styrene, vinyltoluene and α -methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid and crotonic acid.

These polymerizable monomers may be used alone in 1 or 2 or more.

In addition, from the viewpoint of further improving the alkali developability, the (meth) acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonate group.

Among these, (meth) acrylic resins more preferably contain a structural unit having a carboxyl group, and still more preferably have 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 preferably 10 mass% or more with respect to the total mass of the (meth) acrylic resin from the viewpoint of excellent developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.

The (meth) acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth) acrylate.

The content of the structural unit derived from an alkyl (meth) acrylate in the (meth) acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 90% by mass, based on all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin is preferably a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate, and more preferably a resin composed of only a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate.

Further, 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.

The (meth) acrylic resin preferably has at least 1 kind selected from a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and more preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate.

The total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate in the (meth) acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on all the structural units of the (meth) acrylic resin. The upper limit is not particularly limited, and may be 100 mass% or less, preferably 80 mass% or less.

The (meth) acrylic resin preferably has at least 1 kind selected from a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate and at least 1 kind selected from a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate.

The total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate is preferably 60/40 to 80/20 in terms of a mass ratio to the total content of the structural unit derived from acrylic acid and the structural unit derived from alkyl acrylate.

The (meth) acrylic resin preferably has an ester group at a terminal thereof in view 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 a polymerization initiator used for synthesis. The (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

In another preferred embodiment of the binder polymer, an alkali-soluble resin is used.

For example, the binder polymer is preferably a binder polymer having an acid value of 60mgKOH/g or more from the viewpoint of developability.

Further, for example, from the viewpoint of facilitating the formation of a strong film by thermal crosslinking with the crosslinking component by heating, the binder polymer is more preferably a resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing resin), and still more preferably a (meth) acrylic resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing (meth) acrylic resin).

When the binder polymer is a resin having a carboxyl group, for example, a thermally crosslinkable compound such as a blocked isocyanate compound is added to thermally crosslink the resin, whereby the three-dimensional crosslinking density can be increased. In addition, the moisture and heat resistance can be improved by dehydrating and hydrophobizing the carboxyl group of the resin having a carboxyl group.

The carboxyl group-containing (meth) acrylic resin having an acid value of 60mgKOH/g or more is not particularly limited as long as the above-mentioned acid value condition is satisfied, and can be appropriately selected from known (meth) acrylic resins.

For example, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph [0025] of Japanese patent application laid-open No. 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs [0033] to [0052] of Japanese patent application laid-open No. 2010-237589, or the like can be preferably used.

Another preferable embodiment of the binder polymer is a styrene-acrylic acid copolymer.

In the present specification, the styrene-acrylic acid copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic acid compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth) acrylic acid compound is preferably 30% by mass or more, and more preferably 50% by mass or more, based on all the structural units of the copolymer. The upper limit is often 100 mass% or less.

The content of the structural unit 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 the total structural units of the copolymer.

The content of the structural unit derived from the (meth) acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20 to 95% by mass, based on all the structural units of the copolymer.

The binder polymer preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

Examples of the monomer forming the structural unit having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer 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, vinylbenzyl alcohol and the like. Among them, benzyl (meth) acrylate is preferable.

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

[ chemical formula 4]

When the binder polymer contains 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 preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on all the structural units of the binder polymer.

The content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 60 mol% based on all the structural units of the binder polymer.

The content of the structural unit represented by the formula (S) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, further preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%, based on all the structural units of the binder polymer.

In the present specification, when the content of the "structural unit" is defined by a molar ratio, the meaning of the "structural unit" is the same as that of the "monomer unit". In the present specification, the "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 contains a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be a monocyclic ring or a polycyclic ring. Among them, the binder polymer more preferably has a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isophorone ring.

Among these, preferred are rings obtained by fusing 2 or more aliphatic hydrocarbon rings, and more preferred is a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 ] ^2,6 ]Decane ring).

Examples of the monomer forming a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

The binder polymer preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[ chemical formula 5]

In the formula (Cy), R ^M Represents a hydrogen atom or a methyl group, R ^Cy Represents a 1-valent group having an aliphatic hydrocarbon ring structure.

R in the formula (Cy) ^M Preferably methyl.

R in the formula (Cy) ^Cy The aliphatic hydrocarbon cyclic structure-containing 1-valent group preferably has 5 to 20 carbon atoms, more preferably has 6 to 16 carbon atoms, and yet more preferably has 8 to 14 carbon atoms.

And R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (2) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure.

And R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (2) is preferably a ring structure in which 2 or more aliphatic hydrocarbon rings are fused, and more preferably a ring structure in which 2 to 4 aliphatic hydrocarbon rings are fused.

And R in the formula (Cy) ^Cy Preferred is a group in which an oxygen atom of-C (= O) O-in the formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferred is cyclohexyl or dicyclopentyl, and further preferred is dicyclopentyl.

The binder polymer may have 1 kind of structural unit having an aliphatic hydrocarbon ring structure alone or 2 or more kinds.

When the binder polymer contains 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, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass, based on all the structural units of the binder polymer.

The content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

The content of the structural unit represented by the formula (Cy) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

When the binder polymer contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass, based on all the structural units of the binder polymer.

The total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units of the binder polymer.

The total content of the structural unit represented by the formula (S) and the structural unit represented by the formula (Cy) in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol%, based on all the structural units of the binder polymer.

The binder polymer preferably comprises structural units having acid groups.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group, and a carboxyl group is preferable.

The structural unit having an acid group is preferably a structural unit derived from (meth) acrylic acid shown below, and more preferably a structural unit derived from methacrylic acid.

[ chemical formula 6]

The binder polymer may contain 1 kind of structural unit having an acid group alone, or may contain 2 or more kinds.

When the binder polymer contains 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, and still more preferably 10 to 30% by mass, based on all the structural units of the binder polymer.

The content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on all the structural units of the binder polymer.

The content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on all the structural units of the binder polymer.

The binder polymer preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

The reactive group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

In the present specification, "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" refers to a group of atoms branched from the main chain.

As the ethylenically unsaturated group, an allyl group or a (meth) acryloyloxy group is more preferable.

Examples of the structural unit having a reactive group include, but are not limited to, those described below.

[ chemical formula 7]

The binder polymer may contain 1 kind of structural unit having a reactive group alone, or may contain 2 or more kinds.

When the binder polymer contains 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, and still more preferably 20 to 40% by mass, based on all the structural units of the binder polymer.

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%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

Examples of a method for introducing a reactive group into the binder polymer include a method in which a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic anhydride is reacted with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group.

Preferred examples of the method for introducing a reactive group into a binder polymer include the following methods: after a polymer having a carboxyl group is synthesized by polymerization, a glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the obtained polymer by polymer reaction, thereby introducing a (meth) acryloyloxy group into the polymer. By this method, a binder polymer having a (meth) acryloyloxy group in a side chain can be obtained.

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

As the binder polymer, polymers X1 to X4 shown below are preferable. The content ratios (a to d) of the respective constituent units shown below, the weight average molecular weight Mw, and the like can be appropriately changed according to the purpose, and among them, the following configuration is preferable from the viewpoint of further improving the effects of the present invention.

(Polymer X1) a:20 to 60 mass%, b:10 to 50 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

(Polymer X2) a:20 to 60 mass%, b:10 to 50 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

(Polymer X3) a:30 to 65 mass%, b:1.0 to 20 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

(Polymer X4) a:1.0 to 20 mass%, b:20 to 60 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

[ chemical formula 8]

Also, the binder polymer may contain a polymer (hereinafter, also referred to as "polymer X") containing a structural unit having a carboxylic anhydride structure.

The carboxylic anhydride structure may be 1 of a chain carboxylic anhydride structure and a cyclic carboxylic anhydride structure, and 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 still more preferably a 5-membered ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit containing in the main chain a 2-valent group obtained by removing 2 hydrogen atoms from a compound represented by the following formula P-1 or a structural unit in which a 1-valent group obtained by removing 1 hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a 2-valent linking group.

[ chemical formula 9]

In the formula P-1, R ^A1a Represents a substituent, n ^1a R is ^A1a May be the same or different, Z ^1a Represents a 2-valent group, n, forming a ring containing-C (= O) -O-C (= O) - ^1a Represents an integer of 0 or more.

As a group consisting of R ^A1a Examples of the substituent include an alkyl group.

As Z ^1a The alkylene group having 2 to 4 carbon atoms is preferable, the alkylene group having 2 or 3 carbon atoms is more preferable, and the alkylene group having 2 carbon atoms is further preferable.

n ^1a Represents an integer of 0 or more. At Z ^1a When it represents an alkylene group having 2 to 4 carbon atoms, n ^1a Preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

n ^1a When an integer of 2 or more is represented, a plurality of R ^A1a May be the same or different. And a plurality of R ^A1a The ring may be formed by bonding to each other, but preferably the ring is formed by not bonding to each other.

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, still more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

Specific examples of the structural unit having a carboxylic anhydride structure are given below, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, rx represents a hydrogen atom, a methyl group, or CH ₂ OH group or CF ₃ Me represents a methyl group.

[ chemical formula 10]

[ chemical formula 11]

The number of the structural units having a carboxylic anhydride structure in the polymer X may be 1 or 2 or more.

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

The photosensitive layer may contain only 1 type of polymer X, or may contain 2 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, even more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass, based on the total mass of the photosensitive layer.

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

The acid value of the adhesive polymer is preferably from 10 to 200mgKOH/g, more preferably from 60 to 200mgKOH/g, still more preferably from 60 to 150mgKOH/g, and particularly preferably from 70 to 125mgKOH/g.

The acid value of the binder polymer was set in accordance with JIS K0070: 1992.

From the viewpoint of developability, the dispersion degree 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 particularly preferably 1.0 to 3.0.

The photosensitive layer may contain only 1 binder polymer, or may contain 2 or more kinds.

The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass, based on the total mass of the photosensitive layer.

Polymeric compounds

The photosensitive layer may contain a polymerizable compound.

The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group, and a radical polymerizable group is preferable.

The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, sometimes simply referred to as "ethylenically unsaturated compound").

As the ethylenically unsaturated group, (meth) acryloyloxy group is preferable.

The ethylenically unsaturated compound in the present specification is a compound other than the above binder polymer, and the molecular weight is preferably less than 5,000.

As one of preferable embodiments of the polymerizable compound, a compound represented by the following formula (M) (also simply referred to as "compound M") can be mentioned.

Q ² -R ¹ -Q ¹ Formula (M)

In the formula (M), Q ¹ And Q ² Each independently represents a (meth) acryloyloxy group, R ¹ Represents a 2-valent linking group having a chain structure.

With respect to Q in the formula (M) ¹ And Q ² From the viewpoint of ease of synthesis, Q is preferably Q ¹ And Q ² Are the same group.

And, from the reactivity point of view, Q in the formula (M) ¹ And Q ² Preference is given to acryloyloxy.

As R in formula (M) ¹ Preferably an alkylene group or an alkyleneoxyalkylene group (-L) ¹ -O-L ¹ -) or polyalkyleneoxyalkylene (- (L) ¹ -O) _p -L ¹ -) more preferably a hydrocarbon group or a polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, still more preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

The hydrocarbon group may have a chain structure in at least a part thereof, and the part other than the chain structure is not particularly limited, and may be, for example, any of 1, preferably an alkylene group or a combination of 1 or more alkylene groups and 1 or more arylene groups among branched, cyclic or linear alkylene groups having 1 to 5 carbon atoms, arylene groups, ether bonds, and combinations thereof, more preferably an alkylene group, and still more preferably a linear alkylene group.

Further, L is as defined above ¹ Each 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 to 10.

And Q in the compound M ¹ And Q ² The number of atoms of the shortest connecting chain connecting the two members is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

In this specification, "connection Q ¹ And Q ² The number of atoms of the shortest connecting chain therebetween "means the number of atoms to be bonded to Q ¹ Attached R ¹ To the atom in (A) is connected to Q ² Attached R ¹ The shortest number of atoms in (2).

Specific examples of the 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, di (meth) acrylate of hydrogenated bisphenol A, di (meth) acrylate of hydrogenated bisphenol F, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol/propylene glycol) di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. The above ester monomers can also be used as mixtures.

Of the above compounds, at least 1 compound selected from 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate is preferable, at least 1 compound selected from 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable, and at least 1 compound selected from 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is further preferable.

Further, as one of preferable embodiments of the polymerizable compound, an ethylenically unsaturated compound having 2 or more functions is exemplified.

In the present specification, "an ethylenically unsaturated compound having 2 or more functions" means a compound having 2 or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth) acryloyl group is preferable.

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The 2-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

Examples of the 2-functional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1, 4-cyclohexanediol di (meth) acrylate.

Examples of commercially available products of 2-functional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ESTETTR A-DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTTR DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (trade name: NK ESTTR A-NOD-N, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), and 1, 6-hexanediol diacrylate (trade name: NK ESTTR A-HD-N, SHIN-NAKARA CHEMICAL Co., manufactured by Ltd.).

The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and can be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound having 3 or more functions 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 a (meth) acrylate compound having a glycerin tri (meth) acrylate skeleton.

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

Examples of the polymerizable compound include caprolactone-modified compounds of (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, SHIN-NAKAMURA CHEMICAL Co., ltd., A-9300-1CL Co., ltd.), (e.g., alkylene oxide-modified compounds of (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) RP-1040, SHIN-NAKAMURA CHEMICAL Co., ltd., EBECRYL ATM-35E, A-9300, DAICEL-ALLNEX LTD. EBECRYL (registered trademark) 135), and ethoxylated glycerol triacrylate (SHIN-NAKAMURA CHEMICAL Co., ltd., NK ESTER A-GLY-9E).

The polymerizable compound may also be a urethane (meth) acrylate compound.

Examples of the urethane (meth) acrylate include urethane di (meth) acrylates, and examples thereof include propylene oxide-modified urethane di (meth) acrylates, and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylates.

Further, as the urethane (meth) acrylate, there may be mentioned a 3-or more-functional urethane (meth) acrylate. The lower limit of the number of functional groups is preferably 6 or more functional groups, and more preferably 8 or more functional groups. The upper limit of the number of functional groups is more preferably 20 or less. Examples of the 3-or more-functional urethane (meth) acrylate include 8UX-015A (manufactured by Taisei Fine Chemical Co., ltd.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), U-15HA (manufactured by Ltd.), UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), KYOEISHA CHEMICAL CO., manufactured by LTD. AH-600 (manufactured by trade name), UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (both manufactured by Nippon Kayaku Co., ltd.).

As a preferable embodiment of the polymerizable compound, an ethylenically unsaturated compound having an acid group can be mentioned.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

Among them, as the acid group, a carboxyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include a 3 to 4-functional ethylenically unsaturated compound having an acid group [ a compound having an acid group (acid value: 80 to 120 mgKOH/g) obtained by introducing a carboxyl group into a pentaerythritol tri-and tetraacrylate (PETA) skeleton ], a 5 to 6-functional ethylenically unsaturated compound having an acid group [ a compound having an acid group (acid value: 25 to 70 mgKOH/g) obtained by introducing a carboxyl group into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton ], and the like.

These ethylenically unsaturated compounds having 3 or more functions of the acid group may be used together with the ethylenically unsaturated compounds having 2 functions of the acid group, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least 1 selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof.

When the ethylenically unsaturated compound having an acid group is at least 1 selected from the group consisting of an ethylenically unsaturated compound having 2 or more functions of a carboxyl group and a carboxylic anhydride thereof, the developability and the film strength are further improved.

The ethylenically unsaturated compound having a carboxyl group and a 2-or more-functional group is not particularly limited, and can be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound having 2 or more functional groups and having a carboxyl group include ARONIX (registered trademark) TO-2349 (TOAGOSEI co., ltd., manufactured), ARONIX (registered trademark) M-520 (TOAGOSEI co., ltd., manufactured), and ARONIX (registered trademark) M-510 (TOAGOSEI co., ltd., manufactured).

As the ethylenically unsaturated compound having an acid group, a polymerizable compound having an acid group described in paragraphs [0025] to [0030] of Japanese patent laid-open No. 2004-239942 is preferable, and the contents described in this publication are incorporated in the present specification.

Examples of the polymerizable compound include 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, a urethane monomer such as a (meth) acrylate compound having a urethane bond, an phthalic acid compound such as γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate and β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, and an alkyl (meth) acrylate.

These may be used alone or in combination of 2 or more.

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid include bisphenol a-based (meth) acrylate compounds such as 2, 2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypolyoxypropyloxy) phenyl) propane and 2, 2-bis (4- ((meth) acryloyloxypolyoxypropyloxy) phenyl) propane, polyethylene glycol di (meth) acrylates having an ethylene oxide number of 2 to 14, polypropylene glycol di (meth) acrylates having an propylene oxide number of 2 to 14, polyethylene glycol polypropylene glycol di (meth) acrylates having an ethylene oxide number of 2 to 14 and a propylene oxide number of 2 to 14, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytrimethylol tri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxy tri (meth) acrylate, trimethylolpropane pentaethoxy tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolpropane tetratrimethyoxymethane acrylate, pentaerythritol tetramethylol (meth) acrylate, pentaerythritol tetramethylol (meth) acrylate, trimethylolpropane triethoxytrimethylolpropane di (meth) acrylate, pentaerythritol tetramethylol (meth) acrylate, and pentaerythritol tetramethylol (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., nippon Kayaku Co., ltd., kayarad (registered trademark) DPCA-20 manufactured by Ltd., SHIN-NAKAMURA CHEMICAL Co., ltd., A-9300-1CL manufactured by Ltd.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., nippon Kayaku Co., ltd., kayarad RP-1040 manufactured by Ltd., SHIN-NAKAMURA CHEMICAL Co., ltd., ATM-35E manufactured by Ltd., A-9300, DAICEL-ALLNEX LTD, EBECRYL (registered trademark) 135 manufactured by Ltd.), ethoxylated glycerides (e.g., SHIN-NAKAMURA CHEMICAL Co., ltd., A-GLY-9E manufactured by Ltd.), and the like.

The polymerizable compound (particularly, an ethylenically unsaturated compound) preferably contains an ester bond, among others, 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, but from the viewpoint of the excellent effect of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes 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.

Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.

One of preferred embodiments of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably, a 2-functional ethylenically unsaturated compound).

The polymerizable compound is preferably a polymerizable compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a 2-functional ethylenically unsaturated compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed, and still more preferably tricyclodecanedimethanol di (meth) acrylate.

The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure.

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.

The proportion of the content of the polymerizable compound having a molecular weight of 300 or less in the polymerizable compound contained in the photosensitive layer is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all the polymerizable compounds contained in the photosensitive layer.

As one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains an ethylenically unsaturated compound having 2 or more functions, more preferably contains an ethylenically unsaturated compound having 3 or more functions, and further preferably contains an ethylenically unsaturated compound having 3 or 4 functions.

In addition, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer containing a structural unit having an aliphatic hydrocarbon ring.

In addition, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and further preferably contains a succinic acid-modified product of 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and dipentaerythritol pentaacrylate.

In addition, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

In addition, as one of preferable embodiments of the photosensitive layer, from the viewpoint of the development residue suppression property and the rust prevention property, the photosensitive layer preferably contains a 2-functional ethylenically unsaturated compound (preferably a 2-functional (meth) acrylate compound) and an ethylenically unsaturated compound having 3 or more functions (preferably a (meth) acrylate compound having 3 or more functions).

The mass ratio of the content of the 2-functional ethylenically unsaturated compound to the content of the 3-or more-functional ethylenically unsaturated compound is preferably 10 to 10, more preferably 30.

The content of the 2-functional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.

The 2-functional ethylenically unsaturated compound in the photosensitive layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.

In addition, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains the compound M and a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.

In addition, as one of preferable embodiments of the photosensitive layer, from the viewpoint of substrate adhesion, development residue suppression property, and rust prevention property, the photosensitive layer preferably contains the compound M and an ethylenically unsaturated compound having an acid group, more preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, further preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having 3 or more functions, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having 3 or more functions, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound.

In addition, as one of preferable embodiments of the photosensitive layer, from the viewpoint of substrate adhesion, development residue suppression property, and rust prevention property, the photosensitive layer preferably contains 1, 9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, still more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

The content of the ethylenic unsaturated compound having 2 or more functions in the ethylenic unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, based on the total content of all the ethylenic unsaturated compounds contained in the photosensitive layer.

The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone in 1 kind or in combination of 2 or more kinds.

The content of the polymerizable compound (particularly, an ethylenically unsaturated compound) in the photosensitive layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, still more preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass, based on the total mass of the photosensitive layer.

Specific pigments-

The photosensitive layer contains a specific pigment.

The specific dye 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 40nm or more.

The type and characteristics of the specific dye contained in the photosensitive layer (photosensitive layer B) and the relationship between the photosensitive layer and the maximum sensitivity wavelength are the same as those of the photosensitive layer a described above, and the preferred embodiments are the same.

In a preferred embodiment, when the maximum sensitivity wavelength of the photosensitive layer exceeds 395nm and is 500nm or less and the photosensitive layer contains a specific pigment having a maximum absorption wavelength of 300 to 395nm, the content of the pigment having a maximum absorption wavelength of 395nm and is 500nm or less (the pigment mentioned here preferably does not include "a pigment having a maximum absorption wavelength that changes by an acid, a base, or a radical") in the photosensitive layer is preferably 2.0 mass% or less, more preferably 1.5 mass% or less, and further preferably 1.0 mass% or less, particularly preferably 0.1 mass% or less, and most preferably 0.01 mass% or less, based on the total mass of the photosensitive layer, from the viewpoint of further excellent effects of the present invention. The lower limit is 0 mass% or more.

Particularly preferred embodiments include the following: when the maximum sensitivity wavelength of the photosensitive layer exceeds 395nm and is 500nm or less and the photosensitive layer contains a specific coloring matter having a maximum absorption wavelength of 300 to 395nm, the coloring matter having a maximum absorption wavelength exceeding 395nm and is 500nm or less in the photosensitive layer is not contained (the coloring matter mentioned here preferably does not include "a coloring matter having a maximum absorption wavelength that changes by an acid, an alkali, or a radical").

In a preferred embodiment, when the photosensitive layer has a maximum sensitivity wavelength of 300 to 395nm and the photosensitive layer contains a specific coloring matter having a maximum absorption wavelength of more than 395nm and 500nm or less, the content of the coloring matter having a maximum absorption wavelength of 300 to 395nm in the photosensitive layer (the coloring matter mentioned here preferably does not include "coloring matter having a maximum absorption wavelength that changes by an acid, an alkali, or a radical") is preferably 2.0 mass% or less, more preferably 1.5 mass% or less, and further preferably 1.0 mass% or less, particularly preferably 0.1 mass% or less, and most preferably 0.01 mass% or less, based on the total mass of the photosensitive layer, from the viewpoint of further excellent effects of the present invention. The lower limit is 0 mass% or more.

Particularly preferred embodiments include the following: when the photosensitive layer has a maximum sensitivity wavelength of 300 to 395nm and contains a specific dye having a maximum absorption wavelength of over 395nm and 500nm or less, the dye having a maximum absorption wavelength of 300 to 395nm in the photosensitive layer is not contained (the dye preferably does not include a "dye whose maximum absorption wavelength is changed by an acid, an alkali, or a radical").

Polymerization initiators

The photosensitive layer may contain a polymerization initiator.

As the polymerization initiator, a photopolymerization initiator is preferable.

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkylphenone structure (hereinafter, also referred to as an "α -aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkylphenone structure (hereinafter, also referred to as an "α -hydroxyalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").

The photopolymerization initiator preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, α -hydroxyalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

Further, as the photopolymerization initiator, for example, the photopolymerization initiators described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-95716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783 can be used.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) [ product name: IRGACURE (registered trademark) OXE-01, manufactured by basf corporation), 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., product ], 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [ trade name: omnirad (registered trade Mark) 907, IGM Resins B.V., manufactured), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one [ trade name: omnirad (registered trademark) 127, manufactured by IGM Resins b.v., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 [ trade name: omnirad (registered trademark) 369, igm Resins b.v., product ], 2-hydroxy-2-methyl-1-phenylpropan-1-one [ trade name: omnirad (registered trademark) 1173, igm Resins b.v., manufactured, 1-hydroxycyclohexyl phenyl ketone [ trade name: omnirad (registered trademark) 184, manufactured by igm Resins b.v., 2-dimethoxy-1, 2-diphenylethan-1-one [ trade name: omnirad (registered trademark) 651, manufactured by IGM Resins B.V., and the like, and oxime ester type photopolymerization initiators [ trade names: lunar (registered trademark) 6, DKKH Management Ltd. ], 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, changzhou Tronly New Electronic Materials Co., manufactured by LTD.), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furancarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (trade name: TR-PBG-326, changzhou Tronly New Electronic Materials Co., manufactured by LTD), 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl) (trade name: 391-dimethyl-3-yl) -propane-1, 2-dione-2- (O-benzoyl) biphenyl, UV-2- (morpholine-1- (4-methyl-ethyl-1, TM-phenyl) -propane-1, 2-dione-2- (O-benzoyl-3-ethyl-carbazole Co., manufactured by LTD., LTD, etc.

The photopolymerization initiator may be used alone in 1 kind, or may be used in 2 or more kinds. When 2 or more kinds are used simultaneously, at least 1 kind selected from oxime-based photopolymerization initiators, α -aminoalkylbenzophenone-based photopolymerization initiators, and α -hydroxyalkylphenone-based photopolymerization initiators is preferably used.

When the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer. The upper limit thereof is preferably 10 mass% or less, and more preferably 5 mass% or less, based on the total mass of the photosensitive composition layer.

-heterocyclic compounds-

The photosensitive layer may include a heterocyclic compound.

The heterocyclic ring of the heterocyclic compound may be any of monocyclic and polycyclic.

Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. The heterocyclic compound preferably has at least 1 atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a nitrogen atom.

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound.

Among the above, the heterocyclic compound is preferably at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound, and more preferably at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound.

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

[ chemical formula 12]

[ chemical formula 13]

Examples of the tetrazole compound include the following compounds.

[ chemical formula 14]

[ chemical formula 15]

Examples of the thiadiazole compound include the following compounds.

[ chemical formula 16]

Examples of the triazine compound include the following compounds.

[ chemical formula 17]

Examples of the rhodanine compound include the following compounds.

[ chemical formula 18]

Examples of the thiazole compound include the following compounds.

[ chemical formula 19]

Examples of the benzothiazole compound include the following compounds.

[ chemical formula 20]

Examples of the benzimidazole compound include the following compounds.

[ chemical formula 21]

[ chemical formula 22]

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

[ chemical formula 23]

The heterocyclic compounds can be used alone in 1 kind, also can be used simultaneously in more than 2 kinds.

When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, still more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass, based on the total mass of the photosensitive layer.

Aliphatic thiol compounds

The photosensitive layer may contain an aliphatic thiol compound.

The photosensitive layer contains an aliphatic thiol compound, and thus curing shrinkage and stress relaxation of a film formed by an ene-thiol reaction between the aliphatic thiol compound and a radical polymerizable compound having an ethylenically unsaturated group are suppressed.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) is preferable.

Among the above, the aliphatic thiol compound is preferably a polyfunctional aliphatic thiol compound in view of the adhesion of the formed pattern (particularly, the adhesion after exposure).

In the present specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having 2 or more thiol groups (also referred to as "mercapto groups") in the molecule.

The polyfunctional aliphatic thiol compound is preferably a low-molecular-weight compound having a molecular weight of 100 or more. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and 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 groups, more preferably 2 to 8 functional groups, and still more preferably 2 to 6 functional groups, from the viewpoint of adhesion of a formed pattern.

Examples of the polyfunctional aliphatic thiol compound 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), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1, 2-ethanedithiol, 1, 3-propane dithiol, 1, 6-hexamethylene dithiol, 2' - (ethylenedithio) diethylthiol, meso-2, 3-dimercapto, and bis (mercaptoethyl) succinate.

Among the above, as the polyfunctional aliphatic thiol compound, at least 1 compound selected from trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane and 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1h, 3h, 5h) -trione is preferable.

Examples of the monofunctional aliphatic thiol compound 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 1 kind of aliphatic thiol compound alone, or may contain 2 or more kinds of 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, still more preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, based on the total mass of the photosensitive layer.

Thermal crosslinkable compounds

The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained. In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group described later is regarded as a thermally crosslinkable compound, and is not regarded as an ethylenically unsaturated compound.

Examples of the thermally crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound and a blocked isocyanate compound. Among them, blocked isocyanate compounds are preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when at least one of the binder polymer and the radical polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to be enhanced.

The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called masked) by a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃ and more preferably 130 to 150 ℃.

The dissociation temperature of the blocked isocyanate means "a temperature of an endothermic peak accompanying deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter".

As the differential scanning calorimeter, for example, a differential scanning calorimeter made by Seiko Instruments Inc. (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited thereto.

Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound [ malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ]), an oxime compound (a compound having a structure represented by-C (= N-OH) -in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).

Among them, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably at least 1 selected from oxime compounds, for example, from the viewpoint of storage stability.

For example, the blocked isocyanate compound preferably has an isocyanurate structure in terms of improving the brittleness of the film, increasing the adhesion force with the transfer target, and the like.

The blocked isocyanate compound having an isocyanurate structure is protected by isocyanurating hexamethylene diisocyanate, for example.

Among the blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferable from the following points of view: compared with a compound having no oxime structure, the dissociation temperature is more easily set to a preferable range and the development residue is easily reduced.

The blocked isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferred.

Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group.

Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and still more preferably an acryloyloxy group.

As the blocked isocyanate compound, commercially available products can be used.

Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, and the like (hereinafter, made by SHOWA DENKO K.), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, and the like, made by Asahi Kasei Corporation).

The thermally crosslinkable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

Hydrogen donor compounds

The photosensitive layer may contain a hydrogen donor compound.

The hydrogen donor compound has the effects of further improving the sensitivity of the photopolymerization initiator to active light, suppressing inhibition of polymerization of the polymerizable compound by oxygen, and the like.

Examples of the hydrogen donor compound include amines and amino acid compounds.

Examples of the amines include compounds described in M.R. Sander et al, "Journal of Polymer Society" at volume 10, 3173 (1972), japanese patent publication No. 44-020189, japanese patent publication No. 51-082102, japanese patent publication No. 52-134692, japanese patent publication No. 59-138205, japanese patent publication No. 60-084305, japanese patent publication No. 62-018537, japanese patent publication No. 64-033104, and Research Disclosure No. 33825. More specifically, 4' -bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (otherwise known as leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline and p-methylthiodimethylaniline are mentioned.

Among them, in view of further excellent effects of the present invention, the amine is preferably at least 1 selected from the group consisting of 4,4' -bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

Among them, N-phenylglycine is preferable as the amino acid compound in view of further improving the effect of the present invention.

Further, examples of the hydrogen donor compound include an organometallic compound (tributyltin acetate, etc.) described in Japanese patent publication No. 48-042965, a hydrogen donor described in Japanese patent publication No. 55-034414, and a sulfur compound (trithiane, etc.) described in Japanese patent publication No. 6-308727.

The hydrogen donor compound can be used alone in 1 kind, also can be used simultaneously more than 2 kinds.

When the photosensitive layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and further preferably 0.03 to 5.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of improvement of the curing rate based on the balance between the polymerization growth rate and the chain transfer.

Other additives-

The photosensitive layer may contain other additives than the above components.

The other additives are the same as those of the photosensitive layer a described above, and the preferable embodiment is also the same.

Impurities-

The photosensitive layer may contain impurities.

The impurities are the same as those of the photosensitive layer a described above, and the preferred embodiment is the same.

Other ingredients-

The photosensitive layer may contain a component other than the above-described components (hereinafter, also referred to as "other component"). Examples of the other components include a colorant, an antioxidant, and particles (for example, metal oxide particles). Further, as other components, there may be mentioned other additives described in paragraphs [0058] to [0071] of Japanese patent laid-open No. 2000-310706.

Particles-

As the particles, metal oxide particles are preferable.

The metal in the metal oxide particles also includes semimetals such As B, si, ge, as, sb and Te.

For example, the average primary particle diameter of the particles is preferably 1 to 200nm, more preferably 3 to 80nm, from the viewpoint of transparency of the cured film.

The average primary particle diameter of the particles is calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is defined as the particle diameter.

Colorants-

The photosensitive layer may contain a small amount of a colorant (pigment, dye, etc.), but preferably contains substantially no colorant, 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, and more preferably less than 0.1% by mass, based on the total mass of the photosensitive layer.

Antioxidants-

Examples of the antioxidant include 3-pyrazolones such as 1-phenyl-3-pyrazolone (also referred to as phenanthrinone), 1-phenyl-4, 4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; p-methyl aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

Among them, from the viewpoint of further improving the effect of the present invention, 3-pyrazolones are preferable, and 1-phenyl-3-pyrazolones are more preferable as the antioxidant.

Characteristics of the photosensitive layer (photosensitive layer B) -

The average thickness of the photosensitive layer was an average value of the thicknesses at 10 points measured by observing a cross section perpendicular to the in-plane direction of the photosensitive layer with a Scanning Electron Microscope (SEM).

(intermediate layer)

In the composition layer, the intermediate layer is present between the thermoplastic resin layer and the photosensitive layer, whereby mixing of components that may occur during formation of a coating film of the thermoplastic resin layer and the photosensitive layer and during storage after formation of the coating film can be suppressed.

As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.

Further, as the intermediate layer, an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in japanese patent laid-open No. 5-072724, can also be used. When the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved, the time load of the exposure apparatus is reduced, and the productivity is improved, so that it is preferable.

The oxygen barrier layer that can be used as the intermediate layer may be appropriately selected from known layers described in the above-mentioned publications and the like. Among these, an oxygen barrier layer having low oxygen permeability and dispersed or dissolved in water or an aqueous alkali solution (a 1 mass% aqueous solution of sodium carbonate at 22 ℃) is preferable.

Hereinafter, each component that the water-soluble resin layer (intermediate layer) may contain will be described.

Water-soluble resins

The water-soluble resin layer (intermediate layer) contains a resin.

The resin contains a water-soluble resin as a part or all thereof.

Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

Further, as the water-soluble resin, a copolymer of (meth) acrylic acid/vinyl compound, or the like can also be used. As the copolymer of (meth) acrylic acid/vinyl compound, a copolymer of (meth) acrylic acid/(meth) allyl acrylate is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable.

When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the composition ratio (% by mol) is, for example, preferably 90/10 to 20/80, more preferably 80/20 to 30/70.

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 still more preferably 10,000 or more. The upper limit value is preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 50,000 or less.

The dispersity (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

In addition, from the viewpoint of further improving the interlayer mixing suppression ability of the water-soluble resin layer (intermediate layer), the resin in the water-soluble resin layer (intermediate layer) is preferably a resin different from the resin contained in the layer disposed on one surface side of the water-soluble resin layer (intermediate layer) and the resin contained in the layer disposed on the other surface side.

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

The water-soluble resin may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the water-soluble resin is not particularly limited, and is preferably 50 mass% or more, and more preferably 70 mass% or more, based on the total mass of the water-soluble resin layer (intermediate layer), from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppressing ability. The upper limit is not particularly limited, and is, for example, preferably 99.9 mass% or less, and more preferably 99.8 mass% or less.

The 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. If the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the interlayer mixing suppression ability is excellent without lowering the oxygen barrier property. Further, the removal time of the water-soluble resin layer (intermediate layer) during development can be suppressed from increasing.

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)

Generally, the thermoplastic resin layer is disposed between the temporary support and the photosensitive layer. The transfer film includes the thermoplastic resin layer, and thus the following property to the substrate in the bonding step of the transfer film and the substrate is improved, and the mixing of air bubbles between the substrate and the transfer film can be suppressed. As a result, adhesion to a layer (for example, a temporary support) adjacent to the thermoplastic resin layer can be ensured.

Examples of the thermoplastic resin layer include paragraphs [0189] to [0193] of Japanese patent application laid-open No. 2014-085643, which are incorporated herein.

Hereinafter, each component that the thermoplastic resin layer may contain will be described.

A layer of thermoplastic resin

The thermoplastic resin layer contains a thermoplastic resin.

As the thermoplastic resin, an alkali-soluble resin is preferable.

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

As the alkali-soluble resin, the alkali-soluble resin contained in the photosensitive layer described above may also 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" refers to a resin containing at least 1 structural unit selected from a structural unit derived from (meth) acrylic acid, a structural unit derived from a (meth) acrylate ester, and a structural unit derived from (meth) acrylamide.

In the acrylic resin, the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylamide is preferably 30% by mass or more, and more preferably 50% by mass or more, based on the total mass of the acrylic resin. The upper limit is preferably 100% by mass or less with respect to the total mass of the acrylic resin.

Among these, the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic ester is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

As the alkali-soluble resin, a resin having an acid group is preferable.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxyl group is preferable.

The alkali-soluble resin preferably contains a structural unit having an acid group, more preferably contains a structural unit having a carboxyl group, and further preferably contains an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoint of developability and adhesion to an adjacent layer.

The acid value of the alkali-soluble resin is preferably 60mgKOH/g or more in view of developability. The upper limit is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, and still more preferably 200mgKOH/g or less.

Among these, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, and more preferably an acrylic resin having a carboxyl group having an acid value of 60mgKOH/g or more.

The acrylic resin having a carboxyl group and an acid value of 60mgKOH/g or more can be suitably selected from known resins, for example.

Specifically, there are paragraphs [0025] of Japanese patent application laid-open No. 2011-095716, paragraphs [0033] to [0052] of Japanese patent application laid-open No. 2010-237589, and paragraphs [0053] to [0068] of Japanese patent application laid-open No. 2016-224162.

The content of the structural unit having a carboxyl group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 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 a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; a group having a cationically polymerizable group such as an epoxy group or an oxetanyl group.

Among these, the polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

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

The thermoplastic resin may be used alone in 1 or 2 or more.

The content of the thermoplastic resin is preferably 10.0 to 99.0% by mass, more preferably 20.0 to 90.0% by mass, further preferably 40.0 to 90.0% by mass, and particularly preferably 60.0 to 90.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of developability and adhesion to an adjacent layer.

Pigment B-

The thermoplastic resin layer may contain a coloring matter (hereinafter, also simply referred to as "coloring matter B") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical.

Except for the following portions, the pigment B has the same meaning as the pigment N, and the preferable embodiment is also the same.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

In view of visibility and resolution of the exposed portion and the unexposed portion, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength of the dye B is changed by an acid and a compound which generates an acid by light, which will be described later.

The pigment B may be used alone in 1 or 2 or more.

The content of the dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6.0% by mass, and still more preferably 0.2 to 5.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of the visibility of the exposed portion and the unexposed portion.

The "content of the coloring matter B" refers to a content of the coloring matter when all the coloring matter B contained in the thermoplastic resin layer is brought into a colored state. Hereinafter, a method for quantifying the content of pigment B will be described by taking a pigment that develops color by a radical as an example

A solution prepared by dissolving pigment B (0.001 g) in 100mL of methyl ethyl ketone and a solution prepared by dissolving pigment B (0.01 g) in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, a photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan ltd.) was added and 365nm light was irradiated, thereby generating radicals and bringing all the dyes B into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured by a spectrophotometer (UV 3100, manufactured by SHIMADZU CORPORATION) under an atmospheric environment to prepare a calibration curve.

Next, the absorbance of the solution in which all the dyes were developed was measured in the same manner as described above except that the thermoplastic resin layer (3 g) was dissolved in methyl ethyl ketone instead of the dye B. The amount of the coloring matter B contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer according to the calibration curve.

Compounds which generate acids, bases or radicals by light (compounds C)

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, also simply referred to as "compound C").

The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving an active ray such as ultraviolet light or visible light.

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 photoacid generator in view of resolution.

Examples of the photoacid generator include a photo cation polymerization initiator that can be contained in the photosensitive layer, and preferred embodiments are the same except for the following points.

The photoacid generator preferably contains at least 1 compound selected from an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.

As the photoacid generator, a photoacid generator having the following structure is also preferable.

[ chemical formula 24]

Photo radical polymerization initiator

The thermoplastic resin layer may contain a photo radical polymerization initiator.

Examples of the photo radical polymerization initiator include photo radical polymerization initiators that can be included in the photosensitive layer, and the same is preferred.

Photo-alkaline-generating agent

The thermoplastic resin composition may contain a photobase generator.

Examples of the photobase generator include known photobase generators.

Specific examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamide, 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, tris (triphenylmethylboronic acid) cobalt hexaammine (III), 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.

The compound C may be used alone in 1 or 2 or more.

The content of the compound C is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

Plasticizers-

The thermoplastic resin layer may contain a plasticizer in terms of resolution, adhesion to an adjacent layer, and developability.

The molecular weight of the plasticizer is preferably smaller than the molecular weight (weight average molecular weight when an oligomer or polymer and having a molecular weight distribution) of 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 which is compatible with the alkali-soluble resin and exhibits plasticization.

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.

As the plasticizer, a polyalkylene glycol compound is preferable.

From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth) acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.

Examples of the (meth) acrylate compound include (meth) acrylate compounds which are polymerizable compounds 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 is preferably not polymerized in exposed portions after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and an adjacent layer.

In addition, as the (meth) acrylate compound, a polyfunctional (meth) acrylate compound having 2 or more (meth) acryloyl groups in 1 molecule is preferable from the viewpoint of resolution of the thermoplastic resin layer, adhesion to an adjacent layer, and developability.

Further, as the (meth) acrylate compound, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.

As a preferred mode of the plasticizer, a combination of an alkylene oxide-modified product of an ethylenically unsaturated compound having 3 or more functions, an alkylene glycol di (meth) acrylate, and a urethane (meth) acrylate having 2 or more functions (preferably, a urethane di (meth) acrylate) is also preferred. In addition, as a preferable embodiment of these compounds, for example, the same compounds described as the polymerizable compounds that can be contained in the photosensitive layer can be given.

The plasticizer may be used alone in 1 or 2 or more.

The content of the plasticizer is preferably 0.5 to 40.0% by mass, more preferably 1.0 to 40.0% by mass, and still more preferably 5.0 to 40.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

Sensitizers

The thermoplastic resin layer may contain a sensitizer.

Examples of the sensitizer include sensitizers that can be contained in the photosensitive layer.

The number of the sensitizer used may be 1 or 2 or more.

The content of the sensitizer is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 8.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of improvement of sensitivity to a light source and visibility of exposed portions and unexposed portions.

Polymerization inhibitors

The polymerization inhibitor may contain impurities.

Examples of the polymerization inhibitor include impurities contained in the photosensitive layer.

From the viewpoint of further improving the effect of the present invention, the content of the polymerization inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 1.0% by mass, based on the total mass of the thermoplastic resin layer.

Other additives-

The thermoplastic resin layer may contain other additives in addition to the above components.

Examples of the other additive include other additives that can be contained in the photosensitive layer.

Impurities-

The thermoplastic resin layer may contain impurities.

Examples of the impurities include impurities that can be contained in the photosensitive layer.

The average thickness (layer thickness) of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. From the viewpoint of developability and resolution, the upper limit is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less.

The method for measuring the average thickness includes a method for measuring the average thickness of the photosensitive layer a.

(other layer)

The composition layer may contain other layers than the photosensitive layer, the intermediate layer, and the thermoplastic resin layer. Examples of the other layer 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 releasability of the temporary support and/or an oxygen barrier ability. The intermediate layer a is preferably a layer dispersed or dissolved in water or an aqueous alkaline solution (1 mass% aqueous solution of sodium carbonate at 22 ℃).

As the intermediate layer a, a water-soluble resin layer containing a water-soluble resin can be used.

Hereinafter, each component that the water-soluble resin layer (intermediate layer a) may contain will be described.

The intermediate layer a contains a water-soluble resin.

Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins (for example, water-soluble cellulose derivatives such as hydroxypropyl cellulose and hydroxypropyl methyl cellulose), acrylamide-based resins, polyether-based resins (for example, polyalkylene oxide-based resins such as polyethylene glycol and polypropylene glycol), gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.

Further, as the water-soluble resin, a copolymer of (meth) acrylic acid/vinyl compound, or the like can also be used. As the copolymer of (meth) acrylic acid/vinyl compound, a copolymer of (meth) acrylic acid/(meth) allyl acrylate is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable. When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the composition ratio (% by mole) is, for example, preferably 90/10 to 20/80, more preferably 80/20 to 30/70.

The water-soluble resin preferably contains 1 or more species selected from polyvinyl alcohol and polyvinyl pyrrolidone, more preferably contains polyvinyl alcohol, and still more preferably contains both polyvinyl alcohol and polyvinyl pyrrolidone. The mixing ratio (mass ratio) of polyvinyl alcohol to polyvinylpyrrolidone is preferably 5/95 to 95/5, more preferably 20/80 to 80/20, and still more preferably 25/75 to 70/25.

Further, as the water-soluble resin, it is preferable to use 1 or more selected from polyvinyl alcohol and polyvinyl pyrrolidone and 1 or more selected from water-soluble cellulose derivatives and polyethers at the same time, and it is more preferable to use 1 or more selected from polyvinyl alcohol and polyvinyl pyrrolidone and water-soluble cellulose derivatives at the same time.

When 1 or more selected from the group consisting of polyvinyl alcohol and polyvinyl pyrrolidone and a water-soluble cellulose derivative are used together as the water-soluble resin, the content of the water-soluble cellulose derivative is preferably less than 10% by mass, and more preferably 5% by mass or less, based on the total content of the polyvinyl alcohol, polyvinyl pyrrolidone and water-soluble cellulose derivative, from the viewpoint of further improving the releasability of the temporary support and/or further improving the oxygen barrier ability. The lower limit is not particularly limited, but is preferably 0.1 mass% or more, for example.

The water-soluble cellulose derivative is not particularly limited, and hydroxyethyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, and the like can be mentioned.

Examples of the polyether include polyethylene glycol and polypropylene glycol.

The content of the water-soluble resin is not particularly limited, and is preferably 40 mass% or more, more preferably 50 mass% or more, based on the total mass of the intermediate layer a, from the viewpoint of further improving the releasability of the temporary support and/or from the viewpoint of further improving the oxygen barrier ability. The upper limit is not particularly limited, and is, for example, 90 mass% or less, preferably 80 mass% or less.

The intermediate layer a may contain other components than the water-soluble resin. Examples of the other components include polyols, alkylene oxide adducts of polyols, phenol derivatives, and amide compounds.

[ modification of transfer film according to embodiment 1 ]

In the upper stage, the transfer film of embodiment 1 is exemplified as an example of a transfer film in which the photosensitive layer contains a specific pigment, but the transfer film in which the photosensitive layer contains a specific pigment is not limited to the above configuration.

Another example of the transfer film in which the photosensitive layer contains the specific pigment is a transfer film having a temporary support, a composition layer, and a protective film in this order, and the composition layer has a 2-layer structure including an intermediate layer a and a photosensitive layer containing the specific pigment in this order from the temporary support side.

Further, another example of the transfer film in which the photosensitive layer contains the specific coloring matter is a transfer film having a temporary support, a photosensitive layer containing the specific coloring matter, and a protective film in this order. In the transfer film of the above embodiment, the composition layer has a single-layer structure of the photosensitive layer.

The transfer film described as a modification of the transfer film according to embodiment 1 may not include a protective film.

[ transfer film of embodiment 2 ]

An example of the embodiment of the transfer film according to embodiment 2 will be described below.

The transfer film 50 shown in fig. 4 includes a temporary support 31, a composition layer 59, and a protective film 41 in this order, and the composition layer 59 includes a thermoplastic resin layer 53, an intermediate layer 55, and a photosensitive layer 57 in this order from the temporary support 31 side. The thermoplastic resin layer 53 contains a specific pigment.

The transfer film 50 shown in fig. 4 is a system in which the protective film 41 is disposed, but the protective film 41 may not be disposed.

The photosensitive layer 57 may contain no specific pigment or a specific pigment.

Hereinafter, each element constituting the transfer film will be described.

The transfer film of embodiment 2 has the same structure as the transfer film of embodiment 1, except that the thermoplastic resin layer contains the specific coloring matter and the photosensitive layer may not contain the specific coloring matter.

< thermoplastic resin layer >

Specific pigments

The thermoplastic resin layer contains a specific pigment.

The specific coloring matter contained in the thermoplastic resin layer has the same meaning as that of the specific coloring matter contained in the photosensitive layer of the transfer film according to embodiment 1, and the preferable embodiment is also the same.

As described above, the specific dye preferably does not include a dye (for example, dye B described later) whose maximum absorption wavelength is changed by an acid, an alkali, or a radical.

In the transfer film according to embodiment 2, as an example of a preferable combination of the maximum sensitivity wavelength of the photosensitive layer and the maximum absorption wavelength of the specific dye, there is a combination of a maximum sensitivity wavelength of the photosensitive layer of 300 to 395nm and a maximum absorption wavelength of the specific dye exceeding 395nm and not more than 500nm. In the above embodiment, the maximum absorption wavelength of the specific dye is preferably 410 to 500nm.

In a preferred embodiment of the thermoplastic resin layer, when the maximum sensitivity wavelength of the photosensitive layer exceeds 395nm and is 500nm or less and the thermoplastic resin layer contains a specific coloring matter having a maximum absorption wavelength of 300 to 395nm, the content of the coloring matter having a maximum absorption wavelength exceeding 395nm and is 500nm or less (the coloring matter referred to herein preferably does not include "a coloring matter (for example, coloring matter B) in which the maximum absorption wavelength changes by an acid, an alkali, or a radical)" in the thermoplastic resin layer is preferably 5.0 mass% or less with respect to the total mass of the thermoplastic resin layer, and from the viewpoint of further excellence in the effect of the present invention, more preferably 2.0 mass% or less, still more preferably 1.0 mass% or less, still more preferably 0.1 mass% or less, and particularly preferably 0.01 mass% or less. The lower limit is 0 mass% or more.

Particularly preferred embodiments of the thermoplastic resin layer include the following: when the maximum sensitivity wavelength of the photosensitive layer exceeds 395nm and is 500nm or less and the thermoplastic resin layer contains a specific dye having a maximum absorption wavelength of 300 to 395nm, the dye having a maximum absorption wavelength exceeding 395nm and is 500nm or less is not contained in the thermoplastic resin layer (the dye is preferably not a "dye (for example, dye B) having a maximum absorption wavelength that changes by an acid, an alkali, or a radical)".

In a preferred embodiment of the thermoplastic resin layer, when the photosensitive layer has a maximum sensitivity wavelength of 300 to 395nm and the photosensitive layer contains a specific coloring matter having a maximum absorption wavelength of more than 395nm and not more than 500nm, the content of the coloring matter having a maximum absorption wavelength of 300 to 395nm in the thermoplastic resin layer (the coloring matter referred to herein preferably does not include "coloring matter (for example, coloring matter B) having a maximum absorption wavelength that changes with an acid, an alkali, or a radical)" is preferably 5.0 mass% or less with respect to the total mass of the thermoplastic resin layer, and from the viewpoint of further excellent effects of the present invention, the content is more preferably 2.0 mass% or less, still more preferably 1.0 mass% or less, still more preferably 0.1 mass% or less, and particularly preferably 0.01 mass% or less. The lower limit is 0 mass% or more.

Particularly preferred embodiments of the thermoplastic resin layer include the following: when the maximum sensitivity wavelength of the photosensitive layer is 300 to 395nm and the thermoplastic resin layer contains a specific coloring matter having a maximum absorption wavelength of over 395nm and 500nm or less, the coloring matter having a maximum absorption wavelength of 300 to 395nm in the photosensitive layer is not contained (the coloring matter mentioned here preferably does not include "a coloring matter having a maximum absorption wavelength which is changed by an acid, an alkali or a radical" (for example, coloring matter B)).

From the viewpoint of further improving the effect of the present invention, the content of the specific coloring matter is preferably 0.01 to 20.0% by mass, more preferably 0.05 to 15.0% by mass, and still more preferably 1.0 to 10.0% by mass, based on the total mass of the thermoplastic resin layer.

Preferred manner of contents of the respective components of the thermoplastic resin layer

As a preferred example of the content of each component in the thermoplastic resin layer, there is a mode including 20.0 to 90.0 mass% of the resin, 5.0 to 40.0 mass% of the plasticizer, 0 to 10.0 mass% of the compound C, and 0.01 to 20.0 mass% of the specific pigment, with respect to the total mass of the thermoplastic resin layer.

As another preferred example of the content of each component in the thermoplastic resin layer, there is a mode including 40.0 to 90.0 mass% of the resin, 5.0 to 40.0 mass% of the plasticizer, 0 to 10.0 mass% of the compound C, and 0.01 to 20.0 mass% of the specific coloring matter, based on the total mass of the thermoplastic resin layer.

Another preferable example of the content of each component in the thermoplastic resin layer includes, for example, a mode including 40.0 to 90.0 mass% of the resin, 5.0 to 40.0 mass% of the plasticizer, 0 to 10.0 mass% of the compound C, and 1.0 to 10.0 mass% of the specific pigment, based on the total mass of the thermoplastic resin layer.

< photosensitive layer >

In the transfer film according to embodiment 2, the photosensitive layer may or may not contain a specific pigment.

The photosensitive layer not containing the specific coloring matter is the same as the photosensitive layer of the transfer film of embodiment 1 described above except that the photosensitive layer does not contain the specific coloring matter, and the preferable embodiment is also the same. Among the photosensitive layers not containing the specific pigment, the photosensitive layer a described above is preferably one not containing the specific pigment in a compounding ratio.

The photosensitive layer containing the specific dye is the same as that of the transfer film of embodiment 1 described above, and the preferred embodiment is the same. Among the photosensitive layers containing a specific pigment, the photosensitive layer a described above is preferable.

Preferred embodiment of the content of each component of the photosensitive layer not containing the specific pigment-

Hereinafter, a preferred embodiment of the content of each component in the photosensitive layer not containing the specific dye will be described.

The photosensitive layer not containing the specific pigment preferably contains a resin, a polymerizable compound, and a polymerization initiator, more preferably contains a resin, a polymerizable compound, a polymerization initiator, and a sensitizer, and further preferably contains a resin, a polymerizable compound, a polymerization initiator, a sensitizer, and a polymerization inhibitor.

Also, the above resin preferably includes an alkali-soluble resin.

As a preferred example of the content of each component in the photosensitive layer, for example, a mode including 10.0 to 90.0 mass% of a resin, 5.0 to 70.0 mass% of a polymerizable compound, and 0.01 to 15.0 mass% of a polymerization initiator with respect to the total mass of the photosensitive layer is given.

As another preferred example of the content of each component in the photosensitive layer, there can be mentioned, for example, a system including 10.0 to 90.0 mass% of a resin, 5.0 to 70.0 mass% of a polymerizable compound, 0.01 to 10.0 mass% of a polymerization initiator, and 0.01 to 5.0 mass% of a sensitizer, based on the total mass of the photosensitive layer.

As another preferred example of the content of each component in the photosensitive layer, there can be mentioned, for example, a system including 10.0 to 90.0 mass% of a resin, 5.0 to 70.0 mass% of a polymerizable compound, 0.01 to 10.0 mass% of a polymerization initiator, 0.01 to 5.0 mass% of a sensitizer, and 0.001 to 0.5 mass% of a polymerization inhibitor, based on the total mass of the photosensitive layer.

[ variation of transfer film according to embodiment 2 ]

In the upper stage section, the transfer film of embodiment 2 is exemplified as an example of a transfer film in which the thermoplastic resin layer contains a specific coloring matter, but the transfer film of the embodiment in which the photosensitive layer contains a specific coloring matter is not limited to the above-described configuration.

Another example of the transfer film in which the thermoplastic resin layer contains the specific coloring matter is a transfer film having a temporary support, a composition layer, and a protective film in this order, and the composition layer has a 3-layer structure including, in this order from the temporary support side, the thermoplastic resin layer containing the specific coloring matter, an intermediate layer, and a photosensitive layer containing the specific coloring matter. As the photosensitive layer containing the specific pigment, the photosensitive layer in the transfer film of embodiment 1 can be applied.

The transfer film described as a modification of the transfer film according to embodiment 2 may not include a protective film.

In addition to the embodiments described in embodiment 1 and embodiment 2, an embodiment in which a specific dye is included in the intermediate layer in the composition layer may be used.

[ method for manufacturing transfer film ]

The method for producing the transfer film according to embodiment 1 and embodiment 2 (hereinafter also referred to as "method for producing a transfer film") is not particularly limited, and a known method can be used.

For example, as a method for manufacturing the transfer film 30 shown in fig. 3 and the transfer film 40 shown in fig. 4, for example, a method including the steps of: a step of forming a thermoplastic resin layer by applying a thermoplastic resin composition to the surface of the temporary support to form a coating film and further drying the coating film; a step of forming an intermediate layer by applying a water-soluble resin composition to the surface of the thermoplastic resin layer to form a coating film and further drying the coating film; and a step of applying the composition for forming a photosensitive layer on the surface of the intermediate layer to form a coating film and further drying the coating film to form a photosensitive layer.

A protective film is pressure-bonded to the photosensitive layer of the laminate manufactured by the above-described manufacturing method, thereby manufacturing the transfer film 30 shown in fig. 3 and the transfer film 40 shown in fig. 4.

The transfer film 30 shown in fig. 3 and the transfer film 40 shown in fig. 4 may be produced, wound, and stored as a roll-like transfer film. The roll transfer film is directly provided in a roll form in a step of bonding to a substrate by a roll-to-roll method described later.

In addition, as a method for manufacturing the transfer film 30 shown in fig. 3 and the transfer film 40 shown in fig. 4, a method for manufacturing a photosensitive layer and an intermediate layer on a protective film, and then forming a thermoplastic resin layer on the surface of the intermediate layer may be used.

< thermoplastic resin composition and method for forming thermoplastic resin layer >

The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and a known method can be used. For example, the thermoplastic resin composition can be formed by applying the thermoplastic resin composition to a temporary support and then drying the thermoplastic resin composition as needed.

The thermoplastic resin composition preferably contains the various components forming the thermoplastic resin layer and a solvent. In the thermoplastic resin composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the thermoplastic resin layer.

The solvent is not particularly limited as long as it can dissolve or disperse the components other than the solvent, and a known solvent can be used. The solvent is the same as the solvent contained in the photosensitive composition described later, and the preferred embodiment is the same.

The content of the solvent is preferably 50 to 1,900 parts by mass, and 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-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, and the like).

< 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 a known method can be used. For example, the resin composition can be formed by applying a water-soluble resin composition to a thermoplastic resin layer and then drying the composition as necessary.

The water-soluble resin composition preferably contains various components and a solvent for forming the intermediate layer (water-soluble resin layer). In the water-soluble resin composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the water-soluble resin layer.

The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least 1 selected from water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and water-miscible organic solvents.

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

The solvent can be used alone in 1, can also use more than 2.

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still 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-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, and the like).

< 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 a known method can be used. For example, the photosensitive layer can be formed by applying the photosensitive layer forming composition to the intermediate layer and then drying it as necessary.

The photosensitive layer-forming composition preferably contains the above-described photosensitive layer-forming components and a solvent. In the composition for forming a photosensitive layer, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the photosensitive layer.

The solvent is not particularly limited as long as it can dissolve or disperse the components other than the solvent, and a known solvent can be used. Specifically, for example, there may be mentioned an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol, ethanol, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), an aprotic polar solvent (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetrahydrofuran, etc.), an ester solvent (N-propyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent containing 2 or more of these solvents.

The solvent preferably contains at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these solvents, a mixed solvent containing at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least 3 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 even more preferable.

Examples of the alkylene glycol ether solvent 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 ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

The solvent used may be any one of the solvents described in paragraphs [0092] to [0094] of International publication No. 2018/179640 and the solvent described in paragraph [0014] of Japanese patent application laid-open No. 2018-177889, and these are incorporated herein.

The solvent may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and still 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 coating 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).

As a method for drying a coating film of the composition for forming a photosensitive layer, heating drying and drying under reduced pressure are preferable.

The transfer film according to embodiment 1 and embodiment 2 can be manufactured by attaching a protective film to the photosensitive layer.

The method for bonding the protective film to the photosensitive layer is not particularly limited, and known methods can be used.

Examples of the apparatus for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an automatic cutting laminator.

The laminator is preferably provided with any heatable roller such as a rubber roller, and can be pressurized and heated.

In the case where the intermediate layer a is provided between the temporary support and the photosensitive layer in the method for producing the transfer film, the method for forming the intermediate layer a can be performed in the same manner as the method for forming the water-soluble resin composition and the intermediate layer (water-soluble resin layer) > described above.

[ use of transfer film ]

The transfer film of the present invention is suitable for a substrate with a transparent conductive layer (substrate with a transparent conductive layer) having a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate.

Hereinafter, a substrate with a transparent conductive layer will be described.

< transparent substrate >

The substrate with the transparent conductive layer has a transparent substrate.

Examples of the material of the transparent substrate include a resin material and an inorganic material.

Examples of the resin material include polyesters (e.g., polyethylene terephthalate and polyethylene naphthalate), polyether ether ketone, acrylic resins, cycloolefin polymers, and polycarbonates.

Examples of the inorganic material 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 10 to 100 μm, more preferably 10 to 60 μm, from the viewpoint of the transportability, the electrical characteristics and the film-forming property. The average thickness of the transparent base material was an average value of the thicknesses at 10 points measured by observing a cross section perpendicular to the in-plane direction of the transparent base material with a Scanning Electron Microscope (SEM).

< transparent conductive layer >

The substrate with the transparent conductive layer has transparent conductive layers disposed on both surfaces of the transparent substrate. That is, as shown in fig. 1, the substrate with the transparent conductive layer has a 1 st transparent conductive layer and a 2 nd transparent conductive layer on 2 opposing surfaces of the transparent substrate.

The volume resistivity of the transparent conductive layer is preferably less than 1X 10 ⁶ Omega cm, more preferably smallAt 1X 10 ⁴ Omega cm. The lower limit is 1 Ω cm or more. The volume resistivity is measured by using a known resistivity meter (e.g., resistance tester EC-80P, NAPSON CORPORATION, etc.).

The transparent conductive layer preferably includes at least 1 selected from the group consisting of metal nanowires and metal nanoparticles.

Examples of the metal nanoparticles include metal nanoparticles such as silver nanoparticles, copper nanoparticles, gold nanoparticles, and platinum nanoparticles. Examples of the metal nanowire include a silver nanowire, a copper nanowire, a gold nanowire, and a platinum nanowire, and the silver nanowire or the silver nanowire is preferable in terms of more excellent 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, and still more preferably 0.01 to 10 μm, from the viewpoint of further excellent conductivity and film formability. The average thickness of the transparent conductive layer was measured according to a method following the method for measuring the average thickness of the transparent base material described above.

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

For example, the substrate with the transparent conductive layer may further have another layer on the surface of the transparent conductive layer opposite to the transparent substrate side for the purpose of protecting the transparent conductive layer, controlling electrical characteristics, and controlling adhesion between the transparent conductive layer and the transfer film after the transfer film is bonded to the transparent conductive layer.

The other layer is not particularly limited. The other layer may be any 1 of a layer made of an organic material, a layer made of an inorganic material, a layer in which an inorganic material is dispersed in an organic matrix, a layer in which an organic material is dispersed in an inorganic matrix, and the like.

(method of Forming a substrate with a transparent conductive layer)

The method for forming the substrate with the transparent conductive layer is not particularly limited, and a known method can be used.

Examples of the method for forming the substrate with the transparent conductive layer include a method for forming a transparent conductive layer on a transparent substrate by coating, vacuum deposition, sputtering, plating, or the like.

When the substrate with the transparent conductive layer further has another layer on the surface of the transparent conductive layer opposite to the transparent substrate side, examples of a method for forming the other layer include known methods such as coating, vacuum deposition, sputtering, and lamination.

[ laminate ]

The laminate of the present invention comprises a substrate with a transparent conductive layer and transfer films bonded to both surfaces of the substrate with a transparent conductive layer, wherein the substrate with a transparent conductive layer comprises a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate.

The substrate with a transparent conductive layer included in the laminate is the same as the substrate with a transparent conductive layer described above, and the preferred embodiment is the same.

The transfer film of the present invention described in the upper stage corresponds to the transfer film included in the laminate.

The laminate is formed by bonding the transfer film of the present invention to a substrate having a transparent conductive layer. In the bonding, it is preferable that after the protective film in the transfer film is peeled off, the surface exposed by peeling off the protective film and the transparent conductive layer of the substrate with the transparent conductive layer are bonded. After the bonding, the temporary support in the transfer film may be peeled. In other words, the laminate may or may not have a temporary support.

As one specific example of the laminate, for example, a laminate 20 shown in fig. 1 and 2 can be given.

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

[ Pattern Forming method ]

The pattern forming method of the present invention is a method for forming a pattern by performing exposure treatment and development treatment on a transfer film in a laminate of the present invention, the method including:

a 1 st exposure step of exposing a photosensitive layer (hereinafter, also referred to as a "1 st photosensitive layer") in one transfer film of the laminate;

a 2 nd exposure step of exposing a photosensitive layer (hereinafter, also referred to as a "2 nd photosensitive layer") in the transfer film on the other side of the laminate;

a 1 st developing step of developing the 1 st photosensitive layer exposed in the 1 st exposure step to form a resin pattern; and

and a 2 nd developing step of developing the 2 nd photosensitive layer exposed in the 2 nd exposure step to form a resin pattern.

In the pattern forming method of the present invention, the main wavelength λ of the exposure wavelength in the 1 st exposure step is preferably ₁ The main wavelength λ corresponding to the exposure wavelength in the 2 nd exposure step ₂ Different (in other words, satisfying λ) ₁ ≠λ ₂ The relationship (c).

Hereinafter, each step of the pattern forming method of the present invention will be described in detail.

In the pattern forming method of the present invention, the laminate of the present invention and preferred embodiments thereof are as described above.

[ 1 st Exposure Process ]

The 1 st photosensitive layer exposed in the 1 st exposure step has a change in solubility in a developer between an exposed portion and an unexposed portion. For example, when the 1 st photosensitive layer is a positive photosensitive layer, the exposed portion of the 1 st photosensitive layer has higher solubility in a developer than the unexposed portion. On the other hand, for example, when the 1 st photosensitive layer is a negative photosensitive layer, the exposed portion of the 1 st photosensitive layer has lower solubility in a developer than the unexposed portion.

As a method of exposing the 1 st photosensitive layer, for example, a method using a photomask can be given. For example, by disposing a photomask between the 1 st photosensitive layer and the light source, the 1 st photosensitive layer can be exposed in a pattern through the photomask. By pattern-exposing the 1 st photosensitive layer, exposed portions and unexposed portions can be formed on the 1 st photosensitive layer.

In the 1 st exposure step, the 1 st photosensitive layer is preferably exposed by being brought into contact with a photomask. By exposing the 1 st photosensitive layer to light by contacting it with a photomask (referred to as "contact exposure"), the resolution can be improved.

In addition, in the 1 st exposure step, in addition to the contact exposure, 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. In the case of the lens projection exposure system, an exposure machine having a Numerical Aperture (NA) of an appropriate lens can be used according to a required resolution and a required depth of focus. In the case of the direct exposure method, the photosensitive layer may be directly drawn, or may be subjected to reduction projection exposure through a lens. The exposure may be performed not only in the air but also in a reduced pressure or vacuum, or may be performed by adding a liquid such as water between the light source and the photosensitive layer.

When the temporary support is disposed on the 1 st photosensitive layer, the 1 st photosensitive layer may be exposed through the temporary support, or the 1 st photosensitive layer may be exposed after removing the temporary support from the 1 st photosensitive layer. When the 1 st photosensitive layer is exposed by contact exposure, it is preferable to expose the 1 st photosensitive layer through the temporary support in order to avoid contamination of the photomask and the influence of foreign matter adhering to the photomask on the exposure. When the 1 st photosensitive layer is exposed through the temporary support, it is preferable to perform the 1 st developing step described later after removing the temporary support.

The temporary support used when the 1 st photosensitive layer is exposed through the temporary support is preferably a film that can transmit light irradiated at the time of exposure.

The exposure light source is not limited as long as it can irradiate light in a wavelength region (for example, 365nm or 436 nm) capable of changing the solubility of the 1 st photosensitive layer in the developer. Examples of the exposure light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

Main wavelength λ of exposure wavelength in the 1 st exposure step ₁ And the main wavelength lambda of the exposure wavelength in the 2 nd exposure step ₂ May be the same or different, but preferably are different.

Main wavelength λ of exposure wavelength in the 1 st exposure step ₁ For example, it may be determined in a wavelength region of 10 to 450 nm. For example, the dominant wavelength λ ₁ Preferably in the range of 300 to 400nm or 370 to 450nm, more preferably in the range of 300 to 380nm or 390 to 450 nm.

The exposure wavelength in the 1 st exposure step preferably does not include the wavelength of 365nm. In the present specification, "not including the wavelength 365nm" means that the intensity at the wavelength 365nm is 30% or less when the maximum value of the intensity in all regions of the exposure wavelength (i.e., the intensity indicating the dominant wavelength) is set to 100%. When the maximum value of the intensity in the entire region of the exposure wavelength is 100%, the intensity at the wavelength of 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at a wavelength of 365nm is not particularly limited. The intensity at a wavelength of 365nm is, for example, 0% or more, assuming that the maximum value of the intensity in all regions of the exposure wavelength is 100%.

When the exposure wavelength in the 1 st exposure step does not include the wavelength 365nm, the intensity of the wavelength 365nm in the 1 st exposure step is preferably 30% or less when the exposure wavelength includes the dominant wavelength in the wavelength region of 370 to 450nm and the intensity of the dominant wavelength is 100%, the intensity of the wavelength 365nm is more preferably 30% or less when the exposure wavelength includes the dominant wavelength in the wavelength region of 390 to 450nm and the intensity of the dominant wavelength is 100%, and the intensity of the wavelength 365nm is particularly preferably 30% or less when the exposure wavelength includes the dominant wavelength in the wavelength region of 420 to 450nm and the intensity of the dominant wavelength is 100%. The intensity at a wavelength of 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less, assuming that the intensity at the main wavelength is 100%. The lower limit of the intensity at a wavelength of 365nm is not particularly limited. The intensity at a wavelength of 365nm is, for example, 0% or more, assuming that the intensity at the main wavelength is 100%.

The exposure wavelength in the 1 st exposure step preferably does not include the wavelength 436nm.

In the present specification, "excluding the wavelength 436nm" means that the intensity at the wavelength 436nm is 30% or less when the maximum value of the intensity in all regions of the exposure wavelength is set to 100%. When the maximum value of the intensity in all regions of the exposure wavelength is 100%, the intensity at the wavelength of 436nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at a wavelength of 436nm is not particularly limited. The intensity at a wavelength of 436nm is, for example, 0% or more, assuming that the maximum value of the intensity in all regions of the exposure wavelength is 100%.

When the exposure wavelength in the 1 st exposure step does not include the wavelength 436nm, the intensity of the wavelength 436nm is preferably 30% or less when the exposure wavelength in the 1 st exposure step includes a dominant wavelength in a wavelength region of 300 to 400nm and the intensity of the dominant wavelength is 100%, the intensity of the wavelength 436nm is more preferably 30% or less when the exposure wavelength in the 300 to 380nm includes a dominant wavelength and the intensity of the dominant wavelength is 100%, and the intensity of the wavelength 436nm is particularly preferably 30% or less when the exposure wavelength in the 350 to 380nm includes a dominant wavelength and the intensity of the dominant wavelength is 100%. When the intensity of the main wavelength is 100%, the intensity at a wavelength of 436nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at a wavelength of 436nm is not particularly limited. The intensity at a wavelength of 436nm is, for example, 0% or more, assuming that the intensity at the main wavelength is 100%.

As an embodiment of the exposure wavelength in the first exposure step, an exposure wavelength at which the intensity of the wavelength 365nm is larger than the intensity of the wavelength 436nm (hereinafter, referred to as "condition (1-1)") or an exposure wavelength at which the intensity of the wavelength 436nm is larger than the intensity of the wavelength 365nm (hereinafter, referred to as "condition (1-2)") is preferable. Under the condition (1-1), the intensity at the wavelength of 436nm is preferably 80% or less, more preferably 50% or less, still more preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less, assuming that the intensity at the wavelength of 365nm is 100%. The lower limit of the intensity at a wavelength of 436nm in the condition (1-1) is not particularly limited. In the condition (1-1), the intensity at the wavelength of 436nm is, for example, 0% or more, assuming that the intensity at the wavelength of 365nm is 100%. On the other hand, under the condition (1-2), when the intensity at the wavelength of 436nm is taken as 100%, the intensity at the wavelength of 365nm is preferably 80% or less, more preferably 50% or less, further preferably 20% or less, particularly preferably 10% or less, and most preferably 5% or less. The lower limit of the intensity at 365nm wavelength under the condition (1-2) is not particularly limited. In the condition (1-2), the intensity at the wavelength of 365nm is, for example, 0% or more, assuming that the intensity at the wavelength of 436nm is 100%.

Examples of the method of adjusting the exposure wavelength in the 1 st exposure step include 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, the wavelength of light reaching the 1 st photosensitive layer can be adjusted to a specific range by exposing the 1 st photosensitive layer to light through a filter having wavelength selectivity.

The exposure amount is preferably 5 to 1,000mJ/cm ² More preferably 10 to 500mJ/cm ² More preferably 10 to 200mJ/cm ² . The exposure amount can be determined according to the illumination of the light source and the exposure time. The exposure amount can be measured using a light meter.

In the 1 st exposure step, the 1 st photosensitive layer may be exposed without using a photomask. In the case where the 1 st photosensitive layer is exposed without using a photomask (hereinafter, also referred to as "maskless exposure"), the 1 st photosensitive layer can be exposed by, for example, a direct writing apparatus.

The direct imaging device can directly image the image with the active energy ray. Examples of the light source in the maskless exposure include a laser (e.g., a semiconductor laser, a gas laser, a solid-state laser, etc.) and a short-arc mercury lamp (e.g., an ultra-high pressure mercury lamp) capable of emitting light having a wavelength of 350 to 410 nm. Dominant wavelength λ of exposure wavelength in maskless exposure ₁ And the main wavelength lambda of the exposure wavelength in the 2 nd exposure step ₂ May be the same or different, but preferably are different.

Preferred ranges of exposure wavelengths are as described above. The exposure amount can be determined according to the illuminance of the light source and the moving speed of the laminated body. The traced pattern can be controlled by a computer.

[ 2 nd Exposure Process ]

The 2 nd photosensitive layer exposed in the 2 nd exposure step changes in solubility in a developer between the exposed portion and the unexposed portion. For example, when the 2 nd photosensitive layer is a positive photosensitive layer, the exposed portion of the 2 nd photosensitive layer has higher solubility in a developer than the unexposed portion. On the other hand, for example, when the 2 nd photosensitive layer is a negative photosensitive layer, the exposed portion of the 2 nd photosensitive layer has lower solubility in a developer than the unexposed portion.

As a method of exposing the 2 nd photosensitive layer, for example, a method using a photomask can be given. For example, by disposing a photomask between the 2 nd photosensitive layer and the light source, the 2 nd photosensitive layer can be exposed in a pattern through the photomask. By pattern-exposing the 2 nd photosensitive layer, exposed portions and unexposed portions can be formed on the 2 nd photosensitive layer.

In the 2 nd exposure step, exposure is preferably performed by bringing the laminate into contact with a photomask. By bringing the stacked body into contact with a photomask to perform exposure (also referred to as "contact exposure"), the resolution can be improved.

When the temporary support is disposed on the 2 nd photosensitive layer, the 2 nd photosensitive layer may be exposed through the temporary support, or the 2 nd photosensitive layer may be exposed after removing the temporary support from the 2 nd photosensitive layer. When the exposure is performed on the 2 nd photosensitive layer by contact exposure, it is preferable to perform exposure on the 2 nd photosensitive layer through a temporary support in order to avoid contamination of the photomask and influence of foreign matter adhering to the photomask on the exposure. When the 2 nd photosensitive layer is exposed through the temporary support, it is preferable to perform the 2 nd developing step described later after removing the temporary support.

The temporary support used when the 2 nd photosensitive layer is exposed through the temporary support is preferably a film that can transmit light irradiated at the time of exposure.

The exposure light source is not limited as long as it can irradiate light in a wavelength region (for example, 365nm or 436 nm) in which the solubility of the 2 nd photosensitive layer in the developer can be changed. Examples of the exposure light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

As described above, the main wavelength λ of the exposure wavelength in the 2 nd exposure step ₂ And the main wavelength lambda of the exposure wavelength in the 1 st exposure step ₁ May be the same or different, but preferably are different. Main wavelength λ of exposure wavelength in the 2 nd exposure step ₂ For example, it may be determined in a wavelength region of 10 to 410 nm. For example, the dominant wavelength λ ₂ Preferably in the range of 300 to 400nm or 370 to 450nm, more preferably in the range of 300 to 380nm or 390 to 450 nm. For example, the dominant wavelength λ in the 1 st exposure step is preferable ₁ In the range of 300 to 400nm (preferably 300 to 380 nm), the dominant wavelength λ in the 2 nd exposure step ₂ In the range of 370 to 450nm, preferably 390 to 450 nm. For example, the dominant wavelength λ in the 1 st exposure step is preferable ₁ In the range of 370 to 450nm (preferably 390 to 450 nm), the dominant wavelength λ in the 2 nd exposure step ₂ In the range of 300 to 400nm (preferably 300 to 380 nm).

When the exposure wavelength in the 1 st exposure step does not include the wavelength of 365nm, the exposure wavelength in the 2 nd exposure step preferably does not include the wavelength of 436nm. By using the exposure wavelength described above in the 1 st exposure step and the 2 nd exposure step, each photosensitive layer can be exposed more selectively. When the maximum value of the intensity in all regions of the exposure wavelength is set to 100%, the intensity at a wavelength of 436nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at a wavelength of 436nm is not particularly limited. The intensity at a wavelength of 436nm is, for example, 0% or more, assuming that the maximum value of the intensity in all regions of the exposure wavelength is 100%.

When the exposure wavelength in the 2 nd exposure step does not include the wavelength 436nm, the intensity of the wavelength 436nm is preferably 30% or less when the exposure wavelength in the 2 nd exposure step includes a dominant wavelength in a wavelength region of 300 to 400nm and the intensity of the dominant wavelength is 100%, the intensity of the wavelength 436nm is more preferably 30% or less when the exposure wavelength includes a dominant wavelength in a wavelength region of 300 to 380nm and the intensity of the dominant wavelength is 100%, and the intensity of the wavelength 436nm is particularly preferably 30% or less when the exposure wavelength includes a dominant wavelength in a wavelength region of 350 to 380nm and the intensity of the dominant wavelength is 100%. The intensity at a wavelength of 436nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less, assuming that the intensity of the main wavelength is 100%. The lower limit of the intensity at a wavelength of 436nm is not particularly limited. The intensity at a wavelength of 436nm is, for example, 0% or more, assuming that the intensity at the main wavelength is 100%.

When the exposure wavelength in the 1 st exposure step does not include the wavelength of 436nm, the exposure wavelength in the 2 nd exposure step preferably does not include the wavelength of 365nm. By using the exposure wavelength in the 1 st exposure step and the 2 nd exposure step as described above, the photosensitive layer can be more selectively exposed. When the maximum value of the intensity in the entire region of the exposure wavelength is 100%, the intensity at the wavelength of 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. The lower limit of the intensity at 365nm is not particularly limited. The intensity at a wavelength of 365nm is, for example, 0% or more, assuming that the maximum value of the intensity in all regions of the exposure wavelength is 100%.

When the exposure wavelength in the 2 nd exposure step does not include the wavelength 365nm, the intensity of the wavelength 365nm in the 2 nd exposure step is preferably 30% or less when the exposure wavelength includes the dominant wavelength in a wavelength region of 370 to 450nm and the intensity of the dominant wavelength is 100%, the intensity of the wavelength 365nm is more preferably 30% or less when the exposure wavelength includes the dominant wavelength in a wavelength region of 390 to 450nm and the intensity of the dominant wavelength is 100%, and the intensity of the wavelength 365nm is more preferably 30% or less when the exposure wavelength includes the dominant wavelength in a wavelength region of 420 to 450nm and the intensity of the dominant wavelength is 100%. The intensity at a wavelength of 365nm is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less, assuming that the intensity at the main wavelength is 100%. The lower limit of the intensity at 365nm is not particularly limited. The intensity at a wavelength of 365nm is, for example, 0% or more, assuming that the intensity at the main wavelength is 100%.

When the exposure wavelength in the 1 st exposure step is "an exposure wavelength at which the intensity at the wavelength of 365nm is larger than the intensity at the wavelength of 436 nm", the exposure wavelength in the 2 nd exposure step is preferably an exposure wavelength at which the intensity at the wavelength of 436nm is larger than the intensity at the wavelength of 365nm (hereinafter, referred to as "condition (2-1)"). The preferable embodiment of the condition (2-1) is the same as the preferable embodiment of the condition (1-2) described in the above-mentioned "1 st exposure step". On the other hand, when the exposure wavelength in the 1 st exposure step is "an exposure wavelength at which the intensity at the wavelength of 436nm is larger than the intensity at the wavelength of 365 nm", the exposure wavelength in the 2 nd exposure step is preferably an exposure wavelength at which the intensity at the wavelength of 365nm is larger than the intensity at the wavelength of 436nm (hereinafter, referred to as "condition (2-2)" in this paragraph). The preferable embodiment of the condition (2-2) is the same as the preferable embodiment of the condition (1-1) described in the above-mentioned "1 st exposure step".

Examples of the method of adjusting the exposure wavelength in the 2 nd exposure step include 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, the wavelength of light reaching the 2 nd photosensitive layer can be adjusted to a specific range by exposing the 2 nd photosensitive layer through a filter having wavelength selectivity.

The exposure amount is preferably 5 to 1,000mJ/cm ² More preferably 10 to 500mJ/cm ² Go forward and go forwardOne-step optimization is 10-200 mJ/cm ² . The exposure can be determined according to the illumination of the light source and the exposure time. The exposure amount can be measured using a light meter.

Wherein the dominant wavelength λ ₁ And the above main wavelength λ ₂ The following is preferred.

The main wavelength λ is a wavelength having a wavelength of light that is different from the main wavelength λ of the main wavelength in the exposure light ₁ Preferably, it is in the range of 250nm or more and 395nm or less, and more preferably in the range of 335nm or more and 395nm or less.

The main wavelength λ is a wavelength having a wavelength of light that is different from the main wavelength λ of the main wavelength in the exposure light ₂ Preferably, the concentration is in the range of over 395nm and 500nm or less, and more preferably in the range of 396nm or more and 456nm or less.

Further, from the viewpoint of suppressing exposure fogging, the dominant wavelength λ is more preferably ₁ In a range of 250nm to 395nm, and the dominant wavelength λ ₂ The dominant wavelength λ is particularly preferably in the range of 395nm to 500nm or less ₁ In the range of 335nm to 395nm, and the dominant wavelength lambda ₂ In the range of 396nm to 456 nm.

In the pattern forming method of the present invention, the exposure amount in the 1 st exposure step and the exposure amount in the 2 nd exposure step may be the same or different.

In the 2 nd exposure step, the 2 nd photosensitive layer may be exposed without using a photomask. In the case where the 1 st photosensitive layer is exposed without using a photomask (hereinafter, may be referred to as "maskless exposure"), the 1 st photosensitive layer can be exposed by, for example, a direct writing apparatus. The direct rendering device can directly render an image with active energy rays. Examples of the light source in the maskless exposure include a laser (e.g., a semiconductor laser, a gas laser, and a solid laser) and a short-arc mercury lamp (e.g., an ultra-high pressure mercury lamp) capable of emitting light having a wavelength of 350 to 410 nm. Dominant wavelength λ of exposure wavelength in maskless exposure ₂ Provided that the main wavelength λ is the same as the exposure wavelength in the 1 st exposure step ₂ Otherwise, it is not limited. Preferred ranges of exposure wavelengths are as described above. Exposure methodThe light quantity can be determined by the illuminance of the light source and the moving speed of the laminate. The traced pattern can be computer controlled.

In the pattern forming method of the present invention, the 1 st exposure step and the 2 nd exposure step may be performed simultaneously or may be performed sequentially. The 1 st exposure step and the 2 nd exposure step may be performed in the order of the 1 st exposure step → the 2 nd exposure step, or in the order of the 2 nd exposure step → the 1 st exposure step. From the viewpoint of further improving productivity, it is preferable to simultaneously perform the 1 st exposure step and the 2 nd exposure step.

In this specification, the phrase "simultaneously performing the 1 st exposure step and the 2 nd exposure step" is not limited to the case where the exposure of the 1 st photosensitive layer and the exposure of the 2 nd photosensitive layer are performed completely simultaneously, and includes the case where a period during which the exposure of the 1 st photosensitive layer is performed overlaps a period during which the exposure of the 2 nd photosensitive layer is performed.

Further, "sequentially performing the 1 st exposure step and the 2 nd exposure step" means that the 1 st photosensitive layer and the 2 nd photosensitive layer are exposed to light in a range where a period of exposing the 1 st photosensitive layer and a period of exposing the 2 nd photosensitive layer do not overlap with each other.

[ 1 st developing step ]

The pattern forming method of the present invention includes a step of forming a 1 st resin pattern by developing the 1 st photosensitive layer that has been exposed (1 st developing step). In the 1 st developing step, for example, a 1 st resin pattern can be formed by removing a portion having relatively high solubility in a developing solution in the exposed 1 st photosensitive layer.

The developing method is not particularly limited, and a known method can be used. For example, the 1 st photosensitive layer can be developed with a developer.

The developing solution is not particularly limited, and a known developing solution can be used. The developer is, for example, the developer described in Japanese patent application laid-open No. 5-072724. A preferable example of the developer is the developer described in paragraph 0194 of International publication No. 2015/093271.

The developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13. In the above-mentioned aqueous alkali developer, the concentration of the compound having a pKa of 7 to 13 is preferably 0.05 to 5mol/L.

As the components other than the above, the developer may contain, for example, an organic solvent and a surfactant which can be mixed with water.

The temperature of the developing solution is preferably 20 to 40 ℃.

The developing method is not particularly limited, and a known method can be used. Examples of the development method include spin immersion development, shower development, spin development, and immersion development.

The 1 st developing step may include a step of performing a heat treatment (also referred to as "post baking") on the 1 st resin pattern.

The heat treatment is preferably performed under an atmosphere of 8.1 to 121.6kPa, more preferably 8.1 to 114.6kPa, and still more preferably 8.1 to 101.3 kPa.

The temperature of the heat treatment is preferably 20 to 250 ℃, more preferably 30 to 170 ℃, and still more preferably 50 to 150 ℃.

The time of the heat treatment is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, and still more preferably 2 to 4 minutes.

The heat treatment may be performed in an air atmosphere or in a nitrogen-substituted atmosphere.

[ 2 nd developing Process ]

The pattern forming method of the present invention includes a step of forming a 2 nd resin pattern by developing the exposed 2 nd photosensitive layer (2 nd developing step). In the 2 nd developing step, for example, a 2 nd resin pattern can be formed by removing a portion having relatively high solubility in a developing solution in the exposed 2 nd photosensitive layer.

The embodiment of the 2 nd developing step is the same as the 1 st developing step described above, and the preferable embodiment is also the same.

In the pattern forming method of the present invention, the 1 st developing step and the 2 nd developing step may be performed simultaneously or sequentially. The 1 st developing step and the 2 nd developing step may be performed in the order of the 1 st developing step → the 2 nd developing step, or in the order of the 2 nd developing step → the 1 st developing step. In view of further improving productivity, it is preferable to perform the 1 st developing step and the 2 nd developing step at the same time.

In the present specification, the phrase "simultaneously performing the 1 st developing step and the 2 nd developing step" is not limited to the case where the 1 st photosensitive layer and the 2 nd photosensitive layer are completely simultaneously developed, and includes the case where a period during which the 1 st photosensitive layer is developed and a period during which the 2 nd photosensitive layer is developed overlap.

Further, "successively performing the 1 st developing step and the 2 nd developing step" means that the 1 st photosensitive layer and the 2 nd photosensitive layer are developed in a range where a period for developing the 1 st photosensitive layer and a period for developing the 2 nd photosensitive layer do not overlap with each other.

A preferred embodiment of the pattern forming method includes an embodiment in which the 1 st exposure step and the 2 nd exposure step are performed simultaneously, and the 1 st development step and the 2 nd development step are performed simultaneously. According to the above embodiment, since the time and environment from the exposure to the development start can be set to be the same, the product quality can be easily stabilized, and the process length can be shortened and the process cost can be reduced.

In another preferred embodiment of the pattern forming method, it is preferable that the 1 st exposure step and the 2 nd exposure step are sequentially performed, or the 1 st developing step and the 2 nd developing step are sequentially performed. For example, in the case where the reaction progress speed after exposure is greatly different in the 1 st photosensitive layer and the 2 nd photosensitive layer or in the case where different exposure light sources need to be arranged apart from the photosensitive layers, it is preferable to sequentially perform the 1 st exposure step and the 2 nd exposure step. For example, when the developer used for developing the 1 st photosensitive layer is different from the developer used for developing the 2 nd photosensitive layer, it is preferable to successively perform the 1 st developing step and the 2 nd developing step.

[ etching Process ]

The pattern forming method preferably further includes an etching step after the developing step.

The etching step is a step of performing at least 1 of the following steps: and etching the 1 st transparent conductive layer using the 1 st resin pattern as a mask, and etching the 2 nd transparent conductive layer using the 2 nd resin pattern as a mask.

By the etching step, the pattern of the 1 st transparent conductive layer and/or the pattern of the 2 nd transparent conductive layer can be formed on the transparent substrate.

Examples of the etching include dry etching and wet etching. The etching is preferably wet etching from the viewpoint of no need for a vacuum process and simplicity of the process. The etching may be performed by the method described in paragraphs 0048 to 0054 of jp 2010-152155 a.

Examples of the etching solution used for wet etching include an acidic etching solution and an alkaline etching solution.

Examples of the acidic etching solution include an aqueous solution containing an acidic component (e.g., hydrochloric acid, sulfuric acid, nitric acid, fluoric acid, and phosphoric acid) and an aqueous solution containing an acidic component and a salt (e.g., ferric chloride, ammonium fluoride, ferric nitrate, and potassium permanganate).

The acidic type etching solution may contain 1 kind of acidic component alone, or may contain 2 or more kinds. The acidic etching solution may contain 1 kind of salt alone, or may contain 2 or more kinds.

Examples of the alkaline type etching solution include an aqueous solution containing an alkaline component [ e.g., sodium hydroxide, potassium hydroxide, ammonium, an organic amine, and a salt of an organic amine (e.g., tetramethylammonium hydroxide ]), and an aqueous solution containing an alkaline component and a salt (e.g., potassium permanganate).

The alkaline type etching solution may contain 1 alkali component alone, or may contain 2 or more alkali components. The alkaline type etching solution may contain 1 kind of salt alone, or may contain 2 or more kinds.

The etching solution may contain a rust inhibitor from the viewpoint of controlling the etching rate. Examples of the rust inhibitor include nitrogen-containing compounds (e.g., triazole-based compounds, imidazole-based compounds, and tetrazole-based compounds).

The temperature of the etching solution is preferably 45 ℃ or lower.

In the pattern forming method of the present invention, it is preferable that the 1 st resin pattern used as a mask and the 2 nd resin pattern used as a mask have excellent resistance in an etching solution of 60 ℃.

In the etching step, the etching treatment of the 1 st transparent conductive layer and the 2 nd transparent conductive layer may be performed simultaneously or sequentially. From the viewpoint of further improving productivity, it is preferable to simultaneously perform the 1 st exposure step and the 2 nd exposure step.

[ cleaning step and drying step ]

The pattern forming method of the present invention may include a cleaning step and a drying step as necessary after the etching step, from the viewpoint of preventing contamination of the production line.

One specific example of the cleaning step is a method of cleaning the laminate with pure water at normal temperature (e.g., 25 ℃). For example, the cleaning time can be set appropriately within a range of 10 to 300 seconds.

As one specific example of the drying step, a method of drying the laminate using a blower is given. The blower pressure is preferably 0.1 to 5kg/cm ² 。

[ Whole surface Exposure Process ]

The pattern forming method of the present invention may include a step of performing full-surface exposure on at least one of the 1 st resin pattern and the 2 nd resin pattern (hereinafter, also referred to as a "full-surface exposure step"). The entire surface exposure step is preferably performed before the removal step described later. The pattern forming method of the present invention includes a full-surface exposure step, and thus has an effect of further improving the reactivity of a pattern remaining after development and/or improving the removability of a resin pattern in a removal step described later.

For example, the resin pattern formed of a positive photosensitive layer is subjected to a full-surface exposure step, thereby further improving the removability in a removal step to be described later. On the other hand, the resin pattern formed of the negative photosensitive layer is further cured in the entire surface exposure step, whereby the process resistance of the resin pattern is improved.

The term "full-surface exposure" refers to exposure of the region of the substrate with the transparent conductive layer, in which the 1 st resin pattern and the 2 nd resin pattern are arranged. The region on the substrate with the transparent conductive layer where the 1 st resin pattern is not arranged and the region on the substrate with the transparent conductive layer where the 2 nd resin pattern is not arranged may be exposed or unexposed. From the viewpoint of further excellent convenience, the entire surface of the substrate with the transparent conductive layer is preferably exposed.

The exposure light source is not particularly limited, and a known light source can be used. Examples of the exposure light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

From the viewpoint of removability, the exposure wavelength preferably includes a wavelength of 365nm or a wavelength of 436nm.

The exposure amount is preferably 5 to 1,000mJ/cm from the viewpoint of removability ² More preferably 10 to 800mJ/cm ² More preferably 100 to 500mJ/cm ² 。

From the viewpoint of removability, the exposure amount is preferably not less than the exposure amount in at least one of the 1 st exposure step and the 2 nd exposure step, and more preferably greater than the exposure amount in at least one of the 1 st exposure step and the 2 nd exposure step.

The exposure illumination is preferably 5 to 25,000mW/cm ² More preferably 20 to 20,000mW/cm ² More preferably 30 to 15,000mW/cm ² . By increasing the illuminance, the time required for the entire exposure is shortened.

[ heating procedure ]

The pattern forming method of the present invention may include a step of heating at least one of the 1 st resin pattern and the 2 nd resin pattern (hereinafter, also referred to as a "heating step") at least one of during the whole exposure step, before the whole exposure step is performed, and before the removal step described later is performed.

The pattern forming method of the present invention includes a heating step, and thus the 1 st resin pattern and the 2 nd resin pattern can be easily removed. For example, in a resin pattern formed of a positive photosensitive layer, the reaction rate of a photoacid generator and the reaction rate of a generated acid with a positive photosensitive composition can be increased, and thus the removal performance can be improved.

The heating device is not particularly limited, and a known heating device can be used. Examples of the heating device include an infrared heater, a hot air blower, and a convection oven.

From the viewpoint of removability, the heating temperature is preferably 30 to 100 ℃, more preferably 30 to 80 ℃, and particularly preferably 30 to 60 ℃.

The heating time is preferably 1 to 600 seconds, more preferably 1 to 120 seconds, and particularly preferably 5 to 60 seconds from the viewpoint of removability. Here, the "heating time" refers to a time from the time when the surface of the substrate with the transparent conductive layer reaches a set value, and does not include a time during temperature rise.

The heating environment is preferably air (relative humidity: 10 to 90% RH). The heating environment may be an inert gas (e.g., nitrogen and argon).

The pressure is preferably atmospheric pressure.

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

[ removal Process ]

The pattern forming method of the present invention may include a step of removing at least one of the 1 st resin pattern and the 2 nd resin pattern (hereinafter, also referred to as a "removal step"). Hereinafter, the 1 st resin pattern and the 2 nd resin pattern may be collectively referred to as a "resin pattern".

As a method of removing the resin pattern, for example, a method of using a chemical such as a removing liquid is given, and as one specific example, a method of immersing the laminate in a removing liquid is given.

As the removing liquid, a removing liquid capable of dissolving or dispersing the resin pattern is preferable.

The temperature of the removing solution is preferably 30 to 80 ℃ and more preferably 50 to 80 ℃.

The immersion time in the removing solution is preferably 1 to 30 minutes.

From the viewpoint of further improving the removability, the removing liquid is preferably aqueous.

The content of water in the removal liquid is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.

The removing solution preferably contains an inorganic base component or an organic base component.

Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary to tertiary amine compounds and quaternary ammonium salt compounds.

Among these, the removal liquid more preferably contains an organic alkali component from the viewpoint of further improving the removability. The content of the organic alkali component in the removal solution is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the removal solution, from the viewpoint of further improving the removal property.

From the viewpoint of removability, the removing solution preferably contains a surfactant. The surfactant is not particularly limited, and a known surfactant can be used.

From the viewpoint of removability, the content of the surfactant is preferably 0.1 to 10% by mass based on the total mass of the removal liquid.

The removal solution also preferably contains a water-soluble organic solvent. Examples of the water-soluble organic solvent include dimethyl sulfoxide, a lower alcohol, a glycol ether, and N-methylpyrrolidone.

Examples of the method of bringing the removal liquid into contact with the resin pattern in the removal step include a spray coating method, a shower method, and a spin coating immersion method.

As the removing liquid, the removing liquids described in Japanese patent application laid-open Nos. 11-021483, 2002-129067, 07-028254, 2001-188363, 04-048633 and 5318773 can be applied.

The removal of the 1 st resin pattern and the removal of the 2 nd resin pattern may be performed simultaneously or sequentially. From the viewpoint of productivity, the removal of the 1 st resin pattern and the removal of the 2 nd resin pattern are preferably performed simultaneously.

[ volume-to-volume approach ]

The pattern forming method of the present invention is preferably performed 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, the step of winding out at least the laminate and the step of winding up at least the laminate are provided before and after at least 1 step, respectively, whereby the laminate can be processed while being carried.

[ other procedures ]

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

(step of decreasing reflectance of visible ray)

The pattern forming method of the present invention may include the steps of: the first transparent conductive layer 1 and the second transparent conductive layer 2 are partially or entirely reduced in visible light reflectance.

As the treatment for reducing the visible light reflectance, for example, oxidation treatment is given. For example, when the 1 st transparent conductive layer and the 2 nd transparent conductive layer contain copper, the visible light reflectance of the 1 st transparent conductive layer and the 2 nd transparent conductive layer can be reduced by oxidizing copper to form copper oxide.

Preferable embodiments of the treatment for reducing the reflectance of visible light are described in paragraphs 0017 to 0025 of Japanese patent application laid-open No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese patent application laid-open No. 2013-206315, and the contents of these are incorporated herein by reference.

[ method for producing Circuit Board ]

The method for manufacturing a circuit board 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 the circuit board include a printed circuit board and a touch panel sensor.

Examples

The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. The scope of the invention should therefore not be construed in a limiting sense by the examples presented below. Unless otherwise specified, "part(s)" and "%" are based on mass.

[ abbreviation ]

Hereinafter, the following compounds are each referred to for short.

(Binder)

"AA-1": propylene glycol monomethyl ether acetate solution of a styrene/methacrylic acid/methyl methacrylate copolymer (solid content concentration: 30.0% by mass, ratio of monomers: 52% by mass/29% by mass/19% by mass, mw:70,000)

"AA-3": propylene glycol monomethyl ether acetate solution of a copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (solid content concentration: 40.0% by mass, mw:13,000, ratio of monomers: 78% by 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, SHIN-NAKAMURA CHEMICAL Co., ltd.)

"AB-3": NK ESTER A-DCP (Dicyclodecane dimethanol diacrylate, SHIN-NAKAMURA CHEMICAL Co., ltd., manufactured by Ltd.)

"AB-4":8UX-015A (polyfunctional urethane (meth) acrylate, manufactured by Taisei Fine Chemical Co., ltd.)

"AB-5": aronitixo-2349 (a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid derivatives of dipentaerythritol pentaacrylate, TOAGOSEI co., ltd.)

"AB-7": NK ESTER A-HD-N (1, 6-hexanediol diacrylate, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.)

"AB-8": NK ESTER HD-N (1, 6-hexanediol dimethacrylate, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.)

(initiator/photoacid generator)

"AC-1": B-CIM (polymerization initiator, manufactured by Ltd., kurogane Kasei Co., ltd.)

"AC-11": a compound having the structure shown below (photoacid generator, synthesized by the method described in paragraph 0227 of Japanese patent laid-open publication No. 2013-047765)

[ chemical formula 25]

(sensitizer)

"AC-5": coumarin 7 (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 Corporation)

(polymerization inhibitor)

"AD-1": TDP-G (Kawaguchi Chemical Industry Co., LTD. Manufactured)

"AD-2": 1-phenyl-3-pyrazolone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

"AD-3": N-nitroso-N-phenylhydroxylamine aluminum (manufactured by FUJIFILM Wako Pure Chemical Corporation)

(pigments (except for pigments whose maximum absorption wavelength is changed by acid, alkali or radical))

"AE-3": solvent yellow 56 (manufactured by Tokyo Chemical Industry Co., ltd., substance absorbing light of 436 nm)

"AE-8": diethylamino-phenylsulfonyl-based ultraviolet absorbers (365 nm light-absorbing substance manufactured by Daito Chemical Co., ltd.; ltd.)

"AE-15": bonasorb UA3911 (ORIENT CHEMICAL INDUSTRIES CO., LTD, substance absorbing light of 405 nm)

"AE-16": bonasorb UA3912 (ORIENT CHEMICAL INDUSTRIES CO., LTD, substance absorbing light of 405 nm)

"AE-17": FDB-009 (YAMADA CHEMICAL CO., LTD. Manufactured, substance absorbing 405nm light)

"AE-18": a compound represented by the following structural formula (a substance which absorbs light at 405 nm)

[ chemical formula 26]

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

[ chemical formula 27]

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

[ chemical formula 28]

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

[ chemical formula 29]

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

[ chemical formula 30]

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

[ chemical formula 31]

(other additives)

"AE-1": colorless crystal violet (Tokyo Chemical Industry Co., ltd.)

"AE-2": N-Phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)

"AE-12": CBT-1 (carboxybenzotriazoles, JOHOKU CHEMICAL CO., LTD products)

"AE-13": f-552 (surfactant, DIC Corporation)

"AE-24": isonicotinamide (Tokyo Chemical Industry Co., ltd., manufactured by Ltd.)

"AE-25":1,2, 4-triazole (Tokyo Chemical Industry Co., ltd., manufactured by Ltd.)

"AE-26":1, 1-oxalyldiimidazole (Tokyo Chemical Industry Co., ltd.)

"AE-27": a compound having a structure shown below (dye which develops color by acid)

[ chemical formula 32]

(solvent)

"AF-1": methyl Ethyl Ketone (SANKYO CHEMICAL CO., LTD. Manufactured)

"AF-2": propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

"AF-3": methanol (MITSUBISHI GAS CHEMICAL COMPANY, manufactured by INC.)

Examples 1 to 6 and comparative examples 1 to 3

Resin patterns were formed on both surfaces of the transparent base material by the following method.

[ transfer printing film production ]

Each transfer film for transferring the photosensitive layer to 2 surfaces (a surface and B surface) of the transparent substrate facing each other was prepared according to the formulation described in table 2. Each of the transfer films for the a-side and the B-side has a temporary support, a photosensitive layer disposed on the temporary support, and a protective film in this order. For example, in example 1, the transfer film for surface a had a temporary support, a photosensitive layer formed on the temporary support using the composition for forming a photosensitive layer of the formulation a-1, and a protective film. The transfer film for B-side has a temporary support, a photosensitive layer formed on the temporary support using the composition for forming a photosensitive layer of the formula B-1, and a protective film. The formulations of the photosensitive layer-forming compositions are shown in table 1. The transfer film used in examples 2 to 6 and comparative examples 1 to 3 was produced in the same manner as in example 1, except that the formulation numbers of the photosensitive layer forming compositions were changed in accordance with table 2.

Specifically, transfer films for the a-side and the B-side were produced by the following methods.

The photosensitive layer-forming composition of the formulation No. described in Table 2 was applied to a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) by a slit nozzle until the coating width became 1.0m and the layer thickness after drying became 3.0 μm. The photosensitive layer-forming composition on the temporary support was dried in a convection oven at 100 ℃ for 2 minutes to form a photosensitive layer. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was attached to the photosensitive layer to prepare a transfer film. For example, in example 1, a transfer film having a temporary support, a photosensitive layer formed from the photosensitive layer forming composition of the formulation a-1, and a protective film in this order was prepared as a transfer film for the a-side. As the transfer film for B-side, a transfer film was produced which sequentially had a temporary support, a photosensitive layer formed from the composition for forming a photosensitive layer of the formulation B-1, and a protective film.

[ production of laminate ]

The transfer film selected according to the description in table 2 was cut into a 50cm square, and then the protective film was peeled off from the transfer film. Next, transfer films were laminated on 2 opposed surfaces (A surface and B surface) of a transparent substrate (polyethylene terephthalate film, thickness: 40 μm) under lamination conditions of a roll temperature of 90 ℃ and a line pressure of 0.8MPa and a line speed of 3.0 m/min. In the above procedure, a laminate was produced.

Hereinafter, the photosensitive layer in the transfer film bonded to the a surface of the transparent substrate may be referred to as a "1 st photosensitive layer", and the photosensitive layer in the transfer film bonded to the B surface of the transparent substrate may be referred to as a "2 nd photosensitive layer". The laminate has a structure of temporary support/1 st photosensitive layer/transparent substrate/2 nd photosensitive layer/temporary support.

[ Pattern formation ]

Without peeling off the temporary support, a glass mask (duty ratio 1. At this time, the glass masks are arranged on both surfaces of the laminate such that the line patterns of the glass masks are orthogonal to each other in a plan view. Subsequently, the 1 st photosensitive layer and the 2 nd photosensitive layer are simultaneously exposed. When the 1 st photosensitive layer and the 2 nd photosensitive layer are simultaneously exposed, the 1 st photosensitive layer is exposed from the side (A surface side) where the 1 st photosensitive layer is disposed with reference to the transparent substrate, and then the 2 nd photosensitive layer is exposed from the side (B surface side) where the 2 nd photosensitive layer is disposed with reference to the transparent substrate.

The exposure conditions were determined as follows.

1 st photosensitive layer: after exposing the 1 st photosensitive layer to light through the above glass mask by using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.), the layer was left for 1 hour, and the exposure amount was set so that the residual pattern width in the pattern portion of 50 μm line/space 50 μm was 49.0 to 51.0 μm during development.

Photosensitive layer 2: after the 2 nd photosensitive layer was exposed to light using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.) through the above glass mask, the layer was left for 1 hour, and the exposure amount was set so that the residual pattern width in the pattern portion of line 50 μm/space 50 μm was 49.0 to 51.0 μm during development.

In the table, the following terms and symbols described in the column "exposure conditions" have the following meanings, respectively.

"excluding 365nm": the exposure was carried out using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.) with a short wavelength cut-off filter (model number: LU0422, cut-off wavelength: 422nm, asahi Spectra Co., manufactured by Ltd.). The dominant wavelength was 436nm. When the intensity of the dominant wavelength is defined as 100%, the intensity at a wavelength of 365nm is 0.5% or less.

"excluding 436nm": the exposure was carried out using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.) through a band-pass filter for mercury exposure (model: HB0365, center wavelength: 365nm, asahi Spectra Co., manufactured by Ltd.). The dominant wavelength is 365nm. When the intensity of the main wavelength is defined as 100%, the intensity at a wavelength of 436nm is 0.5% or less.

"-": the exposure was performed using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.) without using a filter having wavelength selectivity.

After leaving for 1 hour after exposure, the temporary support was peeled off, and then, a resin pattern was formed by development. For development, shower development was performed for 30 seconds using a 1.0% potassium carbonate aqueous solution (developer) at 28 ℃. The 1 st photosensitive layer and the 2 nd photosensitive layer are simultaneously developed.

In this order, a transparent substrate (hereinafter, also referred to as a "substrate with a resin pattern") having a transparent substrate, a 1 st resin pattern formed from a 1 st photosensitive layer on one (a) of the 2 opposed surfaces of the transparent substrate, and a 2 nd resin pattern formed from a 2 nd photosensitive layer on the other (B) surface was formed.

[ evaluation ]

The resin-patterned substrates prepared in examples 1 to 6 and comparative examples 1 to 3 were used to evaluate the resolution and exposure fogging, respectively. The evaluation results are shown in table 2.

Resolution

In the resin pattern, the line width of the pattern having the highest resolution is set as the final resolution. From the final resolution, the resolution was evaluated according to the following criteria. In addition, E is a case where the side wall portion of the pattern has high roughness or a case where a significant smear is generated and the pattern is continuous with an adjacent line pattern. For evaluation, D is preferable, C is more preferable, B is further preferable, and a is particularly preferable.

(evaluation criteria)

A: less than 10 μm

B: more than 10 μm and 18 μm or less

C: more than 18 μm and 20 μm or less

D: more than 20 μm and not more than 30 μm

E: over 30 μm or not distinguishable

< atomization by exposure >

The surface of the substrate with the resin pattern was observed for non-exposed portions (limited to portions where the surface of the transparent base material on the side opposite to the non-exposed portions was exposed, hereinafter, the same as in this paragraph), and exposure fogging was evaluated according to the following criteria. When exposure fogging occurs, a residue derived from the photosensitive layer is observed in the unexposed portion.

(evaluation criteria)

A: when observed by an optical microscope at a magnification of 50 times, no residue was found on either the side where the 1 st photosensitive layer was disposed with respect to the transparent substrate or the side where the 2 nd photosensitive layer was disposed with respect to the transparent substrate.

B: when observed with an optical microscope at a magnification of 50 times, a residue was found on at least one of the side where the 1 st photosensitive layer was disposed based on the transparent substrate and the side where the 2 nd photosensitive layer was disposed based on the transparent substrate.

Tables 1 and 2 are shown below.

The unit of the amount (addition amount) of each component shown in table 1 is part by mass.

In table 2, "maximum sensitivity wavelength" refers to the maximum sensitivity wavelength of the photosensitive layer. The method of measuring the maximum sensitivity wavelength of the photosensitive layer is as described above.

The "dye maximum absorption wavelength" represents the maximum absorption wavelength (unit: nm) of the dye. The method for measuring the maximum absorption wavelength of the dye is as described above.

In each of the items of the photosensitive layer and the thermoplastic resin layer, "dye 1" and "dye 2" represent dyes having a maximum absorption wavelength in a wavelength range of 300 to 500nm contained in the layer.

In table 2, "absorbance of the dye at the maximum sensitivity wavelength of the photosensitive layer" indicates that when 1 dye is contained in the photosensitive layer, the absorbance of the 1 dye is measured by the above-described measurement method. When the number of the pigments contained in the photosensitive layer is 2 or more, the 2 or more pigments are mixed to a mixing ratio (mass ratio) in the layer, and the absorbance value in the mixed state is measured by the above-described measurement method.

It is found that the resolution of the resin pattern is excellent and exposure fogging is suppressed in the substrate with the resin pattern of the example. Therefore, according to the transfer film and the laminate of the present invention, it is possible to form a resin pattern having excellent resolution and to suppress fogging during exposure.

For example, by taking example 1 in which a filter having wavelength selectivity is used as an example, the exposure light on the a-plane can be reflected by the filter having wavelength selectivity for selecting the wavelength of the exposure light on the B-plane, but even if the reflected light occurs, the reflected light can be absorbed by the dye, and the dye can absorb the light having the same or similar wavelength to the maximum sensitivity wavelength of the photosensitive layer on the a-plane in the photosensitive layer on the B-plane side. As a result, deterioration of the resolution on the a-plane due to the reflected light can be suppressed. Further, exposure fogging on the surface B due to exposure light on the surface a can be suppressed.

The exposure light of the B-side can be reflected by a filter having wavelength selectivity for selecting the wavelength of the exposure light of the a-side, but even if the reflected light occurs, the reflected light can be absorbed by a dye that can absorb light having a wavelength that is the same as or close to the maximum sensitivity wavelength of the photosensitive layer of the B-side in the photosensitive layer of the a-side. As a result, the deterioration of the resolution on the B-plane due to the reflected light can be suppressed. Further, exposure fogging on the a-side due to exposure light on the B-side can be suppressed.

Further, for example, when example 3 in which no filter having wavelength selectivity is used is taken as an example, even if the exposure light on the a-surface enters the photosensitive layer on the B-surface through the transparent substrate, the intensity per unit area of light having a wavelength equal to or similar to the maximum sensitivity wavelength of the photosensitive layer on the B-surface side among the entered light is reduced by the action of the pigment contained in the photosensitive layer on the a-surface side. As a result, exposure fogging on the B-plane can be suppressed.

Further, even if the exposure light on the B-side enters the photosensitive layer on the a-side through the transparent base material, the intensity per unit area of light having a wavelength equal to or similar to the maximum sensitivity wavelength of the photosensitive layer on the a-side among the entering light is reduced by the action of the dye contained in the photosensitive layer on the B-side. As a result, exposure fogging on the a-plane can be suppressed.

Further, the dye introduced on both the A-side and the B-side has a difference of 40nm or more in the maximum absorption wavelength from the maximum sensitivity wavelength of the photosensitive layer, and thus the resolution of the resin pattern is excellent.

From the comparison of examples 1 to 6, it was confirmed that a resin pattern having a further excellent resolution can be formed when the maximum sensitivity wavelength of the B-plane is 450nm or less.

It was confirmed from the comparison of examples that a resin pattern having a higher resolution can be formed without including a dye having the same or similar maximum sensitivity wavelength as that of the photosensitive layer (comparison of examples 1 and 2 with examples 5 and 6).

[ examples 11 to 31 and comparative examples 4 to 6 ]

[ transfer printing film production ]

Each transfer film for transferring the photosensitive layer to 2 surfaces (a surface and B surface) of the transparent substrate facing each other was prepared according to the formulation described in table 4. Each of the transfer films for the a-side and the B-side has a structure including a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive layer, and a protective film in this order. For example, in example 11, the transfer film for surface A had a temporary support, a thermoplastic resin layer formed from the thermoplastic resin composition of formulation A-1, an intermediate layer formed from the composition (M-1) for forming an intermediate layer described later, a photosensitive layer formed from the composition for forming a photosensitive layer of formulation a-4, and a protective film. The transfer film for B-side comprises a temporary support, a thermoplastic resin layer formed from the thermoplastic resin composition of the formula B-1, an intermediate layer formed from a composition (M-1) for forming an intermediate layer, which will be described later, a photosensitive layer formed from the composition for forming a photosensitive layer of the formula B-6, and a protective film.

The formulation of each photosensitive layer forming composition is shown in table 1, and the formulation of each thermoplastic resin composition is shown in table 3.

A thermoplastic resin composition having a formulation No. shown in Table 4 was applied to a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) by means of a slit nozzle until the application width became 1.0m and the layer thickness after drying became 3.0. Mu.m. Thereafter, the obtained coating film of the thermoplastic resin composition was dried at 80 ℃ for 40 seconds, thereby forming a thermoplastic resin layer.

Subsequently, the obtained thermoplastic resin layer was coated with the intermediate layer forming composition (M-1) using a slit nozzle until the coating width became 1.0M and the layer thickness after drying became 1.2. Mu.m. Thereafter, the coating film of the obtained composition (M-1) for forming an intermediate layer was dried at 80 ℃ for 40 seconds, thereby forming an intermediate layer.

Next, the photosensitive layer was formed by applying the photosensitive layer forming composition on the obtained intermediate layer using a slit nozzle until the application width became 1.0m and the layer thickness after drying became 3.0 μm, and drying the resultant in a convection oven at 100 ℃ for 2 minutes. Then, a protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was attached to the photosensitive layer to prepare each transfer film.

For example, in example 11, a transfer film having a temporary support, a thermoplastic resin layer formed from the thermoplastic resin composition of formulation a-1, an intermediate layer, a photosensitive layer formed from the composition for forming a photosensitive layer of formulation a-4, and a protective film in this order was prepared as a transfer film for surface a. Further, as a transfer film for the B-side, a transfer film was produced which sequentially had a temporary support, a thermoplastic resin layer formed from the thermoplastic resin composition of the formulation B-1, an intermediate layer, a photosensitive layer formed from the composition for forming a photosensitive layer of the formulation B-6, and a protective film.

[ preparation of composition (M-1) for intermediate layer formation ]

The following ingredients were mixed to prepare an intermediate layer-forming composition.

Kuraray Poval PVA-4-88LA (Kuraray Co., ltd.): 3.22 parts by mass

Polyvinylpyrrolidone K-30 (NIPPON shokubali co., ltd.): 1.49 parts by mass

MEGAFACE F-444 (manufactured by DIC Corporation): 0.0015 parts by mass

Ion-exchanged water: 38.12 parts by mass

Methanol (MITSUBISHI GAS CHEMICAL COMPANY, inc.): 57.17 parts by mass

[ production of laminate ]

The transfer film selected according to the description in table 4 was cut into a 50cm square, and then the protective film was peeled off from the transfer film. Next, transfer films were laminated on 2 opposed surfaces (A surface and B surface) of a transparent substrate (polyethylene terephthalate film, thickness: 40 μm) under lamination conditions of a roll temperature of 90 ℃ and a line pressure of 0.8MPa and a line speed of 3.0 m/min. In the above procedure, a laminate was produced.

The laminate has a structure of temporary support, thermoplastic resin layer, interlayer, 1 st photosensitive layer, transparent substrate, 2 nd photosensitive layer, interlayer, thermoplastic resin layer, and temporary support.

Using the laminate thus produced, resin-patterned substrates of examples 11 to 31 and comparative examples 4 to 6 were produced in accordance with the method described in the "patterning" section. Using the obtained resin pattern-carrying substrate, the resolution and exposure fogging described in the above "evaluation" item were evaluated. The evaluation results are shown in table 4.

Tables 3 and 4 are shown below.

The unit of the amount (addition amount) of each component shown in table 3 is part by mass.

In table 4, "wavelength of maximum sensitivity" refers to the wavelength of maximum sensitivity of the photosensitive layer. The method of measuring the maximum sensitivity wavelength of the photosensitive layer is as described above.

In table 4, "absorbance of the dye at the maximum sensitivity wavelength of the photosensitive layer" indicates that when the types of the dye used in the photosensitive layer and the thermoplastic resin layer are 1, the absorbance of the 1 dye is measured by the above-described measurement method. When the number of the coloring matters used in the photosensitive layer and the thermoplastic resin layer is 2 or more, the 2 or more coloring matters are mixed in a mixing ratio (mass ratio) in the layer, and the absorbance value in the mixed state is measured by the above-mentioned measuring method.

For example, in the case of example 11 using a filter having wavelength selectivity, although the exposure light on the a-side can be reflected by the filter having wavelength selectivity for selecting the wavelength of the exposure light on the B-side, even if the reflected light occurs, the reflected light can be absorbed by the dye which can absorb the light having the same or similar wavelength to the maximum sensitivity wavelength of the photosensitive layer on the a-side in the thermoplastic resin layer on the B-side. As a result, deterioration in resolution on the a-plane due to the reflected light can be suppressed. Further, exposure fogging of the surface A due to exposure light can be suppressed on the surface B.

The exposure light of the B-side can be reflected by a filter having wavelength selectivity for selecting the wavelength of the exposure light of the a-side, but even if the reflected light is generated, the reflected light can be absorbed by the dye, and the dye can absorb the light having the same or similar wavelength to the maximum sensitivity wavelength of the photosensitive layer of the B-side in the thermoplastic resin layer of the a-side. As a result, exposure fogging and deterioration in resolution on the B-plane due to reflected light can be suppressed. Further, exposure fogging of the A-side due to exposure light of the B-side can be suppressed.

Further, for example, when the description is given by taking example 17 in which no filter having wavelength selectivity is used as an example, even if the exposure light on the a-surface enters the photosensitive layer on the B-surface through the transparent base material, the intensity per unit area of the light having the same or similar wavelength as the maximum sensitivity wavelength of the photosensitive layer on the B-surface side among the entered light is lowered by the action of the coloring matter contained in the thermoplastic resin layer on the a-surface side. As a result, exposure fogging on the B-plane can be suppressed.

Even if the exposure light on the side B enters the photosensitive layer on the side a through the transparent base material, the intensity per unit area of the light having the same or similar wavelength as the maximum sensitivity wavelength of the photosensitive layer on the side a among the entered light is reduced by the action of the coloring matter contained in the thermoplastic resin layer on the side B. As a result, exposure fogging on the a-plane can be suppressed.

Further, since the maximum absorption wavelength of the dye introduced into both the a-plane and the B-plane differs from the maximum sensitivity wavelength of the photosensitive layer by 40nm or more, the resolution of the resin pattern is excellent.

It was confirmed from the comparison of examples that when the specific dye was a non-sensitizing dye, a resin pattern with a higher resolution could be formed (results of examples 16 and 17).

From the comparison of examples, it was confirmed that when the composition layer was composed of the photosensitive layer, the intermediate layer and the thermoplastic resin layer, and the thermoplastic resin layer contained the specific coloring matter, a resin pattern having a more excellent resolution could be formed (comparison of examples 11 to 14).

It was confirmed from the comparison in examples that a resin pattern having a higher resolution can be formed without including a dye having the same or similar maximum sensitivity wavelength as the photosensitive layer (results of examples 14 and 15).

Further, it was confirmed from the results of example 16 that the sensitizing dye functions as a specific dye in the thermoplastic resin layer containing no initiator.

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

In example 19 and examples 21 to 24, since the i-ray absorption ability of the pigment on the B-plane was slightly poor, a part of the exposure light from the B-plane side was transmitted through the a-plane, and the resolution was slightly poor.

Description of the symbols

20-laminate, 5A-first transfer film, 11-substrate 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 substrate, 7A, 7B-transparent conductive layer, 12-mask, 13, 15-filter with 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-interlayer, 37, 57-photosensitive layer, 39, 59-composition layer, 41-protective film.

Claims

1. A transfer film suitable for a substrate with a transparent conductive layer, which has a transparent substrate and transparent conductive layers disposed on both surfaces of the transparent substrate,

the composition layer contains a pigment having an absorption maximum wavelength at a wavelength different from a wavelength of maximum sensitivity of the photosensitive layer,

2. The transfer film according to claim 1,

3. The transfer film according to claim 1 or 2,

the maximum sensitivity wavelength of the photosensitive layer is 300nm to 395nm, and the maximum absorption wavelength of the pigment exceeds 395nm and is less than 500 nm.

4. The transfer film according to claim 1 or 2,

the maximum sensitivity wavelength of the photosensitive layer is over 395nm and below 500nm, and the maximum absorption wavelength of the pigment is 300 nm-395 nm.

5. The transfer film according to claim 1 or 2,

the pigment is a non-sensitizing pigment.

6. The transfer film according to claim 1 or 2,

7. The transfer film according to claim 1 or 2,

the composition layer comprises a sensitizer which is capable of forming a layer,

the sensitizer is at least 1 selected from benzophenone compound, thioxanthone compound, cyanine compound, coumarin compound and merocyanine compound.

8. The transfer film according to claim 1 or 2,

the pigment is contained in the photosensitive layer.

9. The transfer film according to claim 1 or 2,

the composition layer further has a thermoplastic resin layer at a position closer to the temporary support than the photosensitive layer.

10. The transfer film according to claim 9,

the pigment is contained in the thermoplastic resin layer.

11. The transfer film according to claim 1 or 2,

the photosensitive layer further comprises a polymerization inhibitor,

12. A laminate, comprising:

a substrate with a transparent conductive layer, which has a transparent substrate and transparent conductive layers disposed on both sides of the transparent substrate; and

the transfer film according to any one of claims 1 to 11 attached to both sides of the substrate with a transparent conductive layer.

13. The laminate according to claim 12, wherein,

in one transfer film of the laminate, the maximum sensitivity wavelength of the photosensitive layer is 300nm to 395nm, the maximum absorption wavelength of the dye exceeds 395nm and is 500nm or less,

In the transfer film on the other side, the maximum sensitivity wavelength of the photosensitive layer is more than 395nm and 500nm or less, and the maximum absorption wavelength of the dye is 300nm to 395nm.

14. A method for forming a pattern by subjecting the transfer film in the laminate according to claim 12 or 13 to exposure treatment and development treatment,

the pattern forming method includes:

15. The pattern forming method according to claim 14, wherein,

16. The pattern forming method according to claim 14 or 15,

17. The pattern forming method according to claim 14 or 15, comprising:

18. A method of manufacturing a circuit board, comprising the pattern forming method of claim 14 or 15.