WO2022131324A1

WO2022131324A1 - Transfer film, method for producing laminate, and method for producing circuit wiring

Info

Publication number: WO2022131324A1
Application number: PCT/JP2021/046474
Authority: WO
Inventors: 裕之米澤
Original assignee: 富士フイルム株式会社
Priority date: 2020-12-17
Filing date: 2021-12-16
Publication date: 2022-06-23

Abstract

A first problem to be addressed by the present invention is to provide a transfer film that can form a pattern in which a defect caused by re-adhesion failure is suppressed. In addition, a second problem to be addressed by the present invention is to provide a method for producing a laminate and a method for producing a circuit wiring.　This transfer film has a temporary support and a composition layer. The composition layer includes a negative photosensitive composition layer. The negative photosensitive composition layer contains a binder polymer, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, and satisfies requirements 1 and 2.

Description

Manufacturing method of transfer film, laminate, manufacturing method of circuit wiring

The present invention relates to a method for manufacturing a transfer film, a laminate, and a method for manufacturing a circuit wiring.

During the manufacturing process of the touch sensor, the etching resist film and various protective films (electrode protective film, wiring protective film, and interlayer insulating film) are usually formed by a photolithography process using a photoresist.
The photolithography process is a process of exposing a photoresist through a mask and then removing a portion soluble in a developer by development. For example, when the photoresist is a photoresist (negative type photoresist) that is cured by exposure, the curing reaction proceeds in the mask opening, while the curing reaction is suppressed in the unexposed portion shielded by the mask. Therefore, the exposed portion and the unexposed portion have different solubility in the developing solution, and only the unexposed portion having high solubility in the developing solution is removed during the developing process.

Since the number of steps for obtaining a predetermined pattern is small these days, a negative photosensitive composition layer is arranged on an arbitrary substrate by using a transfer film, and a mask is applied to the negative photosensitive composition layer. A method of developing after exposure through a film is widely used.

For example, Patent Document 1 discloses a temporary support and a transfer film having a first transparent layer, a second transparent layer, and a third transparent layer on the temporary support in this order.
In Patent Document 1, specifically, a negative photosensitive composition layer (first transparent layer) containing a temporary support / binder polymer, a polymerizable monomer, and a polymerization initiator / a resin composition containing metal oxide particles. Negative photosensitive layer (second transparent layer) / negative-type photosensitive component containing a low molecular weight component (specifically, a component capable of contributing to a curing reaction such as a polymerizable monomer and a polymerization initiator) contained in the first transparent layer. A transfer film provided with a composition layer (third transparent layer) is disclosed.

Japanese Unexamined Patent Publication No. 2018-0242525

The present inventor prepared a transfer film with reference to Patent Document 1 and examined the pattern forming process. As a result, a component that does not dissolve in a developing solution during the developing step (hereinafter, also referred to as "development undissolved substance"). ) Adhered to the object to be treated, and it was clarified that a defect occurred in the pattern.
Further, as a result of further studies by the present inventor, the adhesion of the undissolved developer to the object to be processed (hereinafter, also referred to as “reattachment failure”) is a half exposure that occurs in the boundary region between the exposed portion and the unexposed portion. It was also clarified that the cause was the low solubility of the part in the developer. The half-exposed portion is intended as a region where a curing reaction occurs due to light leakage caused by diffusion or diffraction of light source light, although the region is originally shielded by a mask. More specifically, FIG. 1 will show that the negative photosensitive composition layer 41 arranged on the substrate 40 is exposed to light (arrows in FIG. 1) through a mask 42 having an opening in a predetermined region. By irradiating, the opening portion of the mask 42 becomes the exposed portion 43, and the region shielded by the mask 42 becomes the unexposed portion 44. The half-exposed unit 45 is a region where a curing reaction occurs due to light leakage caused by diffusion or diffraction of light source light, although it is originally a region shielded by the mask 42.
That is, it was clarified that the component cured in this half-exposed portion has low solubility in the developing solution and becomes an undissolved substance in the developing solution, which causes a reattachment failure.

Therefore, it is an object of the present invention to provide a transfer film capable of forming a pattern in which defects caused by reattachment failure are suppressed.
Another object of the present invention is to provide a method for manufacturing a laminated body and a method for manufacturing a circuit wiring.

As a result of diligent studies, the present inventor has found that the above problems can be solved by the following configuration.

[1] A transfer film having a temporary support and a composition layer.
The composition layer includes a negative photosensitive composition layer, and includes a negative photosensitive composition layer.
The negative photosensitive composition layer contains a binder polymer, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator.
A transfer film that meets the following

requirements

1 and 2.
Requirement 1: The surface of the transfer film opposite to the temporary support side is brought into contact with the glass substrate to form a laminate having the glass substrate, the composition layer, and the temporary support in this order, and the laminate is formed. The thickness of the cured film of the negative photosensitive composition layer in the exposed portion after the body is exposed to a plurality of locations while increasing the exposure amount and the development and cleaning treatment satisfying the following condition A is performed. The measurement was performed, and the points corresponding to the film thickness and the exposure amount at each exposure point were plotted on the orthogonal coordinates with the film thickness of the cured film as the vertical axis and the exposure amount as the horizontal axis, and the film thickness changed substantially. The film thickness at the exposure amount that disappears is used as the reference film thickness, and from the orthogonal coordinates, the exposure amount E10 at which the film thickness of the cured film is 10% of the reference film thickness, and the film thickness of the cured film are When the exposure amount E90, which is 90% of the reference film thickness, is calculated, the relationship of the following formula (1) is satisfied.
Condition A: A development treatment is carried out for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution having a temperature of 30 ° C., and then a cleaning treatment is carried out for 30 seconds using pure water having a temperature of 30 ° C. .. The development process is a shower method, the shower pressure is 0.10 MPa, and the shower flow rate is 1000 mL / min. The washing process is a shower method, the shower pressure is 0.10 MPa, and the shower flow rate is 1000 mL / min.
Equation (1): E10 / E90 ≧ 0.5
Requirement 2: The surface of the transfer film opposite to the temporary support side is brought into contact with the quartz crystal to form a laminate having the quartz crystal, the composition layer, and the temporary support in this order. After irradiating the laminate with ultraviolet rays at twice the exposure amount of E90, when the exposed laminate is immersed in a 1.0 mass% sodium carbonate aqueous solution having a temperature of 30 ° C., crystal vibration occurs. The mass increase rate of the cured film of the negative photosensitive composition layer 30 seconds after the start of immersion, which is determined based on the child microbalance method, is 20% by mass or less.
[2] Further, the transfer film according to [1], which satisfies the following formula (1-1).
Equation (1-1): E10 / E90 ≧ 0.8
In the formula (1-1), the E10 and the E90 are synonymous with the E10 and the E90 in the formula (1), respectively.
[3] The transfer film according to [1] or [2], wherein the mass content ratio of the polymerizable compound to the binder polymer is 0.5 or more.
[4] The transfer film according to any one of [1] to [3], wherein the negative photosensitive composition layer contains a tetrafunctional or higher polymerizable compound.
[5] The transfer film according to any one of [1] to [4], wherein the binder polymer has a radically polymerizable group.
[6] The binder polymer contains a structural unit having a radically polymerizable group.
The transfer film according to [5], wherein the content of the structural unit having a radically polymerizable group is 20% by mass or more with respect to all the structural units in the binder polymer.
[7] The negative photosensitive composition layer further contains a polymerization inhibitor and contains a polymerization inhibitor.
The transfer film according to any one of [1] to [6], wherein the content of the polymerization inhibitor is 5 to 15% by mass with respect to the content of the photopolymerization initiator.
[8] The transfer film according to any one of [1] to [7], wherein the composition layer includes a refractive index adjusting layer.
[9] The transfer film according to any one of [1] to [8], which is used for forming a protective film for a touch panel.
[10] The transfer film according to any one of [1] to [8], which is used for a touch panel electrode pattern forming etching resist.
[11] The surface of the transfer film according to any one of [1] to [8] opposite to the temporary support is brought into contact with a substrate having a conductive layer and bonded to the substrate, the conductive layer, and the like. A bonding step of obtaining a substrate with a composition layer having the composition layer and the temporary support in this order, and
An exposure process for pattern exposure of the composition layer and
A developing step of developing the exposed composition layer to form a protective film pattern that protects the conductive layer.
Further, laminating including a peeling step of peeling the temporary support from the substrate with the composition layer between the bonding step and the exposure step, or between the exposure step and the developing step. How to make a body.
[12] The method for producing a laminate according to [11], wherein the developing step is a step of repeatedly using the developing solution by circulating the developing solution.
[13] The bonding step is a step of bonding the transfer film and the substrate having the conductive layer by roll-to-roll, and at least the long laminated body formed by the bonding step is bonded. The method for producing a laminate according to [11] or [12], wherein the exposure step and the development step are carried out.
[14] The method for manufacturing a laminate according to any one of [11] to [13], wherein the substrate having the conductive layer is a substrate having at least one of a touch panel electrode and a touch panel wiring.
[15] The surface of the transfer film according to any one of [1] to [8] opposite to the temporary support is brought into contact with a substrate having a conductive layer, and the substrate, the conductive layer, and the composition are brought into contact with each other. A bonding step of obtaining a substrate with a layer and a composition layer having the temporary support in this order, and
An exposure process for pattern exposure of the composition layer and
A developing step of developing the exposed composition layer to form a resin pattern,
An etching process for etching the conductive layer in a region where the resin pattern is not arranged, and an etching process.
Further, a method for manufacturing a circuit wiring, comprising a peeling step of peeling the temporary support from the substrate with the composition layer between the bonding step and the exposure step, or between the exposure step and the developing step.

According to the present invention, it is possible to provide a transfer film capable of forming a pattern in which defects caused by reattachment failure are suppressed.
Further, the present invention can provide a method for manufacturing a laminated body and a method for manufacturing a circuit wiring.

It is a schematic diagram for demonstrating the half-exposure part. It is a schematic diagram for demonstrating the sensitivity curve (horizontal axis: exposure amount, vertical axis: film thickness of a negative type photosensitive composition layer) of the transfer film of this invention. It is a schematic diagram for demonstrating the sensitivity curve (horizontal axis: exposure amount, vertical axis: film thickness of a negative type photosensitive composition layer) of the transfer film of the comparative example. It is sectional drawing of the sample used for making a sensitivity curve. It is a figure which exposes the sample of FIG. FIG. 4 is a diagram when the exposed sample of FIG. 4 is developed. It is a schematic diagram for demonstrating a sensitivity curve. It is a schematic diagram which shows an example of the structure of the transfer film of 1st Embodiment. It is a schematic diagram which shows an example of the structure of the transfer film of 2nd Embodiment.

Hereinafter, the present invention will be described in detail.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present specification, in the numerical range described in stages, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value in another numerical range described in stages. .. Further, in the numerical range 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 value shown in the examples.

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

As used herein, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and is preferably 90% or more.
In the present specification, the average transmittance of visible light is a value measured by using a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) as columns. ), THF (tetrahydrofuran) as the eluent, polystyrene as the standard material, and polystyrene as the standard material measured by a gel permeation chromatography (GPC) analyzer. be.
In the present specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
In the present specification, unless otherwise specified, the ratio of the constituent units of the polymer is the mass ratio.
In the present specification, unless otherwise specified, the content of the metal element is a value measured by using an inductively coupled plasma (ICP) spectroscopic analyzer.
In the present specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
In the present specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

In the present specification, "(meth) acrylic" is a concept that includes both acrylic and methacrylic, and "(meth) acryloxy group" is a concept that includes both an acryloxy group and a metaacryloxy group.

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

As used herein, the term "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more. Therefore, for example, the water-soluble resin is intended to be a resin satisfying the above-mentioned solubility conditions.

As used herein, the "solid content" of a composition means a component forming a composition layer formed by using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent is used. Means all ingredients except. Further, if the component forms a composition layer, the liquid component is also regarded as a solid content.

[Transfer film]
The transfer film of the present invention is
A transfer film having a temporary support and a composition layer.
The composition layer includes a negative photosensitive composition layer, and includes a negative photosensitive composition layer.
The negative photosensitive composition layer contains a binder polymer, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator.
Satisfy Requirement 1 and Requirement 2 described later.
With the above configuration, the transfer film of the present invention can form a pattern in which defects caused by reattachment failure are suppressed.

Hereinafter, the presumed mechanism of action of the transfer film of the present invention will be described in comparison with the transfer film of the prior art.
In the following example, a mode in which the composition layer is composed of only the negative photosensitive composition layer (single layer configuration of only the negative photosensitive composition layer) will be described as an example.
For a laminate formed by transferring a transfer film provided with a temporary support and a negative photosensitive composition layer to a substrate (a laminate composed of a substrate / a negative photosensitive composition layer / a temporary support). The thickness of the cured film of the negative photosensitive composition layer in the exposed portion after exposure was performed at a plurality of locations while increasing the exposure amount and development and cleaning treatment were performed under predetermined conditions, and the cured film was measured. The points corresponding to the film thickness and the exposure amount at each exposed point are plotted on the orthogonal coordinates with the film thickness as the vertical axis and the exposure amount as the horizontal axis (hereinafter, the exposure amount with the film thickness of the cured film as the vertical axis). The curve obtained by plotting the points corresponding to the film thickness and the amount of exposure at each exposure point on the orthogonal coordinates with the horizontal axis as the horizontal axis is also called a "sensitivity curve"), and the exposure that the film thickness does not change substantially The film thickness in the amount is used as the reference film thickness, and from the orthogonal coordinates, the exposure amount E10 is 10% of the reference film thickness, and the exposure amount is 90% of the reference film thickness. When E90 is calculated, the transfer film of the present invention is characterized in that the difference between E10 and E90 is small, as shown in FIG. 2A. That is, during the exposure process, curing is suppressed until a predetermined exposure amount is reached, and when the predetermined exposure amount is reached, a chain curing reaction occurs and a sensitivity curve with a steep slope is shown. As a result, the transfer film of the present invention undergoes a curing reaction even if light leakage occurs due to diffusion or diffraction of light source light in a shielded region by a mask during exposure processing, as long as the exposure amount does not reach a predetermined level. Progression is suppressed, and undeveloped undissolved material is less likely to be formed. In particular, the inventors have clarified by this study that when E10 / E90 ≧ 1.5, the reattachment failure can be remarkably suppressed.
On the other hand, in the transfer film of the prior art, as shown in FIG. 2B, the difference between E10 and E90 is large, and a sensitivity curve with a gentle inclination is shown. In a transfer film having such a sensitivity curve, a curing reaction is likely to occur even with light leakage caused by diffusion or diffraction of light source light in a shielded region by a mask during an exposure process, and a developed undissolved substance is likely to be formed.

Further, in this study, the present inventor also suppresses the swelling rate (mass increase rate) of the exposed negative photosensitive composition layer (cured film) by the developer to a predetermined value or less, which also causes a reattachment failure. We also know that it is one of the factors that suppress it. If the swelling rate (mass increase rate) is too large, the half-exposed portion, which is insufficiently cured, swells with the developing solution and is easily deformed to cause desorption, which may cause a reattachment failure. Further, when the cured film is swollen, the elastic modulus is lowered, so that the undissolved developer liquid is likely to adhere to the surface of the swollen cured film, and a reattachment failure is likely to occur.
In this study, the present inventor has clarified that when the above-mentioned mass increase rate is 20% by mass or less, the reattachment failure can be remarkably suppressed.

Further, the transfer film of the present invention is suitable for a developing process in which a developing solution is circulated and the developing solution is repeatedly used.
When the developer is used repeatedly, the solubility of the developer is usually lowered due to the developer fatigue, and reattachment failure due to the undissolved developer is likely to occur. On the other hand, in the transfer film of the present invention, as described above, the generation of undissolved developer in the developing solution due to the half-exposed portion is suppressed, so that even if the developing solution is used repeatedly, it is contained in the developing solution. Undissolved developer is less likely to occur.

Further, the transfer film of the present invention is suitable for a method for producing a laminate in a roll tool process. In the roll-to-roll process, the area in which the transport roller contacts the work is large. Therefore, if the undissolved developer solution adheres to the work after the development process, the undissolved developer solution is pressed against the work, and a reattachment failure is likely to occur.
On the other hand, in the transfer film of the present invention, as described above, the generation of undissolved developer due to the half-exposed portion is suppressed, so that the undissolved developer adheres to the work after the development process. Is unlikely to occur.

In the following, the fact that the pattern reattachment failure formed by the transfer film of the present invention is more excellent may be referred to as "the effect of the present invention is more excellent".

Hereinafter, the transfer film of the present invention will be described.
The transfer film of the present invention has a temporary support and a composition layer arranged on the temporary support, and the composition layer includes a negative photosensitive composition layer.
The composition layer is not particularly limited as long as it includes a negative photosensitive composition layer.
Further, the composition layer may have a single layer structure or may have a structure of two or more layers. When the composition layer contains a composition layer other than the negative photosensitive composition layer, examples of the other composition layer include a refractive index adjusting layer, a thermoplastic resin layer, and an intermediate layer.
Further, the transfer film may have a structure in which a protective film (hereinafter, also referred to as “cover film”) is provided on the composition layer. The composition layer does not contain a protective film.

The transfer film of the present invention satisfies the following

requirements

1 and 2.
Requirement 1: The surface of the transfer film opposite to the temporary support side is brought into contact with the glass substrate to form a laminate having the glass substrate, the composition layer, and the temporary support in this order, and the laminate is formed. The thickness of the cured film of the negative photosensitive composition layer in the exposed portion after the body is exposed to a plurality of locations while increasing the exposure amount and the development and cleaning treatment satisfying the following condition A is performed. The measurement was performed, and the points corresponding to the film thickness and the exposure amount at each exposure point were plotted on the orthogonal coordinates with the film thickness of the cured film as the vertical axis and the exposure amount as the horizontal axis, and the film thickness changed substantially. The reference film thickness is the film thickness at the exposure amount that disappears, and from the orthogonal coordinates, the exposure amount E10 is 10% of the reference film thickness, and the film thickness is 90% of the reference film thickness. When the exposure amount E90 is calculated, the relationship of the following formula (1) is satisfied. The fact that the film thickness does not substantially change can be mentioned, for example, that the change in film thickness before and after the treatment under the following condition A is 3.0% or less.
Condition A: A development treatment is carried out for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution having a temperature of 30 ° C., and then a cleaning treatment is carried out for 30 seconds using pure water having a temperature of 30 ° C. .. The development process is a shower method, the shower pressure is 0.10 MPa, and the shower flow rate is 1000 mL / min. The washing process is a shower method, the shower pressure is 0.10 MPa, and the shower flow rate is 1000 mL / min.
Equation (1): E10 / E90 ≧ 0.5

As a method for measuring the film thickness of the cured film of the negative photosensitive composition layer, a stylus type film thickness meter (for example, "DekTak150" manufactured by Bruker Co., Ltd.) can be used for the measurement.
When the transfer film has a protective film, the protective film is peeled off, and then the transfer film after the protective film is peeled off is transferred to the glass substrate.
Further, when the transfer film has another composition layer (for example, a thermoplastic resin layer and an intermediate layer) between the temporary support and the negative photosensitive composition layer, the transfer film is transferred onto the glass substrate. This comprises a step of removing the other composition layer from the laminated body after subjecting the laminated body to a predetermined ultraviolet irradiation. For example, the other composition layer can be removed from the laminate by treatments such as alkaline development treatment, solvent cleaning, and tape peeling.
When the transfer film has another composition layer (for example, a refractive index adjusting layer) on the side opposite to the temporary support side of the negative photosensitive composition layer, the cured film of the negative photosensitive composition layer. A sensitivity curve is created by plotting the points corresponding to the film thickness and the exposure amount at each exposure point on the orthogonal coordinates with the total film thickness of the above and the other composition layers as the vertical axis and the exposure amount as the horizontal axis. However, by making a correction by subtracting the thickness of the other composition layer from this sensitivity curve, the residual film ratio of the cured film of the negative photosensitive composition layer can be measured.
Further, it is preferable to peel off the temporary support after the laminated body is irradiated with ultraviolet rays and before the development and cleaning treatment satisfying the above-mentioned condition A is performed.
Further, it is preferable that the laminated body irradiated with ultraviolet rays is kept in an environment of 25 ° C. and 60% for 24 hours before the development and cleaning treatment satisfying the above-mentioned condition A is carried out.

Hereinafter, how to obtain the sensitivity curve in Requirement 1 will be described with reference to the drawings.
In the following, a method of obtaining a sensitivity curve of a transfer film composed of a temporary support, a negative photosensitive composition layer, and a protective film will be described as an example.
First, the surface of the transfer film opposite to the temporary support side is brought into contact with the glass substrate, and the transfer film is transferred (laminated) to the glass substrate to prepare a laminated body. When the transfer film has a protective film, the transfer film from which the protective film has been peeled off is transferred to the glass substrate. As shown in FIG. 3, the laminate (sample) thus obtained has a negative photosensitive composition layer 32 having a thickness T and a temporary support 34 on a glass substrate 30.

The transfer can be carried out using a commercially available device (for example, a known laminator such as a vacuum laminator and an auto-cut laminator).
The temperature at which the transfer film is transferred onto the glass substrate is not particularly limited, but is preferably 80 to 150 ° C, more preferably 90 to 120 ° C, for example.
Further, when the transfer film is transferred to the glass substrate, it is preferably carried out by roll-to-roll, and the transport speed at that time is preferably, for example, 0.5 to 5 m / min. More preferably, it is 5 to 3 m / min.
Further, the glass substrate is not particularly limited, but for example, soda glass, non-alkali glass, quartz glass and the like can be used.

Next, using a predetermined light source, ultraviolet irradiation is performed on the negative photosensitive composition layer through the temporary support 34 while increasing the exposure amount. Specifically, while increasing the exposure amount by 10 mJ / cm ² to 5 mJ / cm ² , exposure is performed at 20 or more locations on different positions of the negative photosensitive composition layer. That is, different exposure amounts are exposed to 20 or more different positions on the surface of the negative photosensitive composition layer. More specifically, as shown in FIG. 4, as shown by the white arrows, different parts of the negative photosensitive composition layer are exposed to different exposure amounts. In FIG. 4, exposure is performed at three different positions of the negative photosensitive composition layer 32. The leftmost exposure in FIG. 4 is exposed at an exposure amount of ZmJ / cm ² , the middle exposure is exposed at an exposure amount (Z + 5) mJ / cm ² , and the rightmost exposure is exposed. Exposure is performed in an amount (Z + 5 × 2) mJ / cm ² . In this way, exposure is performed while increasing the exposure amount by 5 mJ / cm ² for each exposed portion.
The area of the exposed portion is not particularly limited, and examples thereof include a length of about 10 mm and a width of about 20 mm.
In addition, 20 or more exposure points are carried out. The upper limit of the number of exposed points is not particularly limited, but it is preferable to carry out the exposure until the film thickness reaches the maximum value and becomes substantially constant, and more preferably 50 or less.
The exposure apparatus is not particularly limited as long as it can irradiate ultraviolet rays, but for example, it is preferable to use an ultrahigh pressure mercury lamp.

After the exposure, the temporary support 34 is peeled off from the exposed laminate, and the exposed negative photosensitive composition layer is subjected to development and cleaning treatment satisfying the above condition A.
The developing and cleaning treatment satisfying the above condition A can be carried out by using a developing machine "YCD-500WA" manufactured by Yamagata Machinery Co., Ltd. and using a "full cone nozzle" as a shower nozzle. Specifically, a development process (development method: shower) for 30 seconds using a developer "YCD-500WA" manufactured by Yamagata Machinery Co., Ltd. and a 1.0 mass% concentration sodium carbonate aqueous solution at a temperature of 30 ° C. Development, shower nozzle: "full cone nozzle", shower pressure: 0.10 MPa, shower flow rate is 1000 mL / min), and then cleaning treatment for 30 seconds using pure water at a temperature of 30 ° C. (cleaning method: Shower washing, shower nozzle: "full cone nozzle", shower pressure: 0.10 MPa, shower flow rate is 1000 mL / min).
After the development and cleaning treatment satisfying the above condition A, drying is performed.
The drying temperature is not particularly limited, but is preferably 30 to 80 ° C, more preferably 30 to 60 ° C, for example.
The drying time is not particularly limited, but is preferably 5 to 30 minutes, more preferably 5 to 10 minutes, for example.

When the development and cleaning treatment satisfying the condition A is performed, a cured film of the negative photosensitive composition layer is obtained at the exposed portion. The film thickness of the cured film at that time varies depending on the exposure amount. For example, FIG. 5 is a view after the film shown in FIG. 4 is subjected to development and cleaning treatment satisfying the condition A, and the cured film 32A at the leftmost exposed portion has the thinnest thickness and the most. The thickness of the cured film 32A at the exposed portion on the right side is the thickest. That is, the relationship is T1 <T2 <T3. In FIG. 5, only the film thicknesses at three points are shown, but in reality, the film thicknesses at 20 or more exposed points are measured.

Next, a plot diagram is created using the data of the exposure amount and the film thickness at each exposed portion. Specifically, the points corresponding to the film thickness and the exposure amount at each exposed portion are plotted on the orthogonal coordinates with the film thickness as the vertical axis and the exposure amount as the horizontal axis. That is, a graph (sensitivity curve) is created with the film thickness at each exposed point on the vertical axis and the exposure amount at each exposed point on the horizontal axis. The unit of the vertical axis is μm, and the unit of the exposure amount is mJ / cm ² . FIG. 6 shows an example of a plot diagram. Each black circle in FIG. 6 corresponds to the result (film thickness and exposure amount) at each exposed portion. In FIG. 6, the number of plots of black circles is smaller than the actual 20 points for the sake of simplicity. Further, a line may be created by connecting the plotted points in the obtained plot diagram.

As shown in FIG. 6, in the plot diagram, the film thickness usually increases as the exposure amount increases in the region A, and the film thickness becomes substantially constant at the maximum value even if the exposure amount increases in the region B. ..
First, in the region A, as the exposure amount increases, the decomposition amount of the photopolymerization initiator increases in the exposure region, and the amount of active species (for example, radicals) generated increases. As a result, the generated active species (for example, radicals) act on the polymerization components such as the polymerizable compound having an ethylenically unsaturated group, and a chain polymerization reaction occurs. As the polymerization reaction progresses, the cured film formed by the polymerization reaction becomes less likely to dissolve in the alkaline developer, the cured film becomes more difficult to be removed at the exposed portion where the exposure amount is large, and the film thickness increases.
After that, when the region B having a certain exposure amount or more is reached, the cured film remains almost, and the film thickness becomes substantially constant at the maximum value. That is, the film thickness does not substantially change. Normally, there are a plurality of points where the film thickness shows the maximum value.
Here, "the film thickness does not substantially change" means that the rate of change in the film thickness at two adjacent plot points is 3% or less. Specifically, it is located in the region B in FIG. 6, and will be described in relation to the film thicknesses ( _TP1, T _P2 , and not shown, respectively) in the adjacent plots P1 and P2. {( _TP2 - _TP1 ) It means that the rate of change represented by / T _P1 } × 100 is 3% or less.
The thickness of the cured film in the region B where the film thickness does not substantially change even if the exposure amount is increased is set as the reference film thickness T100, and the film thickness of the cured film is 10% of the reference film thickness T100. The exposure amount E10 is calculated, and the exposure amount E90 at which the film thickness of the cured film is 90% of the reference film thickness T90 is calculated, and the value of E10 / E90 is calculated based on the obtained numerical values. ..

Requirement 2: The surface of the transfer film opposite to the temporary support side is brought into contact with the crystal oscillator to form a laminate having the crystal oscillator, the composition layer, and the temporary support in this order. After irradiating the laminate with ultraviolet rays at twice the exposure amount of E90, the crystal vibration when the exposed laminate is immersed in a 1.0% by mass concentration sodium carbonate aqueous solution at a temperature of 30 ° C. The mass increase rate of the cured film of the negative photosensitive composition layer 30 seconds after the start of immersion, which is obtained based on the child microbalance method (QCM method), is 20% by mass or less.
The mass increase rate is {(weight of the cured film of the negative photosensitive composition layer after immersion-weight of the cured film of the negative photosensitive composition layer before immersion) / negative photosensitive before immersion. Weight of the cured film of the sex composition layer} × 100.

The mass increase rate based on the QCM method can be measured by a resist development analyzer such as "RDA-Qz3" manufactured by Lithotech Japan.
Further, when the transfer film has another composition layer (for example, a thermoplastic resin layer and an intermediate layer) between the temporary support and the negative photosensitive composition layer, the transfer film is transferred onto the glass substrate. The above-mentioned other composition layer is removed from the laminated body after subjecting the laminated body to the predetermined ultraviolet irradiation. For example, the other composition layer can be removed from the laminate by treatments such as alkaline development treatment, solvent cleaning, and tape peeling.
Further, it is preferable that the laminated body irradiated with ultraviolet rays is kept in an environment of 25 ° C. and 60% for 24 hours before being immersed in a 1.0 mass% sodium carbonate aqueous solution having a temperature of 30 ° C. ..
When the transfer film has another composition layer (for example, a refractive index adjusting layer) on the side opposite to the temporary support side of the negative photosensitive composition layer, the transfer film is transferred onto the glass substrate. In the obtained laminate, the other composition layer is located between the cured negative photosensitive composition layer and the glass substrate. Therefore, when the above-mentioned mass increase rate is measured for the laminate, the mass increase derived from the other composition layers is usually substantially nonexistent or even slight. be. In particular, when the other composition layer is a refractive index adjusting layer, the refractive index adjusting layer is usually extremely thin with respect to the cured negative photosensitive composition layer, and has the above-mentioned mass with respect to the laminate. When the increase rate is measured, the mass increase derived from the refractive index adjusting layer usually does not occur substantially.

The transfer film of the present invention preferably satisfies the following formula (1-1) in that the effect of the present invention is more excellent.
Equation (1-1): E10 / E90 ≧ 0.8
In formula (1-1), E10 and E90 are synonymous with E10 and E90 in formula (1), respectively.

As an example of the means for achieving the

requirements

1 and 2 by the transfer film of the present invention, the compounding ratio of the polymerization inhibitor and the photopolymerization initiator in the negative photosensitive composition layer is adjusted within a predetermined range, and A method of reprecipitating the binder polymer to reduce the content of the residual monomer, adjusting the compounding ratio of the polymerization inhibitor and the photopolymerization initiator in the negative photosensitive composition layer to a predetermined range, and The method of introducing a large amount of radically polymerizable groups into the binder polymer and the compounding ratio of the polymerization inhibitor and the photopolymerization initiator in the negative photosensitive composition layer are adjusted within a predetermined range, and reprecipitated into the binder polymer. Examples thereof include a method of reducing the content of the residual monomer and introducing a large amount of radically polymerizable groups into the binder polymer.

An example of the aspect of the transfer film of the present invention is shown below, but the present invention is not limited thereto.
(1) "Temporary support / Negative photosensitive composition layer / Refractive index adjusting layer / Protective film"
(2) "Temporary support / Negative photosensitive composition layer / Protective film"
(3) "Temporary support / intermediate layer / negative photosensitive composition layer / protective film"
(4) "Temporary support / thermoplastic resin layer / intermediate layer / negative photosensitive composition layer / protective film"
In each of the above configurations, it is also preferable that the negative photosensitive composition layer is a colored resin layer.
The transfer film of the present invention may be used as a transfer film for a protective film or as a transfer film for an etching resist, as will be described later.
The term "for protective film" means a protective film provided to cover the electrodes and / or the wiring for the purpose of protecting the electrodes and / or the wiring, and a protective film for insulating the electrodes (specifically). Is intended as a protective film for insulating electrodes such as bridge wiring).
In the case of a transfer film for a protective film, the structure of the transfer film is preferably, for example, the above-mentioned structure (1) or (2). Further, in the case of using a transfer film for an etching resist, the composition of the transfer film is preferably, for example, the above-mentioned configurations (2) to (4).

When the composition layer of the transfer film further has another composition layer (for example, a refractive index adjusting layer) on the side opposite to the temporary support side of the negative photosensitive composition layer, the sum of the other layers is described above. The thickness is preferably 0.1 to 30%, more preferably 0.1 to 20%, based on the thickness of the negative photosensitive composition layer. In particular, when the other composition layer is a single layer of the refractive index adjusting layer, it is preferably 0.1 to 10%, more preferably 0.1 to 5%.

From the viewpoint of suppressing the generation of bubbles in the bonding step described later, the maximum width of the undulation of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 60 μm or less. The lower limit of the maximum width of the swell is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.
The maximum width of the waviness of the transfer film is a value measured by the following procedure.
First, the transfer film is cut in a direction perpendicular to the main surface so as to have a size of 20 cm in length × 20 cm in width to prepare a test sample. If the transfer film has a protective film, the protective film is peeled off. Next, the test sample is placed on a stage having a smooth and horizontal surface so that the surface of the temporary support faces the stage. After standing still, the surface of the sample sample was scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Co., Ltd.) for a range of 10 cm square in the center of the test sample to obtain a three-dimensional surface image, and the obtained 3 Subtract the minimum concave height from the maximum convex height observed in the 3D surface image. The above operation is performed on 10 test samples, and the arithmetic mean value is defined as the "maximum undulation width of the transfer film".

Hereinafter, the transfer film of the present invention will be described with reference to an example of a specific embodiment. The transfer film of the first embodiment below can be suitably used as a transfer film for a protective film, and the transfer film of the second embodiment below can be suitably used as a transfer film for an etching resist. It is a composition.

[Transfer film of the first embodiment]
Hereinafter, an example of the embodiment of the transfer film of the first embodiment will be described.
The transfer film 10 shown in FIG. 7 has a temporary support 1, a composition layer 2 including a negative photosensitive composition layer 3 and a refractive index adjusting layer 5, and a protective film 7 in this order.
The transfer film 10 shown in FIG. 7 has a form in which the protective film 7 is arranged, but the protective film 7 may not be arranged.
Further, the transfer film 10 shown in FIG. 7 has a form in which the refractive index adjusting layer 5 is arranged, but the refractive index adjusting layer 5 may not be arranged.
Hereinafter, each element constituting the transfer film will be described.

<< Temporary support >>
The transfer film has a temporary support.
The temporary support is a member that supports the composition layer, and is finally removed by a peeling treatment.

The temporary support may have a single-layer structure or a multi-layer structure.
The temporary support is preferably a film, more preferably a resin film. The temporary support is preferably a film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heating.
Examples of the film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a polymethylmethacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.
Among them, a polyethylene terephthalate film is preferable as the temporary support.
Further, it is preferable that the film used as the temporary support is free from deformation such as wrinkles and scratches.

The temporary support is preferably highly transparent from the viewpoint that the pattern can be exposed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.
From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, still more preferably 0.1% or less.
From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, and defects contained in the temporary support is small. The number of fine particles, foreign matter, and defects having a diameter of 1 μm or more in the temporary support is preferably 50 pieces / 10 mm ² or less, more preferably 10 pieces / 10 mm ² or less, further preferably 3 pieces / 10 mm ² or less, and 0. Pieces / 10 mm ² are particularly preferred.

The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and most preferably 5 to 25 μm from the viewpoint of ease of handling and versatility.
The thickness of the temporary support is calculated as an average value of any five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).

For the purpose of improving the adhesion between the temporary support and the composition layer, the side of the temporary support in contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.

When the surface modification of the temporary support is carried out by UV irradiation, the exposure amount is preferably 10 to 2000 mJ / cm ² , and more preferably 50 to 1000 mJ / cm ² . The light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength band of 150 to 450 nm. LED) and the like. As long as the amount of light irradiation is within this range, the lamp output and illuminance are not particularly limited.

Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

Preferred forms of the temporary support include, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019]-[0026] of JP-A-2016-0273363, and International Publication No. 2012 /. The description is given in paragraphs [0041] to [0057] of No. 081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370, and the contents of these publications are incorporated in the present specification.

A layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support from the viewpoint of imparting handleability. The lubricant layer may be provided on one side of the temporary support or on both sides. The diameter of the particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.
The film thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Examples of commercially available temporary supports include Lumirror 16KS40, Lumirror 16FB40 (above, manufactured by Toray Industries, Inc.), Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (above, manufactured by Toyobo Co., Ltd.).

<< Negative Photosensitive Composition Layer >>
The transfer film has a negative photosensitive composition layer.
A pattern can be formed on the transferred body by transferring the negative photosensitive composition layer onto the transferred body and then exposing and developing the layer. In the negative photosensitive composition layer, the exposed portion becomes a cured film due to exposure, and the solubility in a developing solution is lowered.
Hereinafter, the components that can be contained in the negative photosensitive composition layer will be described.

<Binder polymer>
The negative photosensitive composition layer contains a binder polymer.
Examples of the binder polymer include (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and the reaction of epoxy resin with (meth) acrylic acid. Examples thereof include the obtained epoxy acrylate resin and the acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin with the acid anhydride.

One of the preferred embodiments of the binder polymer is a (meth) acrylic resin in that it is excellent in alkali developability and film forming property.
In the present specification, the (meth) acrylic resin means a resin having a structural unit derived from the (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, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
The (meth) acrylic resin may be composed of only a structural unit derived from the (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by 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 ester, (meth) acrylamide, and (meth) acrylonitrile.
Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester. ) Acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate. Meta) Acrylic acid alkyl esters are preferred.
Examples of the (meth) acrylamide include acrylamide such as diacetone acrylamide.

The alkyl group of the (meth) acrylic acid alkyl ester may be linear or may have a branch. Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and (meth) acrylate. Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms such as dodecyl.
Further, the alkyl group of the (meth) acrylic acid alkyl ester may be cyclic. The cyclic alkyl group may be monocyclic or polycyclic. Specific examples include cyclohexyl (meth) acrylate and the like.
As the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.

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

Further, the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
Among them, the (meth) acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth) acrylic acid.

The content of the structural unit having an acid group (preferably the structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability, and is based on the total mass of the (meth) acrylic resin. 10% by mass or more is preferable. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.

Further, it is more preferable that the (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic acid alkyl ester.
The content of the structural unit derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic resin is preferably 50 to 90% by mass, preferably 60 to 90% by mass, based on all the structural units of the (meth) acrylic resin. More preferably, 65 to 90% by mass is further preferable.

As the (meth) acrylic resin, a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester is preferable, and the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid are preferable. A resin composed only of structural units derived from the (meth) acrylic acid alkyl ester is more preferable.
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.

Further, the (meth) acrylic resin may have at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester from the viewpoint that the effect of the present invention is more excellent. It is preferable to have both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate ester.
The total content of the constituent units derived from methacrylic acid and the constituent units derived from methacrylic acid alkyl ester in the (meth) acrylic resin is higher than that of all the constituent units of the (meth) acrylic resin because the effect of the present invention is more excellent. 40% by mass or more is preferable, and 60% by mass or more is more preferable. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

Further, the (meth) acrylic resin is at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid, and acrylic acid, because the effect of the present invention is more excellent. It is also preferable to have at least one selected from the group consisting of the structural unit derived from the acrylic acid alkyl ester and the structural unit derived from the acrylic acid alkyl ester.
From the viewpoint that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester is the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester. The mass ratio is preferably 60/40 to 80/20 with respect to the total content of the ester.

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

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

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

Another preferred embodiment of the binder polymer is a styrene-acrylic copolymer.
In the present specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and is a structural unit derived from the styrene compound. The total content of the structural units derived from the (meth) acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
The lower limit of the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and 20% by mass or more, based on all the structural units of the copolymer. More preferred. The upper limit is preferably 80% by mass or less, more preferably 60% by mass, and even more preferably 50% by mass or less.
The lower limit of the content of the structural unit derived from the (meth) acrylic compound is preferably 1% by mass or more, more preferably 5% by mass or more, based on 10% by mass, based on all the structural units of the copolymer. By mass or more is more preferable, and 20% by mass or more is particularly preferable. The upper limit thereof is preferably 95% by mass or less, more preferably 60% by mass, and even more preferably 30% by mass or less.

The binder polymer preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint that the effect of the present invention is more excellent.
The monomers forming the structural unit having an aromatic ring structure 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 trimmer, etc.). Of these, a monomer having an aralkyl group or styrene is preferable. Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group and the like, and a substituted or unsubstituted benzyl group 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) acrylate having a benzyl group, for example, benzyl (meth) acrylate, and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and the like. Examples include vinylbenzyl alcohol. Of these, benzyl (meth) acrylate is preferable.

Further, it is more preferable that the binder polymer has a structural unit (constituent unit derived from styrene) represented by the following formula (S) from the viewpoint that the effect of the present invention is more excellent.

When the binder polymer has a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is 5 to 90 mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. % Is preferred, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass.
Further, the content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 60 mol%, based on all the structural units of the binder polymer, from the viewpoint of further excellent effect of the present invention. Is more preferable, and 20 to 60 mol% is further preferable.
Further, the content of the structural unit represented by the above formula (S) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention. From 20 to 60 mol% is more preferable, 20 to 60 mol% is further preferable, and 20 to 50 mol% is particularly preferable.
In the present specification, when the content of the "constituent unit" is specified by the molar ratio, the above "constituent unit" shall be synonymous with the "monomer unit". Further, in the present specification, the above-mentioned "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The binder polymer preferably has an aliphatic hydrocarbon ring structure from the viewpoint that the effect of the present invention is more excellent. That is, the binder polymer preferably has a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. Above all, it is more preferable that the binder polymer has a ring structure in which two or more aliphatic hydrocarbon rings are fused.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
Among them, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable because the effect of the present invention is more excellent, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 ^2,6 ] decane) is preferable. Ring) is more preferred.
Examples of the monomer forming a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Further, the binder polymer more preferably has a structural unit represented by the following formula (Cy), and the structural unit represented by the above formula (S) and the following formula. It is more preferable to have a structural unit represented by (Cy).

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

The RM in the formula ( ^Cy ) is preferably a methyl group.
The RCy in the formula ( ^Cy ) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, and a fat having 6 to 16 carbon atoms, because the effect of the present invention is more excellent. It is more preferably a monovalent group having a group hydrocarbon ring structure, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.
Further, the aliphatic hydrocarbon ring structure in RCy of the formula ( ^Cy ) has a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or a norbornane ring structure, because the effect of the present invention is more excellent. It is preferably an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.
Further, the aliphatic hydrocarbon ring structure in RCy of the formula ( ^Cy ) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, from the viewpoint that the effect of the present invention is more excellent. It is more preferable that the ring is a condensed ring of ~ 4 aliphatic hydrocarbon rings.
Further, RCy in the formula ( ^Cy ) is a group in which the oxygen atom of —C (= O) O— in the formula (Cy) and the aliphatic hydrocarbon ring structure are directly bonded, because the effect of the present invention is more excellent. That is, it is preferably an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group.

The binder polymer may have one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.
When the binder polymer has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is higher than that of all the structural units of the binder polymer because the effect of the present invention is more excellent. 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is further preferable.
Further, the content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint that the effect of the present invention is more excellent. 60 mol% is more preferable, and 20 to 50 mol% is even more preferable.
Further, the content of the structural unit represented by the above formula (Cy) in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention. -60 mol% is more preferred, and 20-50 mol% is even more preferred.

When the binder polymer has a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is the present. From the viewpoint of further excellent effect of the invention, 10 to 90% by mass is preferable, 20 to 80% by mass is more preferable, and 40 to 75% by mass is further preferable, based on all the structural units of the binder polymer.
Further, 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 10 with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. It is preferably -80 mol%, more preferably 20-70 mol%, still more preferably 40-60 mol%.
Further, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the binder polymer is the total structural unit of the binder polymer from the viewpoint that the effect of the present invention is more excellent. On the other hand, 10 to 80 mol% is preferable, 20 to 70 mol% is more preferable, and 40 to 60 mol% is further preferable.
Further, the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the binder polymer are given by the following formulas because the effects of the present invention are more excellent. It is preferable to satisfy the relationship shown in (SCy), more preferably to satisfy the following formula (SCy-1), and further preferably to satisfy the following formula (SCy-2).
0.2 ≤ nS / (nS + nCy) ≤ 0.8 Equation (SCy)
0.30 ≤ nS / (nS + nCy) ≤ 0.75 Equation (SCy-1)
0.40 ≤ nS / (nS + nCy) ≤ 0.70 Equation (SCy-2)

The binder polymer preferably has a structural unit having an acid group because the effect of the present invention is more excellent.
Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable.
As the structural unit having the acid group, the structural unit derived from (meth) acrylic acid shown below is preferable, and the structural unit derived from methacrylic acid is more preferable.

The binder polymer may have one type of structural unit having an acid group alone or two or more types.
When the binder polymer has a structural unit having an acid group, the content of the structural unit having an acid group is 5 to 50% by mass with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. It is preferable, 5 to 40% by mass is more preferable, and 10 to 30% by mass is further preferable.
Further, the content of the constituent unit having an acid group in the binder polymer is preferably 5 to 70 mol%, preferably 10 to 50 mol%, based on all the constituent units of the binder polymer, from the viewpoint of further excellent effect of the present invention. More preferably, 20-40 mol% is even more preferable.
Further, the content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol% with respect to all the structural units of the binder polymer from the viewpoint of further excellent effect of the present invention, and is preferably 10 to 50. More preferably, mol%, more preferably 20-40 mol%.

The binder polymer preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint that the effect of the present invention is more excellent.
As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably has a structural unit having an ethylenically unsaturated group in the side chain.
In the present specification, the "main chain" represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to an atomic group branched from the main chain. show.
As the ethylenically unsaturated group, an allyl group or a (meth) acryloxy group is more preferable.
Examples of structural units having a reactive group include, but are not limited to, those shown below.

The binder polymer may have one type of structural unit having a reactive group alone or two or more types.
When the binder polymer has a structural unit having a reactive group, the lower limit of the content of the structural unit having a reactive group is set with respect to all the structural units of the binder polymer because the effect of the present invention is more excellent. 5% by mass or more is preferable, 10% by mass or more is more preferable, 20% by mass or more is further preferable, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
Further, the lower limit of the content of the structural unit having a reactive group in the binder polymer is preferably 5 mol% or more, preferably 10 mol%, based on all the structural units of the binder polymer, from the viewpoint of further improving the effect of the present invention. The above is more preferable, 20 mol% or more is further preferable, 35 mol% or more is particularly preferable, and 40 mol% or more is most preferable. The upper limit thereof is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less.

As a means for introducing a reactive group into a binder polymer, a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a blocked isocyanate are used. Examples thereof include a method of reacting a compound such as a compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
A preferred example of a means for introducing a reactive group into a binder polymer is that a polymer having a carboxy group is synthesized by a polymerization reaction and then glycidyl (meth) acrylate is added to a part of the carboxy group of the obtained polymer by the polymer reaction. Is mentioned as a means for introducing a (meth) acryloxy group into a polymer by reacting with the polymer. By this means, a binder polymer having a (meth) acryloxy group in the side chain can be obtained.
The polymerization reaction is preferably carried out under a temperature condition of 70 to 100 ° C., and more preferably carried out under a temperature condition of 80 to 90 ° C. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is more preferable. The polymer reaction is preferably carried out under temperature conditions of 80 to 110 ° C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

As the binder polymer, the polymers X1 to X4 shown below are preferable from the viewpoint that the effect of the present invention is more excellent. The content ratios (a to d) and the weight average molecular weight Mw of each structural unit shown below can be appropriately changed depending on the intended purpose, but the following configuration is particularly effective in that the effect of the present invention is more excellent. Is preferable.
(Polymer X1) a: 20 to 60% by mass, b: 10 to 50% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
(Polymer X2) a: 20 to 60% by mass, b: 10 to 50% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
(Polymer X3) a: 25 to 65% by mass, b: 1.0 to 20% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.
(Polymer X4) a: 1.0 to 20% by mass, b: 20 to 60% by mass, c: 5.0 to 25% by mass, d: 10 to 50% by mass.

Further, as the binder polymer, since the effect of the present invention is more excellent, a structural unit derived from styrene, a structural unit derived from methyl methacrylic acid, a structural unit derived from -2-hydroxyethyl methacrylate, and methacrylic acid. A polymer containing a structural unit obtained by adding glycidyl methacrylate to an acid is preferable.

Further, the binder polymer may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer X”).
The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
As the ring having a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.

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

In the formula P-1, ^RA1a represents a substituent, ^n1a ^RA1a may be the same or different, and ^Z1a is −C (= O) −OC (= O) −. Represents a divalent group forming a ring containing, and n ^1a represents an integer of 0 or more.

Examples of the substituent represented by ^RA1a include an alkyl group.
As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
When n ^1a represents an integer of 2 or more, a plurality of ^RA1a may be the same or different. Further, although a plurality of ^RA1a may be bonded to each other to form a ring, it is preferable that the RA1a are not bonded to each other to form a ring.

As the structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable. A structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or an itaconic acid anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.

Hereinafter, specific examples of the structural unit having a carboxylic acid anhydride structure will be given, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group, or CF ₃ groups, and Me represents a methyl group.

The structural unit having a carboxylic acid anhydride structure in the polymer X may be one kind alone or two or more kinds.

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

The negative photosensitive composition layer may contain only one kind of polymer X, or may contain two or more kinds of polymer X.
When the negative photosensitive composition layer contains the polymer X, the content of the polymer X is 0.1 with respect to the total mass of the negative photosensitive composition layer because the effect of the present invention is more excellent. It is preferably from 30% by mass, more preferably 0.2 to 20% by mass, still more preferably 0.5 to 20% by mass, still more preferably 1 to 20% by mass.

The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, because the effect of the present invention is more excellent. The upper limit thereof is preferably 120,000 or less, more preferably 60,000 or less, further preferably 35,000 or less, and particularly preferably 30,000 or less.

The acid value of the binder polymer is preferably 10 to 200 mgKOH / g, more preferably 60 to 200 mgKOH / g, further preferably 60 to 150 mgKOH / g, particularly preferably 70 to 1150 mgKOH / g, and most preferably 70 to 125 mgKOH / g. ..
The acid value of the binder polymer can be calculated from, for example, the average content of acid groups in the compound according to the method described in JIS K0070: 1992. The dispersity of the binder polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and 1.0 to 3 from the viewpoint of developability. .0 is particularly preferred.

As the binder polymer, in that the effect of the present invention is more excellent, the weight average molecular weight (Mw) of the binder polymer is 60,000 or less, and the proportion of the structural unit having a radically polymerizable group in the binder polymer is 20 mass. % Or more, more preferably, the weight average molecular weight (Mw) of the binder polymer is 35,000 or less, and the proportion of the structural unit having a radically polymerizable group in the binder polymer is 35% by mass or more. It is more preferable that the weight average molecular weight (Mw) of the binder polymer is 30,000 or less, and the proportion of the structural unit having a radically polymerizable group in the binder polymer is 40% by mass or more.

The negative photosensitive composition layer may contain only one kind of binder polymer, or may contain two or more kinds of binder polymers.
The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 30 to the total mass of the negative photosensitive composition layer from the viewpoint that the effect of the present invention is more excellent. 70% by mass is more preferable, and 30 to 60% by mass is further preferable.

<Polymerizable compound>
The negative photosensitive composition layer contains a polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”).
The ethylenically unsaturated compound is preferably a radically polymerizable compound. As the ethylenically unsaturated group, a (meth) acryloxy group is preferable.
The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited, but one or more is preferable, and two or more are more preferable. The upper limit is not particularly limited, but is, for example, 20 or less.
The ethylenically unsaturated compound in the present specification is a compound other than the binder polymer, and preferably has a molecular weight of less than 5,000.

As one of the preferred embodiments of the ethylenically unsaturated compound, a compound represented by the following formula (M) (simply referred to as “Compound M”) can be mentioned.
^Q2 - ^R1 - ^Q1 formula (M)
In formula (M), Q ¹ and Q ² each independently represent a (meth) acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

It is preferable that Q ^{1 and Q 2 in the formula (M) have the same group as Q 1} ^{and Q 2} ^from ^the viewpoint of ease of synthesis.
Further, Q ¹ and Q ² in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
As R ¹ in the formula (M), an alkylene group, an alkyleneoxyalkylene group (-L ¹ -OL ^1- ), or a polyalkylene oxyalkylene group (-(L)" is used because the effect of the present invention is more excellent. ¹ -O) _p -L ^1- ) is preferable, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, an alkylene group having 4 to 20 carbon atoms is further preferable, and an alkylene group having 6 to 20 carbon atoms is more preferable. Eighteen linear alkylene groups are particularly preferred.
The hydrocarbon group may have a chain structure at least partially, and the portion other than the chain structure is not particularly limited, and is, for example, a branched chain, cyclic, or having 1 to 1 to carbon atoms. It may be any of 5 linear alkylene groups, arylene groups, ether bonds, and combinations thereof, and alkylene groups or groups in which two or more alkylene groups and one or more arylene groups are combined are preferable. , The alkylene group is more preferable, and the linear alkylene group is further preferable.
The above L ¹ independently represents an alkylene group, and an ethylene group, a propylene group, or a butylene group is preferable, and an ethylene group or a 1,2-propylene group is more preferable. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

Further, the number of atoms of the shortest connecting chain connecting between ^Q1 and ^Q2 in the compound M is preferably 3 to 50, more preferably 4 to 40, from the viewpoint of further excellent effect of the present invention. 6 to 20 are more preferable, and 8 to 12 are particularly preferable.
In the present specification, "the number of atoms in the shortest connecting chain connecting between ^Q1 and ^Q2 " means the atoms in ^R1 connected to ^Q1 to the atoms in ^R1 connected to ^Q2 . The shortest number of atoms.

Specific examples of the compound M include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 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, hydrogenated Di (meth) acrylate of bisphenol A, di (meth) acrylate of hydrogenated bisphenol F, polyethylene glycol di (meth) acrylate, polypropylenelen glycol di (meth) acrylate, poly (ethylene glycol / propylene glycol) di (meth) acrylate , And polybutylene glycol di (meth) acrylate. The ester monomer can also be used as a mixture.
Among the above compounds, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, because the effect of the present invention is more excellent. It is preferably at least one compound selected from the group consisting of acrylates and neopentyl glycol di (meth) acrylates, preferably 1,6-hexanediol di (meth) acrylates and 1,9-nonanediol di (1) -nonanediol di (meth) acrylates. More preferably, it is at least one compound selected from the group consisting of a meta) acrylate and a 1,10-decanediol di (meth) acrylate, and the 1,9-nonanediol di (meth) acrylate, and More preferably, it is at least one compound selected from the group consisting of 1,10-decanediol di (meth) acrylate.

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

The bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1,4-cyclohexanediol di (meth) acrylate.

Commercially available products of bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimenanol dimethacrylate (trade name: NK ester A-DCP). Product name: NK ester DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., 1,9-nonandiol diacrylate (trade name: NK ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6 -Hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can be mentioned.

The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Examples thereof include ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerintri (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. Yes, "(tri / tetra) (meth) acrylate" is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
Examples of commercially available trifunctional ethylenically unsaturated compounds include trimethylolpropane triacrylate (“A-TMPT” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
Examples of commercially available products of the tetrafunctional ethylenically unsaturated compound include pentaerythritol tetraacrylate (“A-TMMT” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
Examples of commercially available products of 5- or hexafunctional ethylenically unsaturated compounds include dipentaerythritol polyacrylate (“A-DPH” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.). (Meta) acrylate compound alkylene oxide modified compound (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Dycel Ornex Co., Ltd. ( (Registered trademark) 135, etc.), ethoxylated glycerin triacrylate (NK ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like can also be mentioned.

Further, examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds.
Examples of the urethane (meth) acrylate include urethane di (meth) acrylate, and examples thereof include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
Further, as the urethane (meth) acrylate, a urethane (meth) acrylate having trifunctionality or higher can also be mentioned. As the lower limit of the number of functional groups, 6-functionality or more is more preferable, and 8-functionality or more is further preferable. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher functional urethane (meth) acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H. , And UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.) and the like.

One of the preferred embodiments of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group. Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxy group, and among them, a carboxy group is preferable.
As the ethylenically unsaturated compound having an acid group, a 3- to 4-functional ethylenically unsaturated compound having an acid group [pentaerythritol tri and a tetraacrylate (PETA) skeleton introduced with a carboxy group (acid value: 80 to 80). 120 mgKOH / g)], a 5- to 6-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) skeleton with a carboxy group introduced [acid value: 25 to 70 mgKOH / g)] And so on.
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

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

As the ethylenically unsaturated compound having an acid group, the compounds described in paragraphs [0025] to [0030] of JP-A-2004-239942 are also preferable, and the contents described in this publication are incorporated in the present specification.

Examples of the ethylenically unsaturated compound include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid. , Urethane monomers such as (meth) acrylate compounds with urethane bonds, γ-chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyl Examples thereof include phthalic acid compounds such as oxyethyl-o-phthalate and β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters.
These may be used alone or in combination of two or more.

Examples of the compound obtained by reacting a polyvalent alcohol with an α, β-unsaturated carboxylic acid include 2,2-bis (4-((meth) acrylamide polyethoxy) phenyl) propane and 2,2-bis. Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acrylamide polypropoxy) phenyl) propane and 2,2-bis (4-((meth) acrylamide polyethoxypolypropoxy) phenyl) propane , Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups. And, polyethylene polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate having 2 to 14 propylene oxide groups. , Trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, trimethylolpropane ) Tetra acrylate, tetramethylol methanetri (meth) acrylate, tetramethylol methanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Can be mentioned.
Among them, an ethylene unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and a tetramethylolmethanetri (meth) acrylate, a tetramethylolmethanetetra (meth) acrylate, a trimethylolpropanetri (meth) acrylate, or a trimethylolpropane tri (meth) acrylate is preferable. Di (trimethylolpropane) tetraacrylate is more preferred.

Examples of the ethylenically unsaturated compound include a caprolactone-modified compound of an ethylenically unsaturated compound (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd., etc. ), An alkylene oxide-modified compound of an ethylenically unsaturated compound (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel Ornex Co., Ltd. (Registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like can also be mentioned.

As the ethylenically unsaturated compound, those containing an ester bond are particularly preferable in that the negative photosensitive composition layer after transfer is excellent in developability.
The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but is not ethylene-free having a tetramethylolmethane structure or a trimethylolpropane structure in that the effect of the present invention is excellent. Saturated compounds are preferred, and tetramethylolmethanetri (meth) acrylates, trimethylolmethanetetra (meth) acrylates, trimethylolpropane tri (meth) acrylates, or di (trimethylolpropane) tetraacrylates are more preferred.

From the viewpoint of imparting reliability, the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylene unsaturated compound having a tetramethylol methane structure or a trimethylol propane structure. It is preferable to contain a compound.
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 tricyclodecanedimethanoldi. Examples include (meth) acrylate.

One of the preferred embodiments of the ethylenically unsaturated compound is a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure.
The aliphatic hydrocarbon ring structure is a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure). Is preferable, and a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornan structure, or an isoborone structure is preferable from the viewpoint that the effect of the present invention is more excellent.
As the bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, tricyclodecanedimethanol di (meth) acrylate is particularly preferable.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

As one of the preferred embodiments of the negative photosensitive composition layer, the negative photosensitive composition layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound and preferably contains a trifunctional or higher functional ethylenically unsaturated compound. It is more preferable to contain a tetrafunctional or higher functional ethylenically unsaturated compound in that the effect of the present invention is more excellent.

Further, as one of the preferred embodiments of the negative photosensitive composition layer, the negative photosensitive composition layer has a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an aliphatic hydrocarbon ring. It preferably contains a binder polymer having a structural unit.

Further, as one of the preferred embodiments of the negative photosensitive composition layer, the negative photosensitive composition layer contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group. , And more preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. And, it is more preferable to contain tricyclodecanedimethanol diacrylate and a succinic acid-modified form of dipentaerythritol pentaacrylate.

Further, as one of the preferred embodiments of the negative photosensitive composition layer, the negative photosensitive composition layer includes a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, which will be described later. It preferably contains a thermally crosslinkable compound, and more preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

Further, as one of the preferred embodiments of the negative photosensitive composition layer, the negative photosensitive composition layer is a bifunctional ethylenically unsaturated compound (preferably) from the viewpoint of suppressing development residue and rust resistance. Is preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher (meth) acrylate compound).
The mass ratio of the content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
The content of the bifunctional ethylenically unsaturated compound is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of all the ethylenically unsaturated compounds.
The bifunctional ethylenically unsaturated compound in the negative photosensitive composition layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.

Further, as one of the preferred embodiments of the negative photosensitive composition layer, the negative photosensitive composition layer is bifunctional ethylenically having compound M and an aliphatic hydrocarbon ring structure from the viewpoint of rust resistance. It preferably contains an unsaturated compound.
Further, as one of the preferred embodiments of the negative-type photosensitive composition layer, the negative-type photosensitive composition layer contains the compound M and an acid from the viewpoints of substrate adhesion, development residue inhibitory property, and rust resistance. It is preferable to contain an ethylenically unsaturated compound having a group, and more preferably to contain a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group. , Compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group are more preferably contained. In particular, it contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound. preferable.
Further, as one of the preferred embodiments of the negative type photosensitive composition layer, the negative type photosensitive composition layer has a negative type photosensitive composition layer, and the negative type photosensitive composition layer has substrate adhesion, development residue suppressing property, and rust resistance. From the point of view, it is preferable to contain 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and 1,9-nonandiol diacrylate, tricyclodecanedimethanol diacrylate, and , Polyfunctional ethylenically unsaturated compounds having a carboxylic acid group, preferably 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and ethylene having a carboxylic acid group. It is more preferable to contain a sex unsaturated compound, and it is particularly preferable to contain a 1,9-nonanediol diacrylate, a tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound. ..

Further, as one of the preferred embodiments of the negative photosensitive composition layer, the ratio of the content of the polymerizable compound having a molecular weight of 300 or less among the polymerizable compounds contained in the negative photosensitive composition layer is the negative photosensitive composition layer. With respect to the content of all the polymerizable compounds contained in the sex composition layer, 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.

The negative photosensitive composition layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
The content of the bifunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is 60 to 100% by mass with respect to the total content of all the ethylenically unsaturated compounds contained in the negative photosensitive composition layer. Is preferable, 80 to 100% by mass is more preferable, and 90 to 100% by mass is further preferable.

The ethylenically unsaturated compound may be used alone or in combination of two or more.
The lower limit of the content of the ethylenically unsaturated compound in the negative photosensitive composition layer is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total mass of the negative photosensitive composition layer. , 20% by mass or more is further preferable, 35% by mass or more is further preferable, and 40% by mass or more is particularly preferable. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.
Further, in the negative photosensitive composition layer, the mass content ratio of the ethylenically unsaturated compound to the binder polymer (ethylenically unsaturated compound / binder polymer) is preferably 0.4 or more, preferably 0.5 or more. Is more preferable, 0.6 or more is further preferable, 0.7 or more is particularly preferable, and 0.8 or more is most preferable. The upper limit is not particularly limited, but is preferably 1.5 or less, and more preferably 1.2 or less.

Further, the negative photosensitive composition layer may contain a polymerizable compound other than the ethylenically unsaturated compound (hereinafter, also referred to as “another polymerizable compound”).
The other polymerizable compound is a compound having a polymerizable group other than the ethylene unsaturated group. Examples of the polymerizable group other than the ethylene unsaturated group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable.
The number of polymerizable groups in the other polymerizable compounds is not particularly limited, but one or more is preferable, and two or more are more preferable. The upper limit is not particularly limited, but is, for example, 20 or less.
Further, the other polymerizable compound in the present specification is a compound other than the binder polymer, and preferably has a molecular weight of less than 5,000.

When the negative photosensitive composition layer contains other polymerizable compounds, the content of the ethylenically unsaturated compound is the total mass of the polymerizable compound (total mass of the ethylenically unsaturated compound and other polymerizable compounds). ), 60 to 100% by mass is preferable, 80 to 100% by mass is more preferable, 90 to 100% by mass is further preferable, and 95 to 100% by mass is particularly preferable.
The lower limit of the content of the polymerizable compound (total mass of the ethylenically unsaturated compound and other polymerizable compounds) in the negative photosensitive composition layer is the total mass of the polymerizable compound (ethylene unsaturated compound and 1% by mass or more is preferable, 5% by mass or more is more preferable, 20% by mass or more is further preferable, 35% by mass or more is further preferable, and 40% by mass or more is particularly preferable. preferable. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.

The transfer film of the present invention preferably contains a polyfunctional or higher functional compound in that the effect of the present invention is more excellent. The tetrafunctional or higher functional polymerizable compound is preferably a tetrafunctional or higher ethylenically unsaturated compound (a polymerizable compound having four or more ethylenically unsaturated groups).
The content of the tetrafunctional or higher-functional polymerizable compound is preferably 35% by mass or more, preferably 35% by mass or more, based on the total mass of the polymerizable compound (total mass of the ethylenically unsaturated compound and other polymerizable compounds). It is more preferably 7% by mass or more, further preferably 65% by mass or more, and particularly preferably 70% by mass or more. The upper limit value is not particularly limited, but is preferably 100% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

<Photopolymerization initiator>
The negative photosensitive composition layer contains a photopolymerization initiator. 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 “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α-”. Aminoalkylphenone-based photopolymerization initiator "), photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as" α-hydroxyalkylphenone-based polymerization initiator "), acylphosphine oxide structure. Photopolymerization initiator (hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”) and photopolymerization initiator having an N-phenylglycine structure (hereinafter, “N-phenylglycine-based photopolymerization initiator”). Also referred to as "agent").

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

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

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

The photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, an oxime-based photopolymerization initiator and at least one selected from an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator may be used. preferable.
In the negative photosensitive composition layer, the content of the photopolymerization initiator is preferably 0.1% by mass or more, preferably 0.5% by mass or more, based on the total mass of the negative photosensitive composition layer. Is more preferable, and 1.0% by mass or more is further preferable. The upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the negative photosensitive composition layer.

<Polymerization inhibitor>
In order for the transfer film of the present invention to exert the effect of the present invention, it is preferable that the negative photosensitive composition layer contains a polymerization inhibitor.
The polymerization inhibitor means a compound having a function of delaying or prohibiting a polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.

Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, and 3,7-dioctylphenothiazine; phenoxazine compounds such as phenoxazine; bis [3- (3-tert- Butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-) Di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio)- 6- (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Hindered phenolic compounds such as: 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and nitroso compounds such as N-nitrosophenylhydroxylamine or salts thereof; methylhydroquinone, t-butylhydroquinone, 2, Phenolic compounds such as 5-di-t-butylhydroquinone and 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; copper dibutyldithiocarbamate, diethyldithiocarbamine. Examples thereof include metal salt compounds such as copper acid, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate.
Further, examples of the polymerization inhibitor include thermal polymerization inhibitors, naphthylamines, cuprous chloride and the like described in paragraph 0018 of Japanese Patent No. 4502784.
Among them, the polymerization inhibitor is composed of a phenothiazine compound (phenothiazine and its derivative), a phenoxazine compound such as phenoxazine; a nitroso compound or a salt thereof, and a hindered phenol compound in that the effect of the present invention is more excellent. At least one selected from the group is preferable, and phenolthiazine, phenoxazine, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid], [ethylenebis (oxyethylene)] 2,4 -Bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, or N-nitrosophenylhydroxylamine Aluminum salts are more preferred, and phenothiazine, phenoxazine, or p-methoxyphenol is even more preferred.

The polymerization inhibitor may be used alone or in combination of two or more.
Further, in order for the transfer film of the present invention to exert the effect of the present invention, the content of the polymerization inhibitor in the negative type photosensitive composition layer is 0.10 with respect to the total mass of the negative type photosensitive composition layer. It is preferably ~ 5.0% by mass, more preferably 0.10 to 3.0% by mass, still more preferably 0.10 to 2.0% by mass.
Further, in order for the transfer film of the present invention to exert the effect of the present invention, the content of the polymerization inhibitor is preferably 5 to 15% by mass with respect to the content of the photopolymerization initiator.

The content of the polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.01 to 0.01% by mass with respect to the total mass of the polymerizable compound. 1.0% by mass is more preferable.

<Heterocyclic compound>
The negative photosensitive composition layer may contain a heterocyclic compound.
The heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic complex.
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 one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

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

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

Examples of the tetrazole compound include the following compounds.

Examples of thiadiazole compounds include the following compounds.

Examples of the triazine compound include the following compounds.

Examples of the loadonin compound include the following compounds.

Examples of the thiazole compound include the following compounds.

Examples of the benzothiazole compound include the following compounds.

Examples of the benzimidazole compound include the following compounds.

Examples of the benzoxazole compound include the following compounds.

The heterocyclic compound may be used alone or in combination of two or more.
When the negative photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, preferably 0, based on the total mass of the negative photosensitive composition layer. .10 to 10.0% by mass is more preferable, 0.30 to 8.0% by mass is further preferable, and 0.50 to 5.0% by mass is particularly preferable.

<Alphatic thiol compound>
The negative photosensitive composition layer may contain an aliphatic thiol compound.
When the negative photosensitive composition layer contains an aliphatic thiol compound, an en-thiol reaction can occur between the aliphatic thiol compound and the ethylenically unsaturated compound. As a result, the curing shrinkage of the formed film is suppressed and the stress is relieved.

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

Among the above, as the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferable from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).

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

As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, 2 to 10 functionalities are preferable, 2 to 8 functionalities are more preferable, and 2 to 6 functionalities are further preferable, from the viewpoint of adhesion of the formed pattern.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropanetris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like. 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylol ethanetris (3-mercaptobutyrate) ), Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) Pionate), Dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,2-ethanedithiol, 1, Examples thereof include 3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio) dietanethiol, meso-2,3-dimercaptosuccinic acid, and di (mercaptoethyl) ether.

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

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

The negative photosensitive composition layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.

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

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

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

Examples of the blocking agent having a dissociation temperature of 100 to 160 ° C. include an active methylene compound [malonic acid diester (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonic acid, etc.)] and an oxime compound ( Examples thereof include formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, cyclohexanone oxime and the like, which have a structure represented by -C (= N-OH) -in the molecule).
Among these, as the blocking agent having a dissociation temperature of 100 to 160 ° C., for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is easier to set the dissociation temperature in a preferable range than a compound having no oxime structure, and has less development residue. It is preferable because it is easy to do.

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 radically polymerizable group is preferable.
Examples of the polymerizable group include a (meth) acryloxy group, a (meth) acrylamide group, an ethylenically unsaturated group such as a styryl group, and a group having an epoxy group such as a glycidyl group.
Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth) acryloxy group is more preferable, and an acryloxy group is further preferable.

As the blocked isocyanate compound, a commercially available product can be used.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and blocks. Examples thereof include the Duranate series of molds (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).

The heat-crosslinkable compound may be used alone or in combination of two or more.
When the negative-type photosensitive composition layer contains a heat-crosslinkable compound, the content of the heat-crosslinkable compound is preferably 1 to 50% by mass, preferably 5 to 30% by mass, based on the total mass of the negative-type photosensitive composition layer. % By mass is more preferred.

<Surfactant>
The negative photosensitive composition layer may contain a surfactant.
Examples of the surfactant include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.

As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable.
Commercially available products of fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F -558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS -586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72 -K, DS-21 (above, manufactured by DIC Co., Ltd.), Fluorard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC -105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Co., Ltd.), FluorFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Fluorine 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Co., Ltd.) And so on.
Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cut off and the fluorine atom volatilizes. Can also be suitably used. Examples of such fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
Further, as the fluorine-based surfactant, it is also preferable to use a polymer 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.
Further, as the fluorine-based surfactant, a block polymer can also be used.
Further, the fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). A fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound can also be preferably used.
Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Examples thereof include Megafuck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like.

As the fluorine-based surfactant, from the viewpoint of improving environmental suitability, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), may be used. It is preferably a surfactant derived from an alternative material.
Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and the like. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic® L10, L31, L61, L62, 10R5, 17R2 , 25R2 (above, manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (above, manufactured by BASF), Solsparse 20000 (above, manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW -1001, NCW-1002 (above, manufactured by Fujifilm Wako Junyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (above, manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.

Specific examples of the surfactant include DOWSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (above, Toray Dow). (Made by Corning Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF- 643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445 , TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (above, manufactured by Big Chemie) and the like.

The surfactant may be used alone or in combination of two or more.
When the negative photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, preferably 0, based on the total mass of the negative photosensitive composition layer. 0.01 to 1.0% by mass is more preferable, and 0.05 to 0.80% by mass is further preferable.

<Hydrogen donating compound>
The negative photosensitive composition layer may contain a hydrogen donating compound.
The hydrogen donating compound has an action of further improving the sensitivity of the photopolymerization initiator to active light rays and suppressing the inhibition of the polymerization of the polymerizable compound by oxygen.

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

Examples of amines include M.I. R. "Journal of Polymer Society" by Sander et al., Vol. 10, pp. 3173 (1972), JP-A-44-020189, JP-A-51-081022, JP-A-52-134692, JP-A-59-138205. Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 60-0843305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, and Research Disclosure No. 33825. More specifically, 4,4'-bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (also known as leucocrystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl. Examples thereof include dimethylaniline and p-methylthiodimethylaniline.
Among them, at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane is used as amines because the effect of the present invention is more excellent. preferable.

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 because the effect of the present invention is more excellent.

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. 55-0344414, and JP-A-6. Sulfur compounds (Tritian and the like) described in JP-A-308727 can also be mentioned.

The hydrogen donating compound may be used alone or in combination of two or more.
When the negative photosensitive composition layer contains a hydrogen donating compound, the content of the hydrogen donating compound is such that the curing rate is improved by the balance between the polymerization growth rate and the chain transfer. 0.01 to 10.0% by mass is preferable, 0.01 to 8.0% by mass is more preferable, and 0.03 to 5.0% by mass is further preferable, based on the total mass of the above.

<Impurities, etc.>
The negative photosensitive composition layer may contain a predetermined amount of impurities.
Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed as impurities, so the following content is preferable.

The content of impurities in the negative photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis. The content of impurities in the negative photosensitive composition layer can be 1 ppb or more or 0.1 ppm or more on a mass basis.

As a method of setting impurities in the above range, a material having a low impurity content is selected as a raw material for the negative photosensitive composition layer, and contamination of the negative photosensitive composition layer is prevented during formation of the negative photosensitive composition layer. , Cleaning and removal. By such a method, the amount of impurities can be kept within the above range.

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

Content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the negative photosensitive composition layer. Is preferably less. The content of these compounds in the negative photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis. The lower limit is based on mass and can be 10 ppb or more, and can be 100 ppb or more. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.

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

<Residual monomer>
The negative photosensitive composition layer may contain residual monomers of each structural unit of the binder polymer (eg, alkali-soluble resin) described above.
The content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less with respect to the total mass of the binder polymer from the viewpoint of patterning property and reliability. Is more preferable. The lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable.
The residual monomer of each structural unit of the binder polymer is preferably 3,000 mass ppm or less, preferably 600 mass ppm or less, based on the total mass of the negative photosensitive composition layer from the viewpoint of patterning property and reliability. More preferably, 100 mass ppm or less is further preferable. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

The amount of residual monomer of the monomer when synthesizing the binder polymer by the polymer reaction is also preferably in the above range. For example, when glycidyl acrylate is reacted with the carboxylic acid side chain to synthesize a binder polymer, the content of glycidyl acrylate is preferably in the above range.
The amount of the residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
The amount of the residual monomer can be reduced by purifying the binder polymer by a method such as reprecipitation.

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

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

When the negative photosensitive composition layer contains particles, it may contain only one kind of particles having different metal species and sizes, or two or more kinds.
The negative photosensitive composition layer does not contain particles, or when the negative photosensitive composition layer contains particles, the content of the particles is relative to the total mass of the negative photosensitive composition layer. , 0% by mass and 35% by mass or less, and more preferably 0% by mass or more and 10% by mass or less with respect to the total mass of the negative photosensitive composition layer, which does not contain particles or contains particles. , Particles are not contained, or the content of the particles is more preferably more than 0% by mass and 5% by mass or less with respect to the total mass of the negative photosensitive composition layer, and the particles are not contained or the particles are contained. The amount is more preferably more than 0% by mass and 1% by mass or less with respect to the total mass of the negative photosensitive composition layer, and it is particularly preferable that the amount does not contain particles.

-Colorant-
The negative photosensitive composition layer may contain a trace amount of a colorant (pigment, dye, etc.), but for example, from the viewpoint of transparency, it is preferable that the layer does not contain a colorant substantially.
When the negative photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the negative photosensitive composition layer. preferable.

-Antioxidant-
Examples of the antioxidant include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-. 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
Among them, 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant because the effect of the present invention is more excellent.

When the negative photosensitive composition layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, preferably 0.005% by mass, based on the total mass of the negative photosensitive composition layer. % Or more is more preferable, and 0.01% by mass or more is further preferable. The upper limit is not particularly limited, but is preferably 1% by mass or less.

<Thickness of negative photosensitive composition layer>
The thickness of the negative photosensitive composition layer is not particularly limited, but is often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, in that the effect of the present invention is more excellent. 9.0 μm or less is particularly preferable. As the lower limit, 0.60 μm or more is preferable, and 1.5 μm or more is more preferable, because the strength of the film obtained by curing the negative photosensitive composition layer is excellent.
The thickness of the negative photosensitive composition layer can be calculated as, for example, an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).

<Refractive index of negative photosensitive composition layer>
The refractive index of the negative photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

<Color of negative photosensitive composition layer>
The negative photosensitive composition layer is preferably achromatic. Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field)) has an L ^* value of 10 to 90 in the CIE1976 (L *, a *, b *) color space. The a ^* value is preferably −1.0 to 1.0, and the b ^* value is preferably −1.0 to 1.0.

The pattern (cured film of the negative photosensitive composition layer) obtained by curing the negative photosensitive composition layer is preferably achromatic.
Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field)) has a pattern L ^* value of 10 to 90 in the CIE1976 (L *, a *, b *) color space. The a ^* value of the pattern is preferably −1.0 to 1.0, and the b ^* value of the pattern is preferably −1.0 to 1.0.

<Humidity permeability of negative photosensitive composition layer>
The moisture permeability of the pattern (cured film of the negative photosensitive composition layer) obtained by curing the negative photosensitive composition layer at a film thickness of 40 μm is 500 g / m ^2/24 hr or less from the viewpoint of rust prevention. It is preferably 300 g / m ^2/24 hr or less, and even more preferably 100 g / m ^2/24 hr or less.
The moisture permeability is determined by exposing the negative photosensitive composition layer with an i-line at an exposure amount of 300 mJ / cm ² and then post-baking at 145 ° C. for 30 minutes to obtain a negative photosensitive composition layer. Is measured with a cured film.

<Dissolution rate of negative photosensitive composition layer>
The dissolution rate of the negative photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and 0. 20 μm / sec or more is more preferable. From the viewpoint of the edge shape of the pattern, 5.0 μm / sec or less is preferable, 4.0 μm / sec or less is more preferable, and 3.0 μm / sec or less is further preferable. Specific preferable numerical values are, for example, 1.0 μm / sec, 0.8 μm / sec and the like. The dissolution rate of the negative photosensitive composition layer in a 1.0 mass% sodium carbonate aqueous solution per unit time shall be measured as follows.
A negative-type photosensitive composition layer (within a film thickness of 1.0 to 10 μm) formed on a glass substrate from which the solvent has been sufficiently removed is subjected to a negative solution using a 1.0 mass% sodium carbonate aqueous solution at 25 ° C. Shower development is performed until the type photosensitive composition layer is completely melted (however, the maximum is 2 minutes).
It is obtained by dividing the film thickness of the negative photosensitive composition layer by the time required for the negative photosensitive composition layer to melt completely. If it does not melt completely in 2 minutes, calculate in the same way from the amount of change in film thickness up to that point. A shower nozzle of 1/4 MINJJX030PP manufactured by Ikeuchi Co., Ltd. is used, and the shower pressure is 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1,800 mL / min.

<Foreign matter in the negative photosensitive composition layer>
From the viewpoint of pattern formation, the number of foreign substances having a diameter of 1.0 μm or more in the negative photosensitive composition layer is preferably 10 pieces / mm ² or less, and more preferably 5 pieces / mm ² or less. preferable. The number of foreign substances shall be measured as follows. From the normal direction of the surface of the negative photosensitive composition layer, any five regions (1 mm × 1 mm) on the surface of the negative photosensitive composition layer are visually observed using an optical microscope. Then, the number of foreign substances having a diameter of 1.0 μm or more in each region is measured, and they are arithmetically averaged to calculate the number of foreign substances.

<< 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 a polyolefin film such as a polypropylene film and a polyethylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film. Be done.
Further, as the protective film, a resin film made of the same material as the above-mentioned temporary support may be used.
Among them, 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 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.
The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and preferably 100 μm or less in terms of relatively low cost.

Further, in the protective film, it is preferable that the number of fish eyes having a diameter of 80 μm or more contained in the protective film is 5 / m ² or less.
The term "fish eye" refers to foreign substances, undissolved substances, oxidative deterioration substances, etc. of the material when the material is thermally melted, kneaded, extruded, and used to produce a film by a biaxial stretching method, a casting method, or the like. Was incorporated into the film.

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

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

<< Preferable relationship between temporary support, negative photosensitive composition layer, and protective film >>
As for the transfer film, it is preferable that the physical characteristics of the temporary support, the negative photosensitive composition layer, and the protective film show the following aspects.
The transfer film preferably satisfies one or more of preferred embodiments 1, preferred embodiments 2, preferred embodiments 3, preferred embodiments 4, and preferred embodiments 5, and more preferably all of them.

"Breaking elongation of the cured film obtained by curing the negative photosensitive composition layer" is performed by exposing the negative photosensitive composition layer having a thickness of 20 μm to 120 mJ / cm ² with an ultrahigh pressure mercury lamp and curing it, and then using a high pressure mercury lamp. The cured film after further exposure at 400 mJ / cm ² and heated at 145 ° C. for 30 minutes is measured by a tensile test.
The "arithmetic mean roughness Ra of the surface of the temporary support on the negative photosensitive composition layer side" can be measured by the following method. Using a three-dimensional optical profiler (New View7300, Zygo), a surface profile of the object to be measured is obtained under the following conditions. As the measurement and analysis software, Microscope Application of MetroPro ver8.3.2 is used. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the object to be measured is obtained.
The method for measuring the "arithmetic mean roughness Ra of the surface of the protective film on the negative photosensitive composition layer side" is the measurement of the "arithmetic mean roughness Ra of the surface of the temporary support on the negative photosensitive composition layer side". It is carried out in the same way as the method.

... preferred embodiment 1
It is preferable that the physical characteristics of the temporary support, the negative photosensitive composition layer, and the protective film of the transfer film 1 satisfy all of the following conditions (P1) to (P3).
(P1) The breaking elongation of the cured film obtained by curing the negative photosensitive composition layer at 120 ° C. is 15% or more.
(P2) The arithmetic mean roughness Ra of the surface of the temporary support on the negative photosensitive composition layer side is 50 nm or less.
(P3) The arithmetic mean roughness Ra of the surface of the protective film on the negative photosensitive composition layer side is 150 nm or less.

... preferred embodiment 2
The physical characteristics of the temporary support of the transfer film 1 and the negative photosensitive composition layer preferably satisfy the following formula (1).
X × Y <1500 formula (1)
Here, in the formula (1), X represents the value (%) of the elongation at break at 120 ° C. of the cured film obtained by curing the negative photosensitive composition layer, and Y represents the negative photosensitive composition of the temporary support. It represents the value (nm) of the arithmetic mean roughness Ra of the surface on the material layer side.
In the above formula (1), the value represented by X × Y is preferably 750 or less.

... preferred embodiment 3
The photosensitive physical properties of the transfer film 1 preferably satisfy the following condition (P4).
(P4) The breaking elongation at 120 ° C. is more than twice as large as the breaking elongation at 23 ° C. of the cured film obtained by curing the negative photosensitive composition layer.

... preferred embodiment 4
The physical characteristics of the temporary support of the transfer film 1 and the negative photosensitive composition layer preferably satisfy the following formula (2).
Y ≤ Z formula (2)
Here, in the formula (2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the surface of the temporary support on the negative photosensitive composition layer side, and Z represents the negative photosensitive of the protective film. It represents the value (nm) of the arithmetic mean roughness Ra of the surface on the composition layer side.

<< Refractive index adjustment layer >>
The transfer film preferably has a refractive index adjusting layer.
As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjusting layer include a binder polymer, a polymerizable compound, a metal salt, and particles.
The method for controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method using a resin having a predetermined refractive index alone, a method using a resin and particles, and a composite of a metal salt and a resin are used. Is mentioned.

Examples of the binder polymer and the polymerizable compound include the binder polymer and the polymerizable compound described in the section of the above-mentioned "negative photosensitive composition layer".

Examples of the particles include metal oxide particles and metal particles.
The type of the metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles. The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

The average primary particle size of the particles is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency of the cured film.
The average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.

Specific examples of the metal oxide particles include zirconium oxide particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles), silicon dioxide particles (SiO ₂ particles), and a composite thereof. At least one selected from the group consisting of particles is preferred.
Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable because the refractive index can be easily adjusted.

Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F74). Fired Zirconium Oxide Particles (CIK Nanotech Co., Ltd., Product Name: ZRPGM15WT% -F75), Fired Zirconium Oxide Particles (CIK Nanotech Co., Ltd., Product Name: ZRPGM15WT% -F76), Zirconium Oxide Particles (Nano Youth OZ-S30M, Nissan) Examples include (manufactured by Chemical Industry Co., Ltd.) and zirconium oxide particles (Nano Youth OZ-S30K, manufactured by Nissan Chemical Industry Co., Ltd.).

The particles may be used alone or in combination of two or more.
The content of the particles in the refractive index adjusting layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, still more preferably 40 to 85% by mass, based on the total mass of the refractive index adjusting layer.
When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and 40 to 85% by mass with respect to the total mass of the refractive index adjusting layer. % Is more preferable.

The refractive index of the refractive index adjusting layer is preferably higher than that of the negative photosensitive composition layer.
The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and even more preferably 1.78 or less.
The refractive index is a refractive index having a wavelength of 550 nm at 25 ° C.

The thickness of the refractive index adjusting layer is preferably 50 to 500 nm, more preferably 55 to 110 nm, and even more preferably 60 to 100 nm.
The thickness of the refractive index adjusting layer is calculated as an average value of any five points measured by cross-sectional observation with a scanning electron microscope (SEM).

<< Method for Producing Transfer Film of First Embodiment >>
The method for producing the transfer film of the first embodiment is not particularly limited, and a known method can be used.
As a method for producing the transfer film 10, for example, a negative-type photosensitive composition layer-forming composition is applied to the surface of the temporary support 1 to form a coating film, and the coating film is further dried to make a negative. The step of forming the mold photosensitive composition layer 3 and the composition for forming a refractive index adjusting layer are applied to the surface of the negative photosensitive composition layer 3 to form a coating film, and the coating film is further dried. A method including a step of forming the refractive index adjusting layer 5 and a method including the step of forming the refractive index adjusting layer 5 can be mentioned.

The transfer film 10 is manufactured by crimping the protective film 7 onto the refractive index adjusting layer 5 of the laminate manufactured by the above-mentioned manufacturing method.
The method for producing the transfer film of the first embodiment includes a step of providing the protective film 7 so as to be in contact with the surface of the refractive index adjusting layer 5 opposite to the side having the temporary support 1. 1. It is preferable to manufacture a transfer film 10 including a negative photosensitive composition layer 3, a refractive index adjusting layer 5, and a protective film 7.
After the transfer film 10 is manufactured by the above-mentioned manufacturing method, the transfer film 10 may be wound up to prepare and store the transfer film in the form of a roll. The roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.

The method for producing the transfer film 10 is to form the refractive index adjusting layer 5 on the protective film 7 and then form the negative photosensitive composition layer 3 on the surface of the refractive index adjusting layer 5. There may be.
Further, as a method for producing the transfer film 10, the negative type photosensitive composition layer 3 is formed on the temporary support 1, and the refractive index adjusting layer 5 is separately formed on the protective film 7, and the negative type photosensitive is formed. A method may be used in which the refractive index adjusting layer 5 is bonded to the sex composition layer 3.

<Composition for forming a negative photosensitive composition layer and a method for forming a negative photosensitive composition layer>
In terms of excellent productivity, the negative photosensitive composition layer in the transfer film has components (for example, a binder polymer, an ethylenically unsaturated compound, and photopolymerization initiation) constituting the negative photosensitive composition layer described above. It is desirable that the film is formed by a coating method using a composition for forming a negative photosensitive composition layer containing an agent, etc.) and a solvent. Specifically, as a method for producing a transfer film of the first embodiment, a composition for forming a negative photosensitive composition layer is applied onto a temporary support to form a coating film, and the coating film is dried. Is preferable in this method to form a negative photosensitive composition layer.

An organic solvent is preferable as the solvent that can be contained in the composition for forming the negative photosensitive composition layer. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , N-Propanol, and 2-Propanol.

Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250 ° C. can be used, if necessary.

The solvent may be used alone or in combination of two or more.
The total solid content of the negative-type photosensitive composition layer-forming composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, based on the total mass of the negative-type photosensitive composition layer-forming composition. It is preferable, and 5 to 30% by mass is more preferable.
That is, the content of the solvent in the composition for forming the negative photosensitive composition layer is preferably 20 to 95% by mass, preferably 60 to 95% by mass, based on the total mass of the composition for forming the negative photosensitive composition layer. 95% by mass is more preferable, and 70 to 95% by mass is further preferable.

The viscosity of the composition for forming a negative photosensitive composition layer at 25 ° C. is, for example, preferably 1 to 50 mPa · s, more preferably 2 to 40 mPa · s, and further preferably 3 to 30 mPa · s from the viewpoint of coatability. preferable. Viscosity is measured using a viscometer. As the viscometer, for example, a viscometer manufactured by Toki Sangyo Co., Ltd. (trade name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

The surface tension of the negative photosensitive composition layer forming composition at 25 ° C. is, for example, preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and 15 to 40 mN / m from the viewpoint of coatability. More preferred. Surface tension is measured using a tensiometer. As the surface tension meter, for example, a surface tension meter manufactured by Kyowa Interface Science Co., Ltd. (trade name: Acoustic Surface Tensiometer CBVP-Z) can be preferably used. However, the tensiometer is not limited to the above-mentioned tensiometer.

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

As a method for drying the coating film of the negative photosensitive composition layer forming composition, heat drying and vacuum drying are preferable. In addition, in this specification, "drying" means removing at least a part of the solvent contained in a composition. Examples of the drying method include natural drying, heat drying, and vacuum drying. The above methods can be applied alone or in combination.
The drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher. The upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

<Composition for forming a refractive index adjusting layer and a method for forming the refractive index adjusting layer>
The composition for forming the refractive index adjusting layer preferably contains various components forming the above-mentioned refractive index adjusting layer and a solvent. In the composition for forming a refractive index adjusting 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 refractive index adjusting layer described above. be.
The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, with water or water. A mixed solvent with a water-miscible organic solvent is more preferable.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
The solvent may be used alone or in combination of two or more.
The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

The method for forming the refractive index adjusting layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) can be used. Can be mentioned.

Further, the transfer film of the first embodiment can be manufactured by adhering the protective film to the refractive index adjusting layer.
The method of attaching the protective film to the refractive index adjusting layer is not particularly limited, and known methods can be mentioned.
Examples of the device for adhering the protective film to the refractive index adjusting layer include a vacuum laminator and a known laminator such as an auto-cut laminator.
It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.

[Transfer film of the second embodiment]
Hereinafter, an example of the embodiment of the transfer film of the second embodiment will be described.
The transfer film 20 shown in FIG. 8 includes a temporary support 11, a composition layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a negative photosensitive composition layer 17, and a protective film 19 in this order. Have.
The transfer film 20 shown in FIG. 8 has a form in which the protective film 19 is arranged, but the protective film 19 may not be arranged.
Further, the transfer film 20 shown in FIG. 8 has a form in which the thermoplastic resin layer 13 and the intermediate layer 15 are arranged, but the thermoplastic resin layer 13 and the intermediate layer 15 may not be arranged.
Hereinafter, each element constituting the transfer film will be described.
In the transfer film of the second embodiment, examples of the temporary support 11 and the protective film 17 are the same as those of the temporary support 1 and the protective film 9 of the first embodiment described above, and the preferred embodiments are also the same.

<< Negative Photosensitive Composition Layer >>
In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. Etc. are provided inside the touch panel. Generally, for forming a patterned layer, a negative photosensitive composition layer is provided on a substrate using a transfer film or the like, and a mask having a desired pattern for the negative photosensitive composition layer is used. A method of developing after exposure is widely adopted. In the negative photosensitive composition layer, the exposed portion becomes a cured film due to exposure, and the solubility in a developing solution is lowered.

The negative photosensitive composition layer contains a binder polymer, a polymerizable compound having an ethylenically unsaturated group (ethylenically unsaturated compound), and a photopolymerization initiator. Further, it is also preferable that the binder polymer contains an alkali-soluble resin (polymer A or the like which is an alkali-soluble resin) as a part or the whole thereof.
That is, in one embodiment, the negative photosensitive composition layer preferably contains a binder polymer containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator. Such a negative photosensitive composition layer has a binder polymer: 10 to 90% by mass; an ethylenically unsaturated compound: 5 to 70% by mass; photopolymerization initiation, based on the total mass of the negative photosensitive composition layer. Agent: It is preferable to contain 0.01 to 20% by mass.
Hereinafter, each component will be described in order.

<Polymer A (resin)>
The negative photosensitive composition layer preferably contains the polymer A as the binder polymer.
The polymer A is preferably an alkali-soluble resin.
The acid value of the polymer A is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, from the viewpoint of more excellent resolution by suppressing the swelling of the negative photosensitive composition layer due to the developing solution. More preferably less than 190 mgKOH / g.
The lower limit of the acid value of the polymer A is not particularly limited, but 60 mgKOH / g or more is preferable. In terms of more excellent developability, 120 mgKOH / g or more is more preferable, 150 mgKOH / g or more is further preferable, and 170 mgKOH / g or more is particularly preferable.

The acid value (mgKOH / g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be calculated from the average content of acid groups in the compound, for example, according to the method described in JIS K0070: 1992.
The acid value of the polymer A may be adjusted according to the type of the structural unit constituting the polymer A and the content of the structural unit containing the acid group.

The weight average molecular weight of the polymer A is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, further preferably 60,000 or less, particularly preferably 35,000 or less, and most preferably 30,000 or less.
On the other hand, when the weight average molecular weight is 5,000 or more, the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property when the negative photosensitive resin laminate is used. Is preferable. The weight average molecular weight is more preferably 10,000 or more. The edge fuse property refers to the degree of ease with which the negative photosensitive composition layer protrudes from the end face of the roll when it is wound into a roll as a negative photosensitive resin laminate. The cut chip property refers to the degree of ease of chip flying when the unexposed film is cut with a cutter. When this chip adheres to the upper surface of the negative photosensitive resin laminate or the like, it is transferred to the mask in a later exposure process or the like, which causes a defective product. The dispersity of the polymer A 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 degree of dispersion is intended to be the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight). The weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography.

From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is deviated during exposure, the polymer A preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer A. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. When a plurality of types of the polymer A are contained, it is preferable that the average value of the content of the structural unit based on the monomer having an aromatic hydrocarbon group is 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-vinyl benzoic acid). Acids, styrene dimers, styrene trimers, etc.). Of these, a monomer having an aralkyl group or styrene is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content of the structural unit based on styrene is 20 to 70% by mass with respect to the total mass of the polymer A. Is preferable, 25 to 65% by mass is more preferable, 30 to 60% by mass is further preferable, and 30 to 55% by mass is particularly preferable. When the negative photosensitive composition layer contains a plurality of types of polymers A, the content of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.

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

Examples of the monomer having a benzyl group include (meth) acrylate having a benzyl group, for example, benzyl (meth) acrylate, and chlorobenzyl (meth) acrylate; a vinyl monomer having a benzyl group, for example, vinylbenzyl chloride, and the like. Examples include vinylbenzyl alcohol. Of these, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth) acrylate, the content of the structural unit based on the benzyl (meth) acrylate is the total mass of the polymer A. On the other hand, 25 to 95% by mass is preferable, 50 to 95% by mass is more preferable, 60 to 90% by mass is further preferable, 70 to 90% by mass is particularly preferable, and 75 to 90% by mass is most preferable.

The polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, at least one of the first monomers described later, and / or described below. It is preferably obtained by polymerizing with at least one of the second monomers.

The polymer A containing no structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and is preferably the first single amount. It is more preferable to obtain it by copolymerizing at least one kind of the body and at least one kind of the second monomer described later.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid anhydride, maleic acid semi-ester and the like. .. Among these, (meth) acrylic acid is preferable.
The content of the structural unit based on the first monomer in the polymer A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 30% by mass with respect to the total mass of the polymer A. % Is more preferable.
It is preferable that the content is 5% by mass or more from the viewpoint of developing good developability and controlling edge fuseability. It is preferable that the content is 50% by mass or less from the viewpoint of high resolution of the resist pattern and the shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, cyclohexyl (meth) acrylates, and (meth) acrylates such as 2-ethylhexyl (meth) acrylates; acetic acid. Examples thereof include esters of vinyl alcohols such as vinyl; and (meth) acrylonitrile. Of these, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
The content of the structural unit based on the second monomer in the polymer A is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 15% by mass or more, based on the total mass of the polymer A. It is preferable, and 17% by mass or more is particularly preferable. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less.
As one aspect of the content of the structural unit based on the second monomer in the polymer A, 1 to 60% by mass is preferable, 5 to 60% by mass is more preferable, 15 to 50% by mass is further preferable, and 17 ~ 45% by mass is particularly preferable.

When the polymer A contains a monomer-based structural unit having an aralkyl group and / or a styrene-based monomer-based structural unit, it suppresses line width thickening and deterioration of resolution when the focal position shifts during exposure. It is preferable from the viewpoint of For example, a copolymer containing a methacrylic acid-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene-based constituent unit, a methacrylic acid-based constituent unit, a methyl methacrylate-based constituent unit, a benzyl methacrylate-based constituent unit, and a styrene. A copolymer or the like containing a structural unit based on the above is preferable.
In one embodiment, the polymer A has 25 to 55% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of a structural unit based on the first monomer, and a second. It is preferably a polymer containing 15 to 45% by mass of a constituent unit based on a monomer. In another embodiment, the polymer contains 70 to 90% by mass of a structural unit based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of a structural unit based on the first monomer. Is preferable. In another embodiment, the structural unit based on the monomer having an aromatic hydrocarbon group is 25 to 70% by mass, the structural unit based on the first monomer is 15 to 25% by mass, and the second unit amount. It is preferably a polymer containing 1 to 5% by mass of a body-based structural unit.

The polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain. By using a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. .. The group having an alicyclic structure may be a monocyclic ring or a polycyclic ring.
Specific examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and (. Isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate. And so on. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate or tert-butyl methacrylate are more preferable.
Specific examples of the monomer having a group having an alicyclic structure in the 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 can be mentioned. More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth). -3-Methyl-1-adamantyl acrylate, -3,5-dimethyl-1-adamantyl (meth) acrylate, -3-ethyladamantyl (meth) acrylate, -3-methyl-5-methyl (meth) acrylate Ethyl-1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2 -Methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-mentanoindene (meth) acrylate-5- Il, Octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, -1-mentyl (meth) acrylate, tricyclodecane (meth) acrylate, -3-hydroxy- (meth) acrylate 2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl, (meth) acrylic Examples thereof include acid (nor) bornyl, (meth) acrylate isobornyl, (meth) acrylate fentyl, (meth) acrylate-2,2,5-trimethylcyclohexyl, and (meth) acrylate cyclohexyl. Among these (meth) acrylic acid esters, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid -2-adamantyl, fentyl (meth) acrylate, 1-mentyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferred, cyclohexyl (meth) acrylate, (nor) bornyl, (meth) acrylate, Isobornyl (meth) acrylate, -2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate are more preferred.

As an example of a preferred embodiment of the polymer A, the polymer A preferably has a reactive group, and more preferably has a structural unit having a reactive group.
As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. When the polymer A has an ethylenically unsaturated group, the polymer A preferably has a structural unit having an ethylenically unsaturated group in the side chain.
As the ethylenically unsaturated group, an allyl group or a (meth) acryloxy group is more preferable.

The polymer A may have one type of structural unit having a reactive group alone or two or more types.
When the polymer A has a structural unit having a reactive group, the lower limit of the content of the structural unit having a reactive group is set with respect to all the structural units of the polymer A from the viewpoint that the effect of the present invention is more excellent. 5% by mass or more is preferable, 10% by mass or more is more preferable, 20% by mass or more is further preferable, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less.
Further, the lower limit of the content of the structural unit having a reactive group in the polymer A is preferably 5 mol% or more with respect to all the structural units of the polymer A from the viewpoint that the effect of the present invention is more excellent. More preferably, it is more preferably mol% or more, further preferably 20 mol% or more, particularly preferably 35 mol% or more, and most preferably 40 mol% or more. The upper limit thereof is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less.

The polymer A, which is a binder polymer, has a weight average molecular weight (Mw) of 60,000 or less and has a radical polymerizable group in the polymer A in that the effect of the present invention is more excellent. The ratio of the structural units is preferably 20% by mass or more, the weight average molecular weight (Mw) of the polymer A is 35,000 or less, and the ratio of the structural units having radical polymerizable groups in the polymer A is It is more preferably 35% by mass or more, the weight average molecular weight (Mw) of the polymer A is 30,000 or less, and the proportion of the structural unit having a radical polymerizable group in the polymer A is 40% by mass or more. Is more preferable.

The polymer A may be used alone or in combination of two or more.
When two or more kinds are used, two kinds of polymer A containing a structural unit based on a monomer having an aromatic hydrocarbon group may be mixed and used, or based on a monomer having an aromatic hydrocarbon group. It is preferable to use a mixture of the polymer A containing a structural unit and the polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group. In the latter case, the ratio of the polymer A containing the structural unit based on the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total mass of the polymer A. More preferably, 80% by mass or more is preferable, and 90% by mass or more is more preferable.

In the synthesis of the polymer A, a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is prepared by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol. Is preferably added in an appropriate amount and heated and stirred. In some cases, a part of the mixture is added dropwise to the reaction solution for synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The glass transition temperature Tg of the polymer A is preferably 30 to 135 ° C. By using the polymer A having a Tg of 135 ° C. or lower, it is possible to suppress the line width thickening and the deterioration of the resolution when the focal position at the time of exposure is deviated. From this viewpoint, the Tg of the polymer A is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. Further, it is preferable to use the polymer A having a Tg of 30 ° C. or higher from the viewpoint of improving the edge fuse resistance. From this viewpoint, the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.

As the polymer A, the alkali-soluble resin described in the description of the thermoplastic resin layer described later may be used.

The negative photosensitive composition layer may contain a resin other than the above as the polymer A.
Other resins include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, and poly. Examples thereof include benzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

In order to achieve the effect of the invention, it is preferable that the polymer A is purified by reprecipitation. By purifying the polymer A by reprecipitation, the amount of residual monomers can be reduced. As a result, it is difficult to form a half-exposed portion.

The content of the polymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and even more preferably 40 to 40% by mass, based on the total mass of the negative photosensitive composition layer. 60% by mass is particularly preferable. It is preferable that the content of the polymer A is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content of the polymer A is 10% by mass or more from the viewpoint of improving the edge fuse resistance.

<Polymerizable compound>
The negative photosensitive composition layer contains a polymerizable compound.
Here, the polymerizable compound is a compound other than the above-mentioned polymer A, and preferably has a molecular weight of less than 5,000.
The negative photosensitive composition layer contains a polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as “ethylenically unsaturated compound”) as a polymerizable compound.
The ethylenically unsaturated compound is preferably a radically polymerizable compound. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) acryloyl group, a styryl group, a maleimide group and the like, and a (meth) acryloyl group is preferable.
The number of ethylenically unsaturated groups in the ethylenically unsaturated compound is not particularly limited, but one or more is preferable, and two or more are more preferable. The upper limit is not particularly limited, but is, for example, 20 or less.

As the ethylenically unsaturated compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferable in that the photosensitivity of the negative photosensitive composition layer is more excellent, and the ethylenically unsaturated compound is contained in one molecule. A compound having two or more ethylenically unsaturated groups (polyfunctional ethylenically unsaturated compound) is more preferable.
Further, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less in terms of excellent resolution and peelability. More preferred.

Bifunctional or trifunctional ethylenically having two or three ethylenically unsaturated groups in one molecule in that the balance between photosensitivity, resolution and releasability of the negative photosensitive composition layer is better. It is preferable to contain an unsaturated compound, and more preferably to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.
The content of the bifunctional ethylenically unsaturated compound in the negative photosensitive composition layer with respect to the total mass of the polymerizable compound is 20 from the viewpoint of excellent peelability with respect to the total mass of the negative photosensitive composition layer. By mass or more is preferable, more than 40% by mass is more preferable, and 55% by mass or more is further preferable. The upper limit is not particularly limited and may be 100% by mass. That is, all the polymerizable compounds may be bifunctional ethylenically unsaturated compounds.
As the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.

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

The mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound in the negative photosensitive composition layer is preferably 40% or more, more preferably 50% by mass or more, from the viewpoint of better resolution. , 55% by mass or more is more preferable, and 60% by mass or more is particularly preferable. The upper limit is not particularly limited, but from the viewpoint of peelability, for example, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less. preferable.

Examples of the aromatic ring contained in the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring. Heterocycles and fused rings thereof are mentioned, and aromatic hydrocarbon rings are preferable, and benzene rings are more preferable. The aromatic ring may have a substituent.
The polymerizable compound B1 may have only one aromatic ring or may have two or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the negative photosensitive composition layer due to the developing solution.
Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and a bisphenol derived from bisphenol F (2,2-bis (4-hydroxyphenyl) methane). Examples thereof include an F structure and a bisphenol B structure derived from bisphenol B (2,2-bis (4-hydroxyphenyl) butane), and a bisphenol A structure is preferable.

Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.
Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.
The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated in the present specification.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
Examples of the 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.). , 2,2-Bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) , 2,2-Bis (4- (methacryloxidedecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane ( BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10) bisphenol A Diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can be mentioned.

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

In the general formula B1, R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, respectively. A represents C ₂ H ₄ . B represents C ₃ H ₆ . n1 and n3 are independently integers of 1 to 39, and n1 + n3 are integers of 2 to 40. n2 and n4 are independently integers of 0 to 29, and n2 + n4 are integers of 0 to 30. The sequence of constituent units of-(AO)-and-(BO)-may be random or block. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side.
In one embodiment, n1 + n2 + n3 + n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Further, n2 + n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, and particularly preferably 0.

The polymerizable compound B1 may be used alone or in combination of two or more.
The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive composition layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin exudes from the end of the transfer member), 70% by mass or less is preferable, and 60% by mass or less is more preferable.

The negative photosensitive composition layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.
The polymerizable compound other than the polymerizable compound B1 is not particularly limited and may be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound. Examples include compounds.

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

Examples of the bifunctional 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 tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the like. 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol 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. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, isocyanuric acid tri (meth) acrylates, glycerintri (meth) acrylates, and alkylene oxide modified products thereof.
Here, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. , "(Tri / tetra) (meth) acrylate" is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.
Examples of the ethylenically unsaturated compound having 5 to 6 or more functionalities include dipentaerythritol polyacrylate (“A-DPH” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
In one embodiment, the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more trifunctional or higher. It is more preferable to contain an ethylenically unsaturated compound. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound is (total mass of the polymerizable compound B1): (total mass of the trifunctional or higher ethylenically unsaturated compound) = 1: 1. It is preferably ~ 5: 1, more preferably 1.2: 1 to 4: 1, and even more preferably 1.5: 1 to 3: 1.
Further, in one embodiment, the negative photosensitive composition layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified product of the trifunctional or higher ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Etc.), alkylene oxide-modified (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd., etc.), Acrylate glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M- 510 (manufactured by Toagosei Co., Ltd.) can be mentioned.

Further, as the ethylenically unsaturated compound, a polymerizable compound having an acid group (carboxy group or the like) may be used. The acid group may form an acid anhydride group. Polymerizable compounds having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei), Aronix (registered trademark) M-520 (manufactured by Toagosei), and Aronix (registered trademark) M-510 (registered trademark). Toagosei Co., Ltd.). As the ethylenically unsaturated compound having an acid group, for example, the compounds described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.

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

Further, the polymerizable compound may contain a polymerizable compound other than the ethylenically unsaturated compound (hereinafter, also referred to as “another polymerizable compound”).
The other polymerizable compound is a compound that polymerizes under the action of a photopolymerization initiator described later, and means a compound different from the above-mentioned polymer A. Further, the other polymerizable compound preferably has a molecular weight of less than 5,000.
Examples of the polymerizable group of the other polymerizable compound include a group having a cationically polymerizable group such as an epoxy group and an oxetane group.

<Photopolymerization initiator>
The negative photosensitive composition layer contains a photopolymerization initiator.
The photopolymerization initiator is a compound that initiates the polymerization of a polymerizable compound by receiving active light such as ultraviolet rays, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.

Examples of the photoradical 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, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.

Further, the negative photosensitive composition layer contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitive, visibility of exposed and unexposed areas, and resolution. It preferably contains at least one selected from the group consisting of the body and its derivatives. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.
Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- Examples thereof include (p-methoxyphenyl) -4,5-diphenylimidazole dimer.
Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-bi. Imidazole is also mentioned.

As the photoradical polymerization initiator, for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-09571 and paragraphs 0064-0081 of JP-A-2015-014783 may be used.

Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and TAZ-110 (trade name:). Midori Kagaku Co., Ltd.), Benzophenone, 4,4'-bis (diethylamino) benzophenone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), RadicalOXE01, OXE02, OXE03, OXE04 (BASF), Polymer 651 and 369 (Products) Name: IGM Resins B.V.) and 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Kasei Kogyo Co., Ltd.) Made).

Examples of commercially available photoradical polymerization initiators include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01). , BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF) IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4) -Morphorinyl) Phenyl] -1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name) : Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (commodity) Name: Omnirad 127, manufactured by IGM Resins B.V., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenylketone (trade name: Omnirad 184, IGM Resins B.V.) , 2,2-Dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (Product name: Omnirad TPO H, manufactured by IGM Resins B.V.), Bis (2,4,6-trimethylbenzolyl) Phenylphosphinoxide (Product name: Omnirad 819, manufactured by IGM Resins B.V.), Oxym Ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole (2-( 2-Chlorophenyl) -4, 5-Diphenylimidazole dimer (trade name: B-CIM, manufactured by Carbonyl) and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Kasei Kogyo Co., Ltd.) ), 1- [4- (Phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Joshu Powerful Electronics New Materials Co., Ltd.) , 1,2-Propandione, 3-Cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazole-3-yl]-, 2- (O-acetyloxime) (trade name) : TR-PBG-326, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazole-3-yl)- Propane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.) can be mentioned.
Examples of commercially available photo-radical polymerization initiators include alkylphenone compounds having the trade name “Omnirad 379” (manufactured by IGM Resins B.V.).

The photocationic polymerization initiator (photoacid generator) is a compound that generates an acid by receiving active light rays. As the photocationic polymerization initiator, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable, but its chemical structure is not limited. In addition, a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is used. The generated photocationic polymerization initiator is particularly preferred. The lower limit of pKa is not particularly defined, but is preferably -10.0 or higher, for example.

Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-085643 may be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, the diazomethane compound and the imide sulfonate compound, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149 may be used. Further, as the oxime sulfonate compound, the compound described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.

The negative photosensitive composition layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. preferable.

The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1.0% by mass, based on the total mass of the negative photosensitive composition layer. % Or more is more preferable. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, based on the total mass of the negative photosensitive composition layer. ..

The negative photosensitive composition layer may contain a radical polymerization inhibitor.
Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. Of these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. It is preferable to use a nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the negative photosensitive composition layer.
The preferred content of the radical polymerization inhibitor is the same as in the first embodiment.

<Dye>
The negative photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is also preferable to include a dye (also referred to as "dye N") whose maximum absorption wavelength is changed by an acid, a base, or a radical. When the dye N is contained, the detailed mechanism is unknown, but the adhesion to the adjacent layer (for example, a water-soluble resin layer) is improved, and the resolution is more excellent.

In the present specification, the term "the maximum absorption wavelength is changed by an acid, a base, or a radical" means that the dye in a color-developing state is decolorized by an acid, a base, or a radical, and the dye in a decolorized state is decolorized. It may mean any aspect of a mode in which a color is developed by an acid, a base, or a radical, and a mode in which a dye in a color-developing state changes to a color-developing state of another hue.
Specifically, the dye N may be a compound that changes its color from the decolorized state by exposure and may be a compound that changes its color from the decolorized state by exposure. In this case, it may be a dye whose color development or decolorization state changes due to the generation and action of an acid, a base, or a radical in the negative photosensitive composition layer by exposure, and the negative type by the acid, the base, or the radical. It may be a dye whose color development or decolorization state changes by changing the state (for example, pH) in the photosensitive composition layer. Further, it may be a dye that changes the state of color development or decolorization by directly receiving an acid, a base, or a radical as a stimulus without going through exposure.

Among them, from the viewpoint of visibility and resolution of the exposed and unexposed areas, 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. ..
When the negative photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer is a radical as the dye N from the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion. It is preferable to contain both a dye whose maximum absorption wavelength changes depending on the temperature and a photoradical polymerization initiator.
Further, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, a base, or a radical.

As an example of the color development mechanism of dye N, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to a negative photosensitive composition layer, and a photoradical is applied after exposure. A mode in which a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (for example, a leuco dye) is colored by a radical, acid, or base generated from a polymerization initiator, a photocationic polymerization initiator, or a photobase generator. Can be mentioned.

From the viewpoint of visibility of the exposed and non-exposed areas, the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 to 780 nm at the time of color development, more preferably 550 to 700 nm. It is more preferably ~ 650 nm.
Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of the dye N is the transmission spectrum of the solution containing the dye N (liquid temperature 25 ° C.) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere. Is measured, and the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength) is detected.

Examples of the dye that develops or decolorizes by exposure include leuco compounds.
Examples of the dye that is decolorized by exposure include a leuco compound, a diarylmethane dye, an oxadin dye, a xanthene dye, an iminonaphthoquinone dye, an azomethin dye, and an anthraquinone dye.
As the dye N, a leuco compound is preferable from the viewpoint of visibility of the exposed portion and the non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton. It has a leuco compound (diarylmethane dye) having a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (lodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indrill phthalide dye), and a leuco auramine skeleton. Leuco compounds (leuco-auramine-based dyes) can be mentioned.
Of these, triarylmethane-based dyes or fluorane-based dyes are preferable, and leuco compounds (triphenylmethane-based dyes) or fluorane-based dyes having a triphenylmethane skeleton are more preferable.

The leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and the non-exposed portion. As a result, the lactone ring, sultone ring, or sultone ring of the leuco compound is reacted with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator to change the leuco compound into a closed ring state. The color can be decolorized, or the radical compound can be changed to an open ring state to develop a color. As the leuco compound, a compound having a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop color is preferable, and the lactone ring has a radical or a radical. A compound in which the lactone ring is opened by an acid to develop a color is more preferable.

Examples of the dye N include the following dyes and leuco compounds.
Specific examples of the dyes among the dyes N include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalein, Xylenol Blue, and Methyl. Orange, Paramethyl Red, Congofred, Benzopurpurin 4B, α-Naphtyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malakite Green, Parafuxin, Victoria Pure Blue-Naphthalene Sulfate, Victoria Pure Blue BOH Tsuchiya Chemical Industry Co., Ltd.), Oil Blue # 603 (Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (Orient Chemical Industry Co., Ltd.) , Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green # 502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodoya Chemical Industry Co., Ltd.), m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulfolodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino- 4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p- Diethylaminophenylimino-5-pyrazolone can be mentioned.

Specific examples of the leuco compound among the dyes N include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, and malakite green lactone. Benzoyl leucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-trill-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p) -Truizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methyl) Amino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7 -Xylidinofluorane, 3- (N, N-diethylamino) -6-methyl-7-chlorofluorane, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N) , N-diethylamino) -7- (4-chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorolane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6 -Methyl-7-xylidinofluolane, 3-piperidino-6-methyl-7-anilinofluolane, 3-pyrrolidino-6-methyl-7-anilinofluolane, 3,3-bis (1-ethyl- 2-Methylindole-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethyl Aminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3-( 1-Ethyl-2-methylindol-3-yl) phthalide, and 3', 6'-bis (diphenylamino) spirisobenzofuran-1 (3H), 9'-[9H] xanthene-3-one can be mentioned. ..

The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. It is more preferable to have.
As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate is preferable.

The dye N may be used alone or in combination of two or more.
The content of the dye N is 0.1 mass with respect to the total mass of the negative photosensitive composition layer from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution. % Or more is preferable, 0.1 to 10% by mass is more preferable, 0.1 to 5% by mass is further preferable, and 0.1 to 1% by mass is particularly preferable.

The content of the dye N means the content of the dye when all of the dye N contained in the total mass of the negative photosensitive composition layer is in a colored state. Hereinafter, a method for quantifying the content of dye N will be described by taking a dye that develops color by radicals as an example.
A solution prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone is prepared. Irradicure OXE01 (trade name, BASF Japan, Inc.), a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Then, in an atmospheric atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 3 g of the negative photosensitive composition layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the negative photosensitive composition layer, the content of the dye contained in the negative photosensitive composition layer is calculated based on the calibration curve.
The negative type photosensitive composition layer 3 g is the same as 3 g of the total solid content in the composition for forming the negative type photosensitive composition layer.

<Thermal crosslinkable compound>
When the negative photosensitive composition layer is a negative photosensitive composition layer, it is preferable to contain a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In this specification, the heat-crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but is treated as a heat-crosslinkable compound.
Examples of the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is 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 hydroxy group and a carboxy group, for example, when the resin and / or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film decreases. When a film obtained by curing a negative photosensitive composition layer is used as a protective film, the function tends to be enhanced.
The blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".

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

Examples of the blocking agent having a dissociation temperature of 100 to 160 ° C. include an active methylene compound [malonic acid diester (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonic acid, etc.)] and an oxime compound ( Examples thereof include compounds having a structure represented by -C (= N-OH) -in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketooxime, and cyclohexanone oxime).
Among these, as the blocking agent having a dissociation temperature of 100 to 160 ° C., for example, at least one selected from oxime compounds is preferable from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate to protect it.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has less development residue. It is preferable from the viewpoint of easy operation.

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 radically polymerizable group is preferable.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group.
Among them, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth) acryloxy group is more preferable, and an acryloxy group is further preferable.

As the blocked isocyanate compound, a commercially available product can be used.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko KK), and block type. Examples thereof include the Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
Further, as the blocked isocyanate compound, a compound having the following structure can also be used.

<Other additives>
The negative photosensitive composition layer may contain known additives in addition to the above components, if necessary.
Examples of the additive include sensitizers, plasticizers, heterocyclic compounds (triazole and the like), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide and the like), purine bases (adenine and the like), and surfactants. Agents are mentioned.
Each additive may be used alone or in combination of two or more.

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

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like. As the carboxybenzotriazoles, for example, a commercially available product such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name) can be used.

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

The negative photosensitive composition layer may contain a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example). 1,2,4-triazole), stilben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.

The sensitizer may be used alone or in combination of two or more.
When the negative photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but the sensitivity to the light source is improved and the curing rate is improved by the balance between the polymerization rate and the chain transfer. From the viewpoint, 0.01 to 5% by mass is preferable, and 0.05 to 1% by mass is more preferable with respect to the total mass of the negative photosensitive composition layer.

The negative photosensitive composition layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640. The negative photosensitive composition layer preferably contains a surfactant. Examples of the surfactant include the same surfactants as those of the first embodiment, and the preferred embodiments are also the same.

In addition, the negative photosensitive composition layer includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, and organic or inorganic materials. It may further contain known additives such as anti-precipitation agents.
Additives contained in the negative photosensitive composition layer are described in paragraphs 0165 to 0184 of JP-A-2014-085643, and the contents of this publication are incorporated in the present specification.

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

The layer thickness (thickness) of the negative photosensitive composition layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, and 0.5 to 15 μm. Is more preferable, 0.5 to 10 μm is particularly preferable, and 0.5 to 8 μm is most preferable. As a result, the developability of the negative photosensitive composition layer can be improved, and the resolution can be improved.
Further, in one embodiment, 0.5 to 5 μm is preferable, 0.5 to 4 μm is more preferable, and 0.5 to 3 μm is further preferable.

Further, from the viewpoint of excellent adhesion, the transmittance of light having a wavelength of 365 nm in the negative photosensitive composition layer is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

<Impurities, etc.>
The negative photosensitive composition layer may contain a predetermined amount of impurities.
Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof. Of these, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following content is preferable.

The content of impurities in the negative photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis. The content of impurities may be 1 ppb or more, or 0.1 ppm or more, on a mass basis.

As a method for keeping impurities in the above range, select a composition having a low content of impurities as a raw material, prevent impurities from being mixed in when producing a negative photosensitive composition layer, and wash and remove the impurities. Can be mentioned. By such a method, the amount of impurities can be kept within the above range.

The content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the negative photosensitive composition layer is , Preferably less. The content of these compounds with respect to the total mass of the negative photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
The lower limit can be 10 ppb or more and 100 ppb or more with respect to the total mass of the negative photosensitive composition layer on a mass basis. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Further, it can be quantified by a known measurement method.

<Pigment>
The negative photosensitive composition layer may be a colored resin layer containing a pigment.
In recent years, the liquid crystal display window of an electronic device may have a cover glass having a black frame-shaped light-shielding layer formed on the peripheral edge of the back surface of a transparent glass substrate or the like to protect the liquid crystal display window. be. A colored resin layer can be used to form such a light-shielding layer.
The pigment may be appropriately selected according to the desired hue, and can be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as the effect of the present invention is not impaired. Among them, as the black pigment, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, graphite and the like are preferably mentioned from the viewpoint of optical density, and carbon black is particularly preferable. As the carbon black, from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.

From the viewpoint of dispersion stability, the particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm in terms of number average particle size.
Here, the particle size refers to the diameter of a circle when the area of the pigment particles is obtained from a photographic image of the pigment particles taken with an electronic microscope and a circle having the same area as the area of the pigment particles is considered, and the number average particle size. Is an average value obtained by obtaining the above particle size for any 100 particles and averaging the obtained 100 particle sizes.

As the pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as the white pigment. Specifically, among the white pigments, as the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable, and titanium oxide or zinc oxide is more preferable. Preferably, titanium oxide is more preferred. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
Further, the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be subjected to two or more treatments. As a result, the catalytic activity of titanium oxide is suppressed, and heat resistance, fading and the like are improved.
From the viewpoint of reducing the thickness of the negative photosensitive composition layer after heating, at least one of alumina treatment and zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both alumina treatment and zirconia treatment are particularly preferable. ..

Further, when the negative photosensitive composition layer is a colored resin layer, the negative photosensitive composition layer may further contain a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability. preferable. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, in that the dispersibility is more excellent.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), and Monolite. -Ero GT (CI Pigment Ellow 12), Permanent Ellow GR (CI Pigment Ellow 17), Permanent Yellow HR (CI Pigment Ellow 83), Permanent Carmine FBB (C) I. Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment) Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Above all, C.I. I. Pigment Red 177 is preferred.

When the negative type photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, preferably more than 3% by mass and 35% by mass, based on the total mass of the negative type photosensitive composition layer. More preferably, it is more preferably 5% by mass or more and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.

When the negative photosensitive composition layer contains a pigment other than the black pigment (white pigment and chromatic pigment), the content of the pigment other than the black pigment is preferably 30% by mass or less with respect to the black pigment. It is more preferably from 20% by mass, still more preferably from 3 to 15% by mass.

When the negative photosensitive composition layer contains a black pigment and the negative photosensitive composition layer is formed of a composition for forming a negative photosensitive composition layer, a black pigment (preferably carbon black) is used. Is preferably introduced into a composition for forming a negative photosensitive composition layer in the form of a pigment dispersion.
The dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it with a disperser. The pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle refers to a portion of the medium in which the pigment is dispersed when the pigment is dispersed, and is a liquid, a binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.

The disperser is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, it may be finely pulverized by mechanical grinding using frictional force. For the disperser and fine pulverization, the description of "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, 438, 310) can be referred to.

<< Relationship between temporary support, negative photosensitive composition layer and protective film >>
Also in the second embodiment, it is preferable to satisfy the relationship of the temporary support, the negative photosensitive composition layer and the protective film described in the first embodiment.

<< Thermoplastic resin layer >>
The thermoplastic resin layer is usually arranged between the temporary support and the negative photosensitive composition layer. When the transfer film is provided with the thermoplastic resin layer, the followability to the substrate in the bonding process between 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, the adhesion to the layer adjacent to the thermoplastic resin layer (for example, a temporary support) can be ensured.

The thermoplastic resin layer contains resin. The resin contains a thermoplastic resin in part or in whole. That is, in one embodiment, it is also preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.

<Alkali-soluble resin (thermoplastic resin)>
The thermoplastic resin is preferably an alkali-soluble resin.
Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin. , Polychloride resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to an adjacent layer.
Here, the acrylic resin is at least selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having one kind of structural unit.
As 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) acrylic acid amide is the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the mass.
Among them, the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, preferably 50 to 100% by mass, based on the total mass of the acrylic resin. 100% by mass is more preferable.

Further, the alkali-soluble resin is preferably a polymer having an acid group.
Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferable.
From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and further preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited and can be appropriately selected from known resins and used.
For example, among the polymers described in paragraph 0025 of JP-A-2011-095716, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, described in paragraphs 0033 to 0052 of JP-A-2010-237589. Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more among the polymers of the above, and acrylic containing a carboxy group having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP2016-224162A. Acrylic can be mentioned.
The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 12 to 30% by mass with respect to the total mass of the acrylic resin. Is more preferable.
As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.

The alkali-soluble resin may have a reactive group. The reactive group may be any addition-polymerizable group, and an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxy group; a polyaddition reactive group such as an epoxy group and a (block) isocyanate group may be used. Can be mentioned.

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

The alkali-soluble resin may be used alone or in combination of two or more.
The content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the adjacent layer. 40 to 80% by mass is more preferable, and 50 to 75% by mass is particularly preferable.

<Dye>
The thermoplastic resin layer contains a dye having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm at the time of color development and whose maximum absorption wavelength is changed by an acid, a base, or a radical (also referred to simply as “dye B”). Is preferable.
The preferred embodiment of the dye B is the same as the preferred embodiment of the dye N described above, except for the points described later.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part. ..
From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the thermoplastic resin layer contains both a dye whose maximum absorption wavelength changes depending on the acid as the dye B and a compound that generates an acid by light, which will be described later. It is preferable to include it.

The dye B may be used alone or in combination of two or more.
The content of the dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed portion and the non-exposed portion. , 0.2 to 5% by mass, more preferably 0.25 to 3.0% by mass.

Here, the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of dye B will be described by taking a dye that develops color by radicals as an example.
A solution prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone is prepared. Irradicure OXE01 (trade name, BASF Japan, Inc.), a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Then, in an atmospheric atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve is prepared.
Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
The thermoplastic resin layer (3 g) is the same as the solid content of the composition (3 g).

<Compounds that generate acids, bases, or radicals with light>
The thermoplastic resin layer may contain a compound (also simply referred to as “compound C”) that generates an acid, a base, or a radical by light.
As the compound C, a compound that generates an acid, a base, or a radical by receiving active light such as ultraviolet rays and visible light is preferable.
As the compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

(Photoacid generator)
The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.
Examples of the photoacid generator include a photocationic polymerization initiator that may be contained in the negative-type photosensitive composition layer described above, and the same preferred embodiments are used except for the points described below.

The photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and preferably contains sensitivity, resolution and adhesion. From the viewpoint of sex, it is more preferable to contain an oxime sulfonate compound.
Further, as the photoacid generator, a photoacid generator having the following structure is also preferable.

(Photoradical polymerization initiator)
The thermoplastic resin layer may contain a photoradical polymerization initiator.
Examples of the photo-radical polymerization initiator include a photo-radical polymerization initiator that may be contained in the negative-type photosensitive composition layer described above, and the same preferred embodiments are also used.

(Photobase generator)
The thermoplastic resin composition may contain a photobase generator.
The photobase generator is not particularly limited as long as it is a known photobase generator, and for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyloxime, [[(2, 6-Dinitrobenzyl) Oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4) -Morholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5-diacetyl-4- (2-nitrophenyl) -1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl -4- (2,4-dinitrophenyl) -1,4-dihydropyridine can be mentioned.

Compound C may be used alone or in combination of two or more.
The content of the compound C is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility and resolution of the exposed and non-exposed areas. More preferably by mass.

<Plasticizer>
The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or a polymer and has a molecular weight distribution) than that of an alkali-soluble resin. 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 that is compatible with an alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and is a polyalkylene glycol. Compounds are more preferred. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethyleneoxy structure or a polypropyleneoxy structure.

Further, the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to the adjacent layer, 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 used as a plasticizer include the (meth) acrylate compound described as the polymerizable compound contained in the above-mentioned negative photosensitive composition layer.
In the transfer film, when the thermoplastic resin layer and the negative photosensitive composition layer are directly contacted and laminated, both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth) acrylate compound. Is preferable. This is because the thermoplastic resin layer and the negative photosensitive composition layer each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, the (meth) acrylate compound may not polymerize even in the exposed portion after exposure from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer. preferable.
Further, as the (meth) acrylate compound used as a plasticizer, two or more (meth) in one molecule from the viewpoint of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability. Polyfunctional (meth) acrylate compounds having an acryloyl group are preferred.
Further, as the (meth) acrylate compound used as a plasticizer, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.

The plasticizer may be used alone or in combination of two or more.
The content of the plasticizer is preferably 1 to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of the resolution of the thermoplastic resin layer, the adhesion to the adjacent layer, and the developability. 10 to 60% by mass is more preferable, and 20 to 50% by mass is further preferable.

<Sensitizer>
The thermoplastic resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and examples thereof include a sensitizer that may be contained in the negative photosensitive composition layer described above.

The sensitizer may be used alone or in combination of two or more.
The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, it is 0.01 with respect to the total mass of the thermoplastic resin layer. It is preferably from 5% by mass, more preferably 0.05 to 1% by mass.

<Additives, etc.>
In addition to the above components, the thermoplastic resin layer may contain a known additive such as a surfactant, if necessary.
Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-085643, and the contents described in this publication are incorporated in the present specification.

The layer thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. The upper limit is not particularly limited, but from the viewpoint of developability and resolvability, 20 μm or less is preferable, 10 μm or less is more preferable, and 8 μm or less is further preferable.

<< Middle class >>
In the transfer film 20, the intermediate layer 15 is present between the thermoplastic resin layer 13 and the negative photosensitive composition layer 17, so that the thermoplastic resin layer 13 and the negative photosensitive composition layer 17 are coated and formed. It is possible to suppress the mixing of components that may occur during storage at the time of coating and after coating formation.
As the intermediate layer, a water-soluble resin layer containing a water-soluble resin can be used.
Further, as the intermediate layer, an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-07724, can also be used. When the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, which is preferable.
The oxygen blocking layer used as the intermediate layer may be appropriately selected from the known layers described in the above publications and the like. Of these, an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.) is preferable.

Hereinafter, each component that can be contained in the water-soluble resin layer (intermediate layer) will be described.

The water-soluble resin layer (intermediate layer) contains a resin.
The resin contains a water-soluble resin in part or in whole.
Examples of the resin that can be used as the water-soluble resin include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and their co-weight. Examples include resins such as coalescing.
Further, as the water-soluble resin, a (meth) acrylic acid / vinyl compound copolymer or the like can also be used. As the copolymer of (meth) acrylic acid / vinyl compound, a copolymer of (meth) acrylic acid / allyl (meth) acrylic acid 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 / vinyl compound, the composition ratio (mol%) is preferably 90/10 to 20/80, preferably 80/20 to 30/70. More preferred.

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

The resin in the water-soluble resin layer (intermediate layer) is arranged on one surface side of the water-soluble resin layer (intermediate layer) in order to further improve the ability to suppress the interlayer mixing of the water-soluble resin layer (intermediate layer). It is preferable that the resin is different from the resin contained in the layer to be formed and the resin contained in the layer arranged on the other surface side. For example, when the polymer A is contained in the negative photosensitive composition layer 17 and the thermoplastic resin (alkali-soluble resin) is contained in the thermoplastic resin layer 13, the resin of the water-soluble resin layer (intermediate layer) 15 is contained. Is preferably a resin different from the polymer A and the thermoplastic resin (alkali-soluble resin).

The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, in terms of further improving the oxygen blocking property and the ability to suppress interlayer mixing.

The water-soluble resin may be used alone or in combination of two or more.
The content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more with respect to the total mass of the water-soluble resin layer (intermediate layer) in terms of further improving the oxygen blocking property and the ability to suppress interlayer mixing. , 70% by mass or more is more preferable, 80% by mass or more is further preferable, and 90% by mass or more is particularly preferable. The upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.
The intermediate layer may contain a known additive such as a surfactant, if necessary.

The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen blocking property is not lowered and the ability to suppress interlaminar mixing is excellent. Further, it is possible to suppress an increase in the time for removing the water-soluble resin layer (intermediate layer) during development.

<< Method for Producing Transfer Film of Second Embodiment >>
The method for producing the transfer film of the second embodiment is not particularly limited, and a known method can be used.
As a method for producing the transfer film 20, for example, a thermoplastic resin composition is applied to the surface of the temporary support 11 to form a coating film, and the coating film is further dried to form a thermoplastic resin layer 13. A step of applying a water-soluble resin composition to the surface of the thermoplastic resin layer 13 to form a coating film, and a step of further drying the coating film to form an intermediate layer 15 and a step of forming an intermediate layer 15 on the surface of the intermediate layer 15. Examples thereof include a step of applying a photosensitive composition to form a coating film, and further drying the coating film to form a negative photosensitive composition layer 17.

The transfer film 20 is manufactured by crimping the protective film 19 onto the negative photosensitive composition layer 17 of the laminate manufactured by the above-mentioned manufacturing method.
The method for producing the transfer film of the second embodiment includes a step of providing the protective film 19 so as to be in contact with the surface of the negative photosensitive composition layer 17 opposite to the side having the temporary support 11. It is preferable to produce a transfer film 20 including a temporary support 11, a thermoplastic resin layer 13, an intermediate layer 15, a negative photosensitive composition layer 17, and a protective film 19.
After the transfer film 20 is manufactured by the above-mentioned manufacturing method, the transfer film 20 may be wound up to prepare and store the transfer film in the form of a roll. The roll-type transfer film can be provided as it is in the bonding process with the substrate in the roll-to-roll method described later.

Further, as a method for producing the transfer film 20, the negative type photosensitive composition layer 17 and the intermediate layer 15 are formed on the cover film 19, and then the thermoplastic resin layer 13 is formed on the surface of the intermediate layer 15. It may be a method.

<Composition for forming a thermoplastic resin layer and a method for forming a 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, it can be formed by applying a composition for forming a thermoplastic resin layer on a temporary support and drying it if necessary.
The composition for forming the thermoplastic resin layer preferably contains the above-mentioned various components for forming the thermoplastic resin layer and a solvent. In the composition for forming a thermoplastic resin 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 thermoplastic resin layer described above. be.
The solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, and a known solvent can be used. Examples of the solvent include the same solvents as those contained in the composition for forming a negative photosensitive composition layer described later, and the preferred embodiments are also the same.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the thermoplastic resin layer is not particularly limited as long as it can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) can be used. Can be mentioned.

<Method of forming water-soluble resin composition and intermediate layer (water-soluble resin layer)>
The water-soluble resin composition preferably contains various components forming the above-mentioned intermediate layer (water-soluble resin layer) and a solvent. 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 described above.
The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and water or water-miscible organic. A mixed solvent with a solvent is more preferable.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
The solvent may be used alone or in combination of two or more.
The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 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 can form a layer containing the above components, and for example, known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.) can be used. Can be mentioned.

<Composition for forming a negative photosensitive composition layer and a method for forming a negative photosensitive composition layer>
A negative photosensitive composition layer containing the above-mentioned components (for example, a binder polymer, a polymerizable compound, a polymerization initiator, etc.) and a solvent that constitute the above-mentioned negative photosensitive composition layer in terms of excellent productivity. It is preferably formed by a coating method using a forming composition.
Specifically, as a method for producing a transfer film of the second embodiment, a negative-type photosensitive composition layer-forming composition is applied onto an intermediate layer to form a coating film, and the coating film is subjected to a drying treatment. It is preferable to apply the method to form a negative photosensitive composition layer.

The composition for forming the negative photosensitive composition layer preferably contains various components and a solvent for forming the negative photosensitive composition layer described above. In the composition for forming a negative photosensitive composition layer, the preferable range of the content of each component with respect to the total solid content of the composition is the content of each component with respect to the total mass of the negative photosensitive composition layer described above. It is the same as the preferable range of.
The solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, and a known solvent can be used. Specifically, for example, alkylene glycol ether solvent, alkylene glycol ether acetate solvent, alcohol solvent (methanol, ethanol, etc.), ketone solvent (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvent (toluene, etc.), aprotonic polarity. Examples thereof include a solvent (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetratetra, etc.), an ester solvent (npropyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent containing two or more of these.

The solvent preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable. A mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and at least three types of a cyclic ether solvent is 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 the like. 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.
As the solvent, the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used, and the contents thereof are described in the present specification. Will be incorporated into.
The solvent may be used alone or in combination of two or more.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1200 parts by mass, still more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.

As a method for drying the coating film of the negative photosensitive composition layer forming composition, heat drying and vacuum drying are preferable.
The drying temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher. The upper limit thereof is preferably 130 ° C. or lower, more preferably 120 ° C. or lower. It can also be dried by continuously changing the temperature.
The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

Further, the transfer film of the second embodiment can be produced by adhering the protective film to the negative photosensitive composition layer.
The method of adhering the protective film to the negative photosensitive composition layer is not particularly limited, and known methods can be mentioned.
Examples of the device for adhering the protective film to the negative photosensitive composition layer include a vacuum laminator and a known laminator such as an auto-cut laminator.
It is preferable that the laminator is provided with an arbitrary heatable roller such as a rubber roller and can be pressurized and heated.

[Manufacturing method of laminated body]
By using the above-mentioned transfer film, the composition layer can be transferred to the transferred body.
Above all, the transfer film of the present invention is preferably used for manufacturing a touch panel.
Among them, in the method for producing a laminated body of the present invention, the surface of the transfer film on the opposite side of the temporary support is brought into contact with a substrate having a conductive portion and bonded to the substrate, the conductive layer, the composition layer, and , A bonding step of obtaining a substrate with a composition layer having a temporary support in this order,
An exposure process for pattern exposure of the composition layer and
It comprises a developing step of developing an exposed composition layer to form a protective film pattern that protects the conductive layer.
Further, it is a method for manufacturing a laminated body, which comprises a peeling step of peeling a temporary support from a substrate with a composition layer between a bonding step and an exposure step, or between an exposure step and a developing step. Is preferable.

Further, it is preferable that the method for manufacturing the laminate and the method for manufacturing the circuit wiring of the present invention are carried out by a roll tool process using a roll-shaped transfer film. That is, the bonding step is a step of bonding the transfer film and the substrate having the conductive layer described later by roll-to-roll, and at least the above-mentioned long-shaped laminate formed by the above-mentioned bonding step. It is preferable to carry out the exposure step and the development step.
Hereinafter, the procedure of the above process will be described in detail.

[Lasting process]
In the bonding step, the surface of the transfer film opposite to the temporary support is brought into contact with the substrate having the conductive portion and bonded, and the substrate, the conductive layer, the negative photosensitive composition layer, and the temporary support are bonded. Is a step of obtaining a substrate with a composition layer having the above in this order. If the transfer film has a protective film, the protective film is peeled off and then the bonding step is performed.

In the above bonding, the conductive layer and the surface of the composition layer are pressure-bonded so as to be in contact with each other.
The crimping method is not particularly limited, and a known transfer method and laminating method can be used. Above all, it is preferable that the surface of the composition layer is superposed on a substrate having a conductive portion, and pressure and heating are performed by a roll or the like.
A known laminator such as a vacuum laminator and an auto-cut laminator can be used for bonding.
The laminating temperature is not particularly limited, but is preferably 70 to 130 ° C., for example.

The substrate having a conductive layer has a conductive layer on the substrate, and any layer may be formed if necessary. That is, the substrate having the conductive layer is a conductive substrate having at least a substrate and a conductive layer arranged on the substrate.

Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
Preferred embodiments of the substrate are described, for example, in paragraph [0140] of WO 2018/155193, the contents of which are incorporated herein. As the material of the resin substrate, cycloolefin polymer and polyimide are preferable. The thickness of the resin substrate is preferably 5 μm to 200 μm, more preferably 10 to 100 μm.

The conductive layer is at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. It is preferable to have it.
Further, only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials.
Preferred embodiments of the conductive layer are described, for example, in paragraph [0141] of WO 2018/155193, the contents of which are incorporated herein.

As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and a routing wire is preferable. The above-mentioned substrate can be suitably used as a touch panel substrate.
The transparent electrode may function suitably as a touch panel electrode. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a fine metal wire such as a metal nanowire.
Examples of the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.

Metal is preferable as the material of the routing wiring.
Examples of the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. As the material of the routing wiring, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

The protective film for a touch panel formed by using the negative photosensitive composition layer in the transfer film of the present invention has the electrode and / or the wiring directly or via another layer for the purpose of protecting the electrode and / or the wiring. It may be provided so as to cover the electrodes, or it may be provided as a protective film for insulating the electrodes (specifically, a protective film for insulating the electrodes such as bridge wiring).

[Exposure process]
The exposure step is a step of pattern-exposing the composition layer.
Here, the "pattern exposure" refers to an exposure in a form of exposure in a pattern, that is, a form in which an exposed portion and a non-exposed portion are present.
The positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited and is appropriately adjusted.
It may be exposed from the side opposite to the substrate of the composition layer, or may be exposed from the substrate side of the composition layer.

As the light source for pattern exposure, any light source in a wavelength range capable of curing at least the negative photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Of these, the main wavelength of the exposure light for pattern exposure is preferably 365 nm. The main wavelength is the wavelength having the highest intensity.

Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
The exposure amount is preferably 5 to 200 mJ / cm ² , more preferably 10 to 200 mJ / cm ² .

Preferred embodiments of the light source, exposure amount and exposure method used for exposure are described in, for example, paragraphs [0146] to [0147] of International Publication No. 2018/155193, and these contents are incorporated in the present specification. ..

By performing the exposure step and the development step described later, a protective film pattern that protects at least a part of the conductive layer is formed on the conductive layer on the substrate.

[Peeling process]
The peeling step is a step of peeling the temporary support from the substrate with the composition layer between the bonding step and the exposure step, or between the exposure step and the development step described later.
The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP2010-072589 can be used.

[Development process]
The developing step is a step of developing the exposed composition layer to form a pattern.
The development of the composition layer can be carried out using a developing solution.
An alkaline aqueous solution is preferable as the developing solution. Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxy. Do, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

Examples of the development method include paddle development, shower development, spin development, and dip development, and shower development is preferable.

A preferred embodiment of the developer used in the developing step is, for example, the developer described in paragraph [0194] of International Publication No. 2015/093271.
Further, as a preferable aspect of the developing method for carrying out the developing step, for example, the developing method described in paragraph [0195] of International Publication No. 2015/093271 can be mentioned.

Further, the developing step is preferably a step of repeatedly using the developing solution by circulating the developing solution, the developing method is shower development, and the developing solution is circulated by circulating the developing solution. It is preferable that the process is used repeatedly. Specific embodiments for carrying out the above-mentioned development step include, for example, the development method described in JP-A-2012-137574.

[Post-exposure process and post-baking process]
The method for producing the laminate may include a step of exposing the pattern obtained by the development step (post-exposure step) and / or a step of heating (post-baking step).
When both the post-exposure step and the post-baking step are included, it is preferable to carry out post-baking after post-exposure. The exposure amount of the post exposure is preferably 100 to 5000 mJ / cm ² , more preferably 200 to 3000 mJ / cm ² . The post-bake temperature is preferably 80 to 250 ° C, more preferably 90 to 160 ° C. The post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[Use of laminated body]
The laminate produced by the method for producing a laminate of the present invention can be applied to various devices. Examples of the device provided with the laminated body include an input device and the like, preferably a touch panel, and more preferably a capacitive touch panel. Further, the input device can be applied to a display device such as an organic electroluminescence display device and a liquid crystal display device.
When the laminate is applied to a touch panel, the pattern formed from the composition layer is preferably used as a touch panel electrode or a protective film for the touch panel wiring. That is, the composition layer contained in the transfer film is preferably used for forming the electrode protective film for the touch panel or the wiring protective film for the touch panel.

[Manufacturing method of circuit wiring]
Circuit wiring can also be manufactured by using the transfer film described above.
The method for manufacturing the circuit wiring is not particularly limited as long as it is the method for manufacturing the circuit wiring using the transfer film described above.
Among them, in the method for manufacturing a circuit wiring of the present invention, the surface of the transfer film on the opposite side of the temporary support is brought into contact with the substrate having the conductive layer, and the substrate, the conductive layer, the composition layer, and the temporary support are provided. A bonding step of obtaining a substrate with a composition layer having a body in this order, an exposure step of pattern-exposing the composition layer, and a process of exposing the composition layer to a pattern.
A developing process that develops the exposed composition layer to form a resin pattern,
Temporarily from the substrate with the composition layer between the etching process of etching the conductive layer in the region where the resin pattern is not arranged, and further between the bonding process and the exposure process, or between the exposure process and the developing process. It is preferable that the manufacturing method includes a peeling step of peeling the support.

Hereinafter, a specific procedure of a method for manufacturing a circuit wiring will be described.
The bonding step, the exposure process, the developing process, and the peeling step in the circuit wiring manufacturing method are the same as the bonding step, the exposure step, the developing step, and the peeling step in the above-mentioned laminated body manufacturing method, and are preferred embodiments. Is the same.

[Etching process]
The circuit wiring is manufactured by a manufacturing method including a substrate, a conductive layer (conductive layer of the substrate), and a resin pattern (more preferably, the bonding step, the exposure step, and the developing step. In the laminated body in which the resin pattern is laminated in this order, the step (etching step) of etching the conductive layer in the region where the resin pattern is not arranged is included.
In the etching step, the resin pattern obtained from the negative photosensitive composition layer by the developing step is used as an etching resist, and the conductive layer is etched.
As a method of etching treatment, a known method can be applied. For example, the methods described in paragraphs [0209] to [0210] of JP-A-2017-120435, paragraphs [0048] to JP-A-2010-152155. Examples thereof include the method described in [0054], a wet etching method of immersing in an etching solution, and a dry etching method such as plasma etching.

As the etching solution used for wet etching, an acidic or alkaline etching solution may be appropriately selected according to the etching target.
Examples of the acidic etching solution include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, an acidic component, ferric chloride, ammonium fluoride and Examples thereof include a mixed aqueous solution with a salt selected from potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.
The alkaline etching solution includes an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (tetramethylammonium hydroxide, etc.), and an alkaline component and a salt. Examples thereof include a mixed aqueous solution with (potassium permanganate, etc.). The alkaline component may be a component in which a plurality of alkaline components are combined.

[Removal process]
In the circuit wiring manufacturing method, it is preferable to perform a step (removal step) of removing the remaining resin pattern.
The removing step is not particularly limited and can be performed as needed, but it is preferably performed after the etching step.
The method for removing the remaining resin pattern is not particularly limited, and examples thereof include a method for removing by chemical treatment, and a method for removing with a removing liquid is preferable.
As a method for removing the negative photosensitive composition layer, a substrate having a resin pattern remaining in the removing liquid during stirring having a liquid temperature of preferably 30 to 80 ° C., more preferably 50 to 80 ° C. is 1 to 1 to 1. A method of soaking for 30 minutes can be mentioned.

Examples of the removing liquid include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound and a quaternary ammonium salt compound.
Further, the removing liquid may be used and removed by a known method such as a spray method, a shower method and a paddle method.

[Other processes]
The method for manufacturing the circuit wiring may include any process (other process) other than the above-mentioned process.
For example, a step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089, a new conductive layer is provided on the insulating film described in paragraph [0172] of International Publication No. 2019/022089. Examples thereof include steps of forming, but the process is not limited to these steps.

<Step to reduce visible light reflectance>
The method for manufacturing a circuit wiring may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers of the base material.
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. When the base material has a conductive layer containing copper, the visible light reflectance of the conductive layer can be lowered by oxidizing copper to obtain copper oxide and blackening the conductive layer.
The treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of JP-2013-206315. , The contents of these publications are incorporated herein.

<Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film>
The method for manufacturing a circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed.
The step of forming the insulating film is not particularly limited, and examples thereof include a known method of forming a permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
The step of forming the new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

As a method for manufacturing a circuit wiring, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the base material, and to form a circuit sequentially or simultaneously on the conductive layers formed on both surfaces of the base material. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a base material and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the base material by roll-to-roll.

[Use of circuit wiring]
The circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices. Examples of the device provided with the circuit wiring manufactured by the above manufacturing method include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable. Further, the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
Unless otherwise specified, "part" and "%" are based on mass.

[Preparation of transfer films of Examples 1 to 36 and Comparative Examples 1 to 9 and various evaluations]
[Various components contained in a negative-type photosensitive composition layer-forming composition (hereinafter abbreviated as "photosensitive composition")]
Hereinafter, various components used in the photosensitive composition for forming the negative photosensitive composition layer contained in the transfer films of Examples and Comparative Examples will be described.

<Binder polymer>
(Binder polymer)
The binder polymers shown in Table 2 are shown below. In the copolymers shown below, the composition ratio is based on mass.
B1: MMA / MAA / St = 40/16/44 copolymer (acid value: 104, Mw: 17000)
B2: MMA / MAA / CHMA = 35/25/40 copolymer (acid value: 163, Mw: 17000)
B3: Copolymer of St / MMA / MAA / MAA-GMA = 29/2/19/50 (acid value: 124, Mw: 17000)
B4: Copolymer of St / MMA / MAA / MAA-GMA / HEMA = 27/2/19/50/2 (acid value: 124, Mw: 17000)
B5: Copolymer of St / MMA / MAA / MAA-GMA = 49/2/19/30 (acid value: 124, Mw: 17000)
B6: Copolymer of St / MMA / MAA / MAA-GMA = 29/2/19/50 (acid value: 124, Mw: 42000)
B7: Copolymer of St / MMA / MAA / MAA-GMA = 29/2/19/50 (acid value: 124, Mw: 105000)
B8: Copolymer of St / MMA / MAA / MAA-GMA = 29/8/13/50 (acid value: 83, Mw: 17000)
B9: Copolymer of St / MMA / MAA / MAA-GMA = 29/2/19/50 (acid value: 124, Mw: 17000)
B10: MMA / MAA / St = 40/16/44 copolymer (acid value: 104, Mw: 17000)
B11: Copolymer of St / MMA / MAA / MAA-GMA = 29/2/19/50 (acid value: 124, Mw: 17000)
B12: Copolymer of St / MMA / MAA / BnMA = 45/5/25/25 (acid value: 163, Mw: 17000)
B13: St / MMA / MAA = 31/38/31 copolymer (acid value: 202, Mw: 17000)

The abbreviations for each monomer forming the constituent unit of the binder polymer are as follows.
St: Styrene MAA: Methacrylic acid MMA: Methyl methacrylate MMA-GMA: A unit obtained by adding glycidyl methacrylate to methacrylic acid CHMA: Cyclohexyl methacrylate HEMA: -2-hydroxyethyl methacrylate BnMA: benzyl methacrylate

(Example of synthesis of binder polymer)
Hereinafter, an example of synthesizing the binder polymer will be described. In the following, an example of synthesizing the binder polymer B3 will be described as an example.
In the synthesis of the binder polymer, the binder polymers B1 to B9, B12, and B13 were all subjected to the purification step by the reprecipitation treatment, but the binder polymers B10 and B11 were subjected to the purification treatment by the reprecipitation treatment. There wasn't.

<Synthesis of binder polymer B3>
244.2 parts by mass of propylene glycol monomethyl ether (MFG, manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a three-necked flask and kept at 90 ° C. under nitrogen. There, 6 parts by mass of methyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 207 parts by mass of methacrylic acid (MAA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 87 parts by mass, MFG 188.5 parts by mass, p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.0610 parts by mass, V-601 (dimethyl 2,2'-azobis (2-methylpropionate)) , Wako Pure Chemical Industries, Ltd. (manufactured by Wako Pure Chemical Industries, Ltd.) 16.7 parts by mass of a mixed solution was added dropwise over 3 hours.
After the dropping, the mixture is stirred at 90 ° C. for 1 hour, a mixture of V-601 (2.1 parts by mass) and MFG (5.2 parts by mass) is added, and after stirring for 1 hour, V-601 (2.1 parts by mass) is added. Part) and MFG (5.2 parts by mass) were further added. After stirring for 1 hour, a mixture of V-601 (2.1 parts by mass) and MFG (5.2 parts by mass) was further added. After stirring for 3 hours, 2.9 parts by mass of MFG and 166.9 parts by mass of propylene glycol monomethyl ether acetate (PGMEA, manufactured by Daicel Corporation) were added, and the mixture was stirred until uniform.
To the reaction solution, 1.5 parts by mass of tetramethylammonium bromide (TEAB, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.7 parts by mass of p-methoxyphenol as an addition catalyst were added, and the temperature was raised to 100 ° C. Further, 150 parts by mass of glycidyl methacrylate (GMA, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 100 ° C. for 9 hours to obtain an MFG / PGMEA mixed solution of the binder polymer B3.
100 g of the MFG / PGMEA mixed solution of the binder polymer B3 was added dropwise to 1000 g of ion-exchanged water at 30 ° C. over 30 minutes for reprecipitation treatment, and the binder polymer B3 precipitated as a solid substance was taken out by filtration and used.
The weight average molecular weight of the binder polymer B3 measured by GPC was 17,000 (in terms of polystyrene), and the acid value was 124 mgKOH / g.

Table 1 summarizes the main feature points of the above-mentioned binder.

<Compound with ethylenically unsaturated group>
A-NOD-N: 1,9-nonanediol diacrylate ("A-NOD-N" manufactured by Shin Nakamura Chemical Industry Co., Ltd., bifunctional acrylate)
A-DCP: Tricyclodecanedimethanol diacrylate ("A-DCP" manufactured by Shin Nakamura Chemical Industry Co., Ltd., bifunctional acrylate)
BPE-200: Ethoxylated bisphenol A dimethacrylate ("BPE-200" manufactured by Shin Nakamura Chemical Industry Co., Ltd., bifunctional acrylate)
A-TMPT: Trimethylolpropane triacrylate ("A-TMPT" manufactured by Shin Nakamura Chemical Industry Co., Ltd., trifunctional acrylate)
A-TMMT: Pentaerythritol tetraacrylate ("A-TMMT" manufactured by Shin Nakamura Chemical Industry Co., Ltd., tetrafunctional acrylate)
TO-2349: Mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid derivative of dipentaerythritol pentaacrylate ("Aronix TO-2349" manufactured by Toagosei Co., Ltd., 5 or 6 functional acrylate)
A-DPH: Dipentaerythritol polyacrylate ("A-DPH" manufactured by Shin Nakamura Chemical Industry Co., Ltd., 5-6 functional acrylate)
U-15HA: "U-15HA" manufactured by Shin Nakamura Chemical Industry Co., Ltd. (15-functional urethane acrylate)

<Photopolymerization initiator>
Omni379: Alkylphenone-based compound (“Omnirad 379” manufactured by IGM Resins B.V.)
OXE-02: Oxime ester-based photopolymerization initiator (BASF's "Irgacure OXE02")
OXE-03: Oxime ester-based photopolymerization initiator (BASF's "Irgacure OXE03")
Omni 907: α-Aminoalkylphenone-based Photopolymerization Initiator (“Omnirad 907” manufactured by IGM Resins B.V.)
HABI: 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
API-307: 1- (biphenyl-4-yl) -2-methyl-2-morpholinopropane-1-one (Shenzhen UV-ChemTech Ltd. "APi-307")

<Polymerization inhibitor>
Phenothiazine: Made by Tokyo Chemical Industry Phenoxazine: Made by Tokyo Chemical Industry p-Methoxyphenol: Wako Pure Chemical Industries, Ltd.

<Surfactant>
F-551: Fluorosurfactant, DIC Megafuck R-40: DIC Futergent 710FL: Neos DOWNSIL 8032 ADDITION: Toredau

<Solvent>
1-methoxy-2-propyl acetate: manufactured by Tokyo Chemical Industry Co., Ltd. Methyl ethyl ketone: manufactured by Tokyo Chemical Industry Co., Ltd. Propylene glycol monomethyl ether: manufactured by Tokyo Chemical Industry Co., Ltd.

[Preparation of photosensitive composition]
Each component other than the solvent based on the formulation shown in Table 2, 100 parts by mass of 1-methoxy-2-propyl acetate, 150 parts by mass of methyl ethyl ketone, and 50 parts by mass of propylene glycol monomethyl ether are mixed to form a photosensitive composition (coating). Liquid) was prepared. The numerical values corresponding to the components shown in Table 2 represent the blending amount (parts by mass) of each component.

[Preparation of transfer film]
Transfer films were prepared so as to have the configurations shown in Table 2. Specifically, it is as follows.

<Preparation of transfer film of Example 1>
The photosensitive composition (coating liquid 1) was dried on a 16 μm-thick polyethylene terephthalate film (temporary support, 16KS40 (manufactured by Toray Industries, Inc.)) using a slit-shaped nozzle, and the film shown in Table 2 was dried. The film was adjusted to a thickness and applied, and dried with a hot air convection dryer having a temperature gradient of 75 ° C. to 120 ° C. to remove the solvent to form a negative photosensitive composition layer.
Next, a polypropylene film having a thickness of 25 μm (protective film, Trefan 25A-KW37 (manufactured by Toray Industries, Inc.)) was pressure-bonded onto the negative photosensitive composition layer to prepare a transfer film of Example 1.

<Preparation of Transfer Films of Examples 2-36>
Except that the components other than the solvent of the photosensitive composition (coating liquid 1) were changed to those shown in Table 2 and adjusted to have the film thickness shown in Table 2 after drying, the same as in Example 1. A transfer film of the transfer film of Examples 2 to 36 was prepared by the same method.

<Preparation of transfer films of Comparative Examples 1 to 9>
Except that the components other than the solvent of the photosensitive composition (coating liquid 1) were changed to those shown in Table 2 and adjusted to have the film thickness shown in Table 2 after drying, the same as in Example 1. A transfer film of Comparative Examples 1 to 9 transfer films was prepared by the same method.

[Various measurements of transfer film]
The measurements shown below were carried out for each of the obtained transfer films of Examples and Comparative Examples. Table 2 shows the measurement results.

<Measurement of E10 and E90>
The transfer film from which the protective film was peeled off was transferred onto a glass plate (Eagle XG, Corning Inc.) having a thickness of 0.7 mm under the conditions of a temperature of 100 ° C. and a speed of 4 m / min. Through the temporary support of the transferred material, exposure was performed at 30 points while increasing the exposure amount by 5 mJ from 10 mJ using an ultrahigh pressure mercury lamp, and ultraviolet irradiation was performed.
The UV-irradiated sample was kept in an environment of 25 ° C. and 60% for 24 hours. Then, the temporary support of the sample was peeled off, and a developing process and a cleaning process were carried out using a developing machine YCD-500WA manufactured by Yamagata Machinery Co., Ltd. As the development conditions, a shower development process (shower nozzle: full cone nozzle, shower pressure: 0.10 MPa, shower) while supplying a new liquid using a 1.0 mass% sodium carbonate aqueous solution at a temperature of 30 ° C. The flow rate was 1000 mL / min). The development time was 30 seconds. Immediately after the development treatment, a cleaning treatment (rinsing treatment) was performed using pure water. The cleaning conditions (rinse conditions) were shower cleaning treatment using pure water at a temperature of 30 ° C. (shower nozzle: full cone nozzle, shower pressure: 0.10 MPa, shower flow rate: 1000 mL / min). The washing time was 30 seconds.
After the sample that had been rinsed was sufficiently dried, the film thickness of the cured film of the negative photosensitive composition layer at each exposure amount was measured using a stylus type film thickness meter (DekTak150).
Next, the points corresponding to the film thickness and the exposure amount at each exposed portion are plotted on the Cartesian coordinates with the film thickness of the cured film as the vertical axis and the exposure amount as the horizontal axis, and the film thickness does not substantially change. The film thickness at the exposure amount is used as the reference film thickness, and from the Cartesian coordinates, the exposure amount E10 is 10% of the reference film thickness, and the exposure is 90% of the reference film thickness. The quantity E90 was calculated. The values of E10 / E90 were calculated based on the obtained numerical values.

<Measurement of mass increase rate in developer>
The mass increase rate in the developing solution was determined by the QCM method (RDA-Qz3 manufactured by Lithotech Japan Co., Ltd.).
First, the transfer film from which the protective film was peeled off was transferred onto the crystal oscillator for measurement under the conditions of a temperature of 100 ° C. and a speed of 4 m / min. Ultraviolet irradiation was performed through the temporary support of the transferred material using an ultra-high pressure mercury lamp with an exposure amount twice that of the above-mentioned E90.
The UV-irradiated sample was kept in an environment of 25 ° C. and 60% for 24 hours. Then, the temporary support of the sample was peeled off, the crystal oscillator was attached to the sample holder, and the crystal oscillator was mounted on the QCM development unit. A developer (1.0 mass% sodium carbonate aqueous solution at a temperature of 30 ° C.) was used, and the sample mounted on the QCM unit was immersed in the developer. The mass change was monitored, and the mass increase rate (mass%) of the cured film of the negative photosensitive composition layer was measured 30 seconds after being immersed in the above solution.

[Evaluation of transfer film]
Each of the obtained transfer films of Examples and Comparative Examples was evaluated as shown below. Table 2 shows the evaluation results.

<Evaluation of transfer film 1>
(Evaluation method for reattachment failure)
The film in which the transparent film and the transparent electrode layer were formed on the transparent film substrate was washed, and the transferred films of Examples and Comparative Examples were laminated on the washed film. The film width was 500 mm. The laminating conditions were a transparent film substrate temperature of 100 ° C., a rubber roller temperature of 100 ° C., a linear pressure of 100 N / cm, and a transport speed of 4 m / min.
Ultraviolet irradiation was performed through an exposure mask (an exposure mask in which a line and space pattern having a width of 10 μm is engraved on the entire surface) using an ultrahigh pressure mercury lamp with an exposure amount twice that of E90 described above.
The UV-irradiated sample was kept in an environment of 25 ° C. and 60% for 24 hours. Then, the temporary support of the sample was peeled off, and development treatment was performed using a 1.0 mass% sodium carbonate aqueous solution. The development process was carried out by a roll-to-roll process of a developer circulation system, and the development conditions were a temperature of 30 ° C., a time of 30 seconds, and a shower pressure of 0.10 MPa. Immediately after the development treatment, a rinsing treatment was performed using pure water. The pure water rinsing conditions were a temperature of 30 ° C., a time of 30 seconds, and a shower pressure of 0.10 MPa. A film equivalent to a length of 1000 m was processed.
A 10 × 10 cm size sampling was performed from the last 1 m portion of the treated film, the number of redeposition occurrences of undissolved developed material was measured with an optical microscope, and evaluation was carried out based on the following evaluation criteria. D or higher is a level at which there is no practical problem.
"A" ... No reattachment "B" ... 1 to 2 reattachment "C" ... 3 to 5 reattachment "D" ... 6 reattachment ~ 10 "E" ... 11 to 30 reattachments "F" ... 31 or more reattachments

<Evaluation of transfer film 2>
(Evaluation of transferability)
A substrate having a line-and-space pattern formed of copper having a thickness of 200 nm and a width of 10 μm was prepared on PET (polyethylene terephthalate) having a thickness of 75 μm and a width of 500 mm. The transfer films of Examples and Comparative Examples were laminated in a direction orthogonal to the line of this substrate. The film width was 500 mm. The laminating conditions were a transparent film substrate temperature of 100 ° C., a rubber roller temperature of 100 ° C., a linear pressure of 100 N / cm, and a transport speed of 4 m / min.
The substrate after transfer was visually observed and observed with an optical microscope to evaluate the presence or absence of bubbles. "B" and above are practically acceptable levels.
(Evaluation criteria)
"A" ... Bubbles cannot be seen visually or with an optical microscope "B" ... Bubbles cannot be seen visually, but bubbles can be seen with an optical microscope "C" ... Bubbles can be seen both visually and with an optical microscope

<Evaluation of transfer film 3>
(Evaluation of protective film peelability)
The produced transfer film was cut into A4 size, and the cover film at the end was slightly peeled off. The temporary support at the peeled portion was held with the left hand and the protective film with the right hand, and peeled in the air at a speed of 1 m / min. The state of the transfer film after the protective film was peeled off was visually evaluated. "B" and above are practically acceptable levels.
(Evaluation criteria)
"A" ... The photosensitive composition layer remains on the temporary support side. "B" ... Most of the photosensitive composition layer remains on the temporary support side, but a part of the photosensitive composition layer remains on the protective film side. It is attached.
"C": Most of the photosensitive composition layer is attached to the protective film side.

Table 2 is shown below.
In Table 2, in "Presence / absence of a structural unit having a radically polymerizable group in the binder polymer" in "Characteristic points of the negative photosensitive composition layer", "P" is a configuration in which the binder polymer has a radically polymerizable group. It represents having a unit, and "N" means that the binder polymer does not have a structural unit having a radically polymerizable group.
Further, in Table 2, in the "content of the structural unit having a radically polymerizable group in the binder polymer" in the "characteristic points of the negative photosensitive composition layer", "P" is the radical polymerizable in the binder polymer. The content of the structural unit having a group is 20% by mass or more with respect to all the structural units, and "N" means that the content is less than 20% by mass.
Further, in Table 2, in "presence or absence of a polyfunctional compound having four or more functionalities" in "characteristic points of the negative photosensitive composition layer", "P" indicates that the polymerizable compound has four or more functionalities. "N" means that it does not have a polyfunctional compound having four or more functionalities.
Further, in Table 2, in the "content of the polymerization inhibitor" in the "characteristic points of the negative photosensitive composition layer", in "P", the content of the polymerization inhibitor is the content of the photopolymerization initiator. On the other hand, it represents 5 to 15% by mass, and "N" means that the content is less than 5% by mass or more than 15% by mass.
Further, in Table 2, the "purification treatment of the binder polymer (presence or absence of reprecipitation)" in the "characteristic points of the negative photosensitive composition layer" means whether the binder polymer was purified by reprecipitation after the polymerization. Indicates whether or not. "P" indicates that purification by reprecipitation was performed, and "N" indicates that purification by reprecipitation was not performed.

From the results in Table 2, it was confirmed that the pattern formed by the transfer film of the example suppressed defects due to reattachment failure.
Further, from the evaluation results of the examples, it was confirmed that when the value of E10 / E90 represented by the formula (1) is 0.8 or more, the defects due to the reattachment failure of the formed pattern are further suppressed. rice field.
Further, from the evaluation results of the examples, it was confirmed that when the negative photosensitive composition layer contains a polyfunctional compound having four or more functionalities, defects due to reattachment failure of the formed pattern are further suppressed.
Further, from the comparison of Examples 1 to 10, 35 and 36, it was confirmed that when the binder polymer contains a structural unit having a radically polymerizable group, defects due to reattachment failure of the formed pattern are further suppressed. rice field. In particular, when the weight average molecular weight (Mw) of the binder polymer is 30,000 or less and the proportion of the structural units having radical polymerizable groups in the binder polymer is 40% by mass or more, the formed pattern is re-formed. It was confirmed that defects due to adhesion failure were further suppressed.
Further, from the evaluation results of Examples 1, 3 and 11 to 13, the mass content ratio of the polymerizable compound to the binder polymer (content of the polymerizable compound / content to the binder polymer) is 0. It was confirmed that when the value was 5.5 or more (preferably 0.7 or more), defects due to reattachment failure of the formed pattern were further suppressed.
Further, from the evaluation results of Examples 3 and 10, when the binder polymer is purified by reprecipitation after the polymerization reaction, defects due to reattachment failure of the formed pattern are further suppressed. Was confirmed.
Further, from the evaluation results of Examples 3 and 24 and 25, when the film thickness of the negative photosensitive composition layer is 3.0 μm or less, defects due to reattachment failure of the formed pattern are further suppressed. It was confirmed that it would be done.

On the other hand, the pattern formed by the transfer film of the comparative example did not meet the desired requirements.

[Preparation and evaluation of transfer films of Examples 1A to 36A]
[Preparation of Transfer Films of Examples 1A to 36A]
<Preparation of transfer film of Example 1A>
Example 1 except that a step of forming a refractive index adjusting layer on the negative photosensitive composition layer after forming the negative photosensitive composition layer and before crimping the protective film was carried out by the following procedure. The transfer film of Example 1A (a transfer film having a temporary support, a negative photosensitive composition layer, a refractive index adjusting layer, and a protective film) was produced by the same method as in the above.
(Step of forming the refractive index adjusting layer)
The coating liquid A shown in Table 3 is applied onto the negative photosensitive composition layer using a slit-shaped nozzle after adjusting the thickness to 70 nm after drying, and has a temperature gradient of 40 ° C to 95 ° C. It was dried with a hot air convection dryer to remove the solvent, and a refractive index adjusting layer was formed.
The refractive index of the refractive index adjusting layer was 1.68 at a wavelength of 550 nm at 25 ° C.

<Preparation of Transfer Films of Examples 2A to 36A>
Example 2 except that a step of forming a refractive index adjusting layer on the negative photosensitive composition layer after forming the negative photosensitive composition layer and before crimping the protective film was carried out by the following procedure. The transfer films of Examples 2A to 36A (transfer film having a temporary support, a negative photosensitive composition layer, a refractive index adjusting layer, and a protective film) were prepared by the same method as in ~ 36.
(Step of forming the refractive index adjusting layer)
The coating liquid A shown in Table 3 is applied onto the negative photosensitive composition layer using a slit-shaped nozzle after adjusting the thickness to 70 nm after drying, and has a temperature gradient of 40 ° C to 95 ° C. It was dried with a hot air convection dryer to remove the solvent, and a refractive index adjusting layer was formed.
The refractive index of the refractive index adjusting layer was 1.68 at a wavelength of 550 nm at 25 ° C.

In Table 3, "Compound B" is the following polymer. In the following, the ratio of the repeating units in the formula was 50: 4: 38: 8 in order from the repeating unit on the left side (based on mass).

[Evaluation of Transfer Films of Examples 1A to 36A]
When the above-mentioned [evaluation of transfer film] was carried out, it was confirmed that the transfer films of Examples 1A to 36A had the same evaluation results as the transfer films of Examples 1 to 36, respectively.

[Preparation and evaluation of transfer films of Examples 1B to 36B]
[Preparation of Transfer Films of Examples 1B to 36B]
<Preparation of transfer film of Example 1B>
Example 1 except that a step of forming a refractive index adjusting layer on the negative photosensitive composition layer after forming the negative photosensitive composition layer and before crimping the protective film was carried out by the following procedure. The transfer film of Example 1B (a temporary support, a negative photosensitive composition layer, a refractive index adjusting layer, and a transfer film having a protective film) was produced by the same method as in the above.
(Step of forming the refractive index adjusting layer)
The above-mentioned coating liquid A shown in Table 3 is applied onto the negative photosensitive composition layer so that the thickness after drying is 81 nm using a slit-shaped nozzle, and the temperature gradient is 40 ° C to 95 ° C. The solvent was removed by drying with a hot air convection dryer, and a refractive index adjusting layer was formed.
The refractive index of the refractive index adjusting layer was 1.68 at a wavelength of 550 nm at 25 ° C.

<Preparation of Transfer Films of Examples 2B to 36B>
Example 2 except that a step of forming a refractive index adjusting layer on the negative photosensitive composition layer after forming the negative photosensitive composition layer and before crimping the protective film was carried out by the following procedure. The transfer films of Examples 2B to 36B (transfer film having a temporary support, a negative photosensitive composition layer, a refractive index adjusting layer, and a protective film) were prepared by the same method as in ~ 36.
(Step of forming the refractive index adjusting layer)
The above-mentioned coating liquid A shown in Table 3 is applied onto the negative photosensitive composition layer so that the thickness after drying is 81 nm using a slit-shaped nozzle, and the temperature gradient is 40 ° C to 95 ° C. The solvent was removed by drying with a hot air convection dryer, and a refractive index adjusting layer was formed.
The refractive index of the refractive index adjusting layer was 1.68 at a wavelength of 550 nm at 25 ° C.

[Evaluation of Transfer Films of Examples 1B to 36B]
When the above-mentioned [evaluation of transfer film] was carried out, it was confirmed that the transfer films of Examples 1B to 36B had the same evaluation results as the transfer films of Examples 1 to 36, respectively.

[Preparation and Evaluation of Transfer Films of Examples 1C to 36C]
[Preparation of Transfer Films of Examples 1C to 36C]
<Preparation of Transfer Film of Example 1C>
Example 1 except that a step of forming a refractive index adjusting layer on the negative photosensitive composition layer after forming the negative photosensitive composition layer and before crimping the protective film was carried out by the following procedure. The transfer film of Example 1C (a transfer film having a temporary support, a negative photosensitive composition layer, a refractive index adjusting layer, and a protective film) was produced by the same method as in the above.
(Step of forming the refractive index adjusting layer)
The above-mentioned coating liquid A shown in Table 3 is applied onto the negative photosensitive composition layer so that the thickness after drying is 59 nm using a slit-shaped nozzle, and the temperature gradient is 40 ° C to 95 ° C. The solvent was removed by drying with a hot air convection dryer, and a refractive index adjusting layer was formed.
The refractive index of the refractive index adjusting layer was 1.68 at a wavelength of 550 nm at 25 ° C.

<Preparation of Transfer Films of Examples 2C to 36C>
Example 2 except that a step of forming a refractive index adjusting layer on the negative photosensitive composition layer after forming the negative photosensitive composition layer and before crimping the protective film was carried out by the following procedure. The transfer films of Examples 2C to 36C (transfer film having a temporary support, a negative photosensitive composition layer, a refractive index adjusting layer, and a protective film) were prepared by the same method as in ~ 36.
(Step of forming the refractive index adjusting layer)
The above-mentioned coating liquid A shown in Table 3 is applied onto the negative photosensitive composition layer so that the thickness after drying is 59 nm using a slit-shaped nozzle, and the temperature gradient is 40 ° C to 95 ° C. The solvent was removed by drying with a hot air convection dryer, and a refractive index adjusting layer was formed.
The refractive index of the refractive index adjusting layer was 1.68 at a wavelength of 550 nm at 25 ° C.

[Evaluation of Transfer Films of Examples 1C to 36C]
When the above-mentioned [evaluation of transfer film] was carried out, it was confirmed that the transfer films of Examples 1C to 36C had the same evaluation results as the transfer films of Examples 1 to 36, respectively.

[Examples 1D to 36D: Fabrication and evaluation of a liquid crystal display device provided with a touch panel]
[Preparation of transparent laminate]
A substrate having a refractive index adjusting layer, an ITO transparent electrode pattern, and copper routing wiring formed on a cycloolefin transparent film was prepared.
Using the transfer films of Examples 1A to 36A, Examples 1B to 36B, and Examples 1C to 36C from which the protective film was peeled off, the refractive index adjusting layer, the ITO transparent electrode pattern, and the copper routing wiring were transferred to the transfer film. Laminated at the position covered by. Lamination was performed using a vacuum laminator manufactured by MCK under the conditions of a cycloolefin transparent film temperature: 40 ° C., a rubber roller temperature of 100 ° C., a linear pressure of 3 N / cm, and a transport speed of 4 m / min.
After that, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, the surface of the exposure mask (quartz exposure mask having a pattern for forming an overcoat) and the temporary support are brought into close contact with each other. , Pattern exposure was performed with an exposure amount of 100 mJ / cm ² (i-line) via a temporary support.
After peeling off the temporary support, development treatment was carried out at 30 ° C. for 30 seconds with a 1% by mass aqueous solution of sodium carbonate.
Then, the residue was removed by injecting ultrapure water from the ultrapure water cleaning nozzle onto the transparent film substrate after the development treatment. Subsequently, air is blown to remove water on the transparent film substrate, and post-baking treatment is performed at 145 ° C. for 30 minutes. A transparent laminated body in which the rate adjusting layer and the cured film were laminated in order was formed.
A touch panel was manufactured by a known method using the prepared transparent laminate. A liquid crystal display device provided with a touch panel was manufactured by attaching the manufactured touch panel to a liquid crystal display element manufactured by the method described in paragraphs 097 to 0119 of JP2009-47936A.
It was confirmed that the liquid crystal display device equipped with a touch panel has excellent display characteristics and operates without problems.

1, 11, 34

Temporary support

2, 12

Composition layer

3, 17, 32, 41 Negative type photosensitive composition layer 5 Refraction

rate adjustment layer

7, 19

Protective film

10, 20 Transfer film 13 Thermoplastic resin layer 15 Intermediate Layer 30 Glass substrate 32A Hardened film of negative photosensitive composition layer 40 Base material 42 Mask 43 Exposed part 44 Unexposed part 45 Half exposed part T Negative type photosensitive composition layer thickness T1, T2, T3 Negative type photosensitive Film thickness of the cured film of the sex composition layer T100 Standard film thickness T10 10% film thickness with respect to the standard film thickness T100 T90 90% film thickness with respect to the standard film thickness T100 E10 T90 Exposure amount E90 T90 Exposure amount P1 and P2 when

Claims

A transfer film having a temporary support and a composition layer.
The composition layer contains a negative photosensitive composition layer.
The negative photosensitive composition layer contains a binder polymer, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator.
A transfer film that meets the following requirements 1 and 2.
Requirement 1: The surface of the transfer film opposite to the temporary support side is brought into contact with the glass substrate to form a laminate having the glass substrate, the composition layer, and the temporary support in this order, and the laminate is formed. The thickness of the cured film of the negative photosensitive composition layer in the exposed portion after the body is exposed to a plurality of locations while increasing the exposure amount and the development and cleaning treatment satisfying the following condition A is performed. The measurement was performed, and the points corresponding to the film thickness and the exposure amount at each exposure point were plotted on the orthogonal coordinates with the film thickness of the cured film as the vertical axis and the exposure amount as the horizontal axis, and the film thickness changed substantially. The film thickness at the exposure amount that disappears is used as the reference film thickness, and the exposure amount E10 at which the film thickness of the cured film is 10% of the reference film thickness and the film thickness of the cured film are obtained from the orthogonal coordinates. When the exposure amount E90, which is 90% of the reference film thickness, is calculated, the relationship of the following formula (1) is satisfied.
Condition A: A development treatment is carried out for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution having a temperature of 30 ° C., and then a cleaning treatment is carried out for 30 seconds using pure water having a temperature of 30 ° C. .. The development process is development by a shower method, the shower pressure is 0.10 MPa, and the shower flow rate is 1000 mL / min. Further, the washing treatment is washing by a shower method, the shower pressure is 0.10 MPa, and the shower flow rate is 1000 mL / min.
Equation (1): E10 / E90 ≧ 0.5
Requirement 2: The surface of the transfer film opposite to the temporary support side is brought into contact with the quartz crystal to form a laminate having the quartz crystal, the composition layer, and the temporary support in this order. After irradiating the laminate with ultraviolet rays at twice the exposure amount of E90, when the exposed laminate is immersed in a 1.0 mass% sodium carbonate aqueous solution having a temperature of 30 ° C., crystal vibration occurs. The mass increase rate of the cured film of the negative photosensitive composition layer 30 seconds after the start of immersion, which is determined based on the child microbalance method, is 20% by mass or less.
The transfer film according to claim 1, further satisfying the following formula (1-1).
Equation (1-1): E10 / E90 ≧ 0.8
In the formula (1-1), the E10 and the E90 are synonymous with the E10 and the E90 in the formula (1), respectively.
The transfer film according to claim 1 or 2, wherein the mass content ratio of the polymerizable compound to the binder polymer is 0.5 or more.
The transfer film according to any one of claims 1 to 3, wherein the negative photosensitive composition layer contains a tetrafunctional or higher polymerizable compound.
The transfer film according to any one of claims 1 to 4, wherein the binder polymer has a radically polymerizable group.
The binder polymer contains a structural unit having the radically polymerizable group.
The transfer film according to claim 5, wherein the content of the structural unit having a radically polymerizable group is 20% by mass or more with respect to all the structural units in the binder polymer.
The negative photosensitive composition layer further contains a polymerization inhibitor and contains
The transfer film according to any one of claims 1 to 6, wherein the content of the polymerization inhibitor is 5 to 15% by mass with respect to the content of the photopolymerization initiator.
The transfer film according to any one of claims 1 to 7, wherein the composition layer includes a refractive index adjusting layer.
The transfer film according to any one of claims 1 to 8, which is used for forming a protective film for a touch panel.
The transfer film according to any one of claims 1 to 8, which is used for a touch panel electrode pattern forming etching resist.
The surface of the transfer film according to any one of claims 1 to 8 opposite to the temporary support is brought into contact with a substrate having a conductive layer and bonded to the substrate, the conductive layer, and the composition. A bonding step of obtaining a substrate with a layer and a composition layer having the temporary support in this order, and
An exposure step of pattern-exposing the composition layer and
A developing step of developing the exposed composition layer to form a protective film pattern that protects the conductive layer.
Further, laminating including a peeling step of peeling the temporary support from the substrate with the composition layer between the bonding step and the exposure step, or between the exposure step and the developing step. How to make a body.
The method for manufacturing a laminate according to claim 11, wherein the developing step is a step of repeatedly using the developing solution by circulating the developing solution.
The bonding step is a step of bonding the transfer film and the substrate having the conductive layer by roll-to-roll, and at least the exposure step for the long laminated body formed by the bonding step. The method for producing a laminate according to claim 11 or 12, wherein the development step is carried out.
The method for manufacturing a laminate according to any one of claims 11 to 13, wherein the substrate having the conductive layer is a substrate having at least one of a touch panel electrode and a touch panel wiring.
The surface of the transfer film according to any one of claims 1 to 8, which is opposite to the temporary support, is brought into contact with a substrate having a conductive layer, and the substrate, the conductive layer, the composition layer, and the like. , A bonding step of obtaining a substrate with a composition layer having the temporary supports in this order, and
An exposure step of pattern-exposing the composition layer and
A developing step of developing the exposed composition layer to form a resin pattern,
An etching step of etching the conductive layer in a region where the resin pattern is not arranged, and an etching step of etching the conductive layer.
Further, a method for manufacturing a circuit wiring, comprising a peeling step of peeling the temporary support from the substrate with the composition layer between the bonding step and the exposure step, or between the exposure step and the developing step.