WO2024004430A1

WO2024004430A1 - Transfer film, pattern forming method, and circuit wiring manufacturing method

Info

Publication number: WO2024004430A1
Application number: PCT/JP2023/018834
Authority: WO
Inventors: 壮二石坂; 一真両角
Original assignee: 富士フイルム株式会社
Priority date: 2022-06-30
Filing date: 2023-05-19
Publication date: 2024-01-04
Also published as: TW202402530A

Abstract

Provided are: a transfer film including a temporary support and a transfer layer disposed on the temporary support, the temporary support having a thermal deformation rate of 1.0% or less; and a use for said transfer film.

Description

Transfer film, pattern forming method, and circuit wiring manufacturing method

The present disclosure relates to a transfer film, a pattern forming method, and a circuit wiring manufacturing method.

Since the number of steps required to obtain a predetermined pattern is small, a widely used method is to place a transfer layer on an arbitrary substrate using a transfer film, expose the transfer layer to light through a mask, and then develop it. ing.

For example, International Publication No. 2017/007001 discloses a photosensitive element comprising a support film, an intermediate layer, and a photosensitive layer in this order, wherein the support film has a thickness of 20 μm or more, and the support film contains A photosensitive element is disclosed in which the number of particles with a diameter of 5 μm or more is 30 particles/mm ² or less.

It has been found that with conventional transfer films, when the temporary support is peeled off after the transfer film and the substrate are bonded together, the substrate is deformed. Therefore, it is required to suppress deformation of the substrate.

According to one embodiment of the present invention, a transfer film capable of suppressing deformation of a substrate used in a transfer process is provided.
Further, according to other embodiments of the present invention, a method for forming a pattern using the above transfer film and a method for manufacturing a circuit board are provided.

The present disclosure includes the following aspects.
<1> A transfer film comprising a temporary support and a transfer layer disposed on the temporary support, wherein the temporary support has a thermal deformation rate of 1.0% or less.
<2> The transfer film according to <1>, wherein the transfer layer has a surface free energy of 68.0 mJ/m ² or less on the side facing the temporary support.
<3> The transfer film according to <1> or <2>, wherein the transfer layer is in contact with the surface of the temporary support, and the surface roughness Rmax of the surface of the temporary support on the transfer layer side is 0.5 μm or less.
<4> The transfer film according to any one of <1> to <3>, wherein the transfer layer includes a photosensitive layer.
<5> The transfer film according to <4>, wherein the transfer layer includes an intermediate layer between the temporary support and the photosensitive layer.
<6> The transfer film according to <5>, wherein the transfer layer includes a thermoplastic resin layer between the temporary support and the intermediate layer.
<7> The transfer film according to any one of <1> to <6>, wherein the temporary support has a haze of greater than 2.0%.
<8> The transfer according to any one of <1> to <7>, wherein the total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more contained in the temporary support is more than 30 pieces/mm ² film.
<9> The temporary support is any one of <1> to <8>, including a region in which the total area ratio of optically abnormal regions is larger than 300 ppm when observed with an epi-reflection laser microscope in an area of 13.5 mm ² 1. The transfer film according to item 1.
<10> The transfer film according to any one of <1> to <9>, wherein the temporary support has a thickness of 25 μm or more.
<11> The transfer film according to any one of <4> to <6>, wherein the photosensitive layer contains an alkali-soluble resin having an acid value of 80 mgKOH/g to 250 mgKOH/g.
<12> The transfer film according to any one of <4> to <6>, wherein the photosensitive layer contains an alkali-soluble resin having a crosslinkable group.
<13>
The photosensitive layer is an alkali-soluble layer in which the mass ratio of the content of (meth)acrylic acid ester-derived structural units to the total content of styrene-derived structural units and styrene derivative-derived structural units is 0.3 to 2.5. The transfer film according to any one of <4> to <6>, containing a resin.
<14> The transfer film according to any one of <1> to <13>, wherein the transfer layer has a water content of 0.1% by mass or more based on the total amount of the transfer layer.
<15> The transfer film according to any one of <4> to <6>, wherein the photosensitive layer has a water content of 0.1% by mass or more based on the total amount of the photosensitive layer.
<16> The transfer layer according to any one of <1> to <14>, wherein the content of iron atoms is 0.01 ppm to 10.0 ppm on a mass basis with respect to the total amount of the transfer layer. film.
<17> The photosensitive layer has an iron atom content of 0.01 ppm to 10.0 ppm on a mass basis based on the total amount of the photosensitive layer, described in any one of <4> to <6>. transfer film.
<18> A step of preparing a transfer film including a temporary support and a transfer layer disposed on the temporary support, and placing the transfer film and the substrate on the opposite side of the transfer film from the surface of the temporary support. A step of bonding the substrate so that the surface is in contact with the substrate, a step of peeling off the temporary support to obtain a laminate, a step of exposing the laminate to light in a pattern, and a step of developing the laminate after exposure. forming a pattern, wherein the temporary support has a thermal deformation rate of 1.0% or less.
<19>
A step of preparing a transfer film including a temporary support and a transfer layer disposed on the temporary support; a step of attaching the laminate so that it is in contact with the laminate, a step of peeling off the temporary support to obtain a laminate, a step of exposing the laminate to light in a pattern, and a step of developing the laminate after exposure to form a pattern. A step of plating an area of the substrate where no pattern is placed, and a step of peeling off the pattern, and the temporary support is a circuit wiring having a thermal deformation rate of 1.0% or less. manufacturing method.

FIG. 1 is a schematic diagram showing an example of the configuration of a transfer film according to the present disclosure.

The present disclosure will be described in detail below.
In the present disclosure, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In the present disclosure, in numerical ranges described in stages, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. Moreover, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.

In the present disclosure, each component may contain multiple types of corresponding substances.
In the present disclosure, the term "layer" includes, when observing a region where the layer or film exists, not only the case where the layer or film is formed in the entire region, but also the case where the layer or film is formed only in a part of the region. This also includes cases.

In the present disclosure, the term "step" is used not only to refer to an independent step, but also to include the term "step" even if it cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

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

In the present disclosure, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) refer to columns such as TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all brand names manufactured by Tosoh Corporation). ), using THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard material, and the value calculated using polystyrene as the standard material measured with a gel permeation chromatography (GPC) analyzer. be.

In the present disclosure, unless otherwise specified, ratios of constituent units of polymers are mass ratios.
In the present disclosure, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight average molecular weight (Mw).

In the present disclosure, "(meth)acrylic" is a concept that includes both acrylic and methacrylic. "(Meth)acryloyloxy group" is a concept that includes both acryloyloxy group and methacryloyloxy group. "(Meth)acryloyl group" is a concept that includes both acryloyl group and methacryloyl group.

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

In the present disclosure, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, water-soluble resin is intended to be a resin that satisfies the above-mentioned solubility conditions.

In the present disclosure, the "solid content" of the composition refers to the components forming the composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent is means all ingredients except. In addition, liquid components are also considered solid components as long as they form a composition layer.

In the present disclosure, "thickness" is calculated as the average value of five arbitrary points measured by cross-sectional observation of a target using a SEM (Scanning Electron Microscope).

[Transfer film]
The transfer film according to the present disclosure includes a temporary support and a transfer layer disposed on the temporary support, and the temporary support has a thermal deformation rate of 1.0% or less.

The present inventors have discovered that by setting the thermal deformation rate of the temporary support on the side of the transfer film to be bonded to the substrate in the transfer process to be 1.0% or less, deformation occurring in the substrate in the transfer process is suppressed. .

Conventionally, it has been found that when a temporary support is peeled off after a transfer film is attached to a substrate, the substrate is deformed. This is thought to be because the transfer film is more easily expanded by heat than the substrate, and the transfer film is attached to the substrate in an expanded state. Then, when the temporary support is peeled off, the transfer layer contracts. This is considered to cause deformation of the substrate.

On the other hand, when the transfer film of the present disclosure is used, since the thermal deformation rate of the temporary support is 1.0% or less, expansion and contraction of the transfer film due to heat is unlikely to occur, and the transfer film is adhered to the transfer film. Deformation of the substrates to be matched is suppressed.

Hereinafter, the transfer film according to the present disclosure will be described in detail.

The transfer film according to the present disclosure includes a temporary support and a transfer layer disposed on the temporary support.

In the transfer film, the temporary support and the transfer layer may be directly laminated without any other layer, or the temporary support and the transfer layer may be laminated with another layer interposed therebetween. Further, another layer may be laminated on the surface of the transfer layer opposite to the surface facing the temporary support.

Examples of layers other than the temporary support and the transfer layer include a protective film.

The protective film is preferably placed on the surface of the transfer layer opposite to the surface facing the temporary support.

Furthermore, each layer may be a single layer or a multilayer of two or more layers.

An example of the embodiment of the transfer film according to the present disclosure is shown below, but is not limited thereto.
(1) “Temporary support/transfer layer (photosensitive layer)/protective film”
(2) “Temporary support/transfer layer (intermediate layer/photosensitive layer)/protective film”
(3) “Temporary support/transfer layer (thermoplastic resin layer/intermediate layer/photosensitive layer)/protective film”
In each of the above configurations, the photosensitive layer may be either a negative photosensitive layer or a positive photosensitive layer, but is preferably a negative photosensitive layer. Moreover, it is also preferable that the photosensitive layer is a colored resin layer.

The transfer film according to the present disclosure is preferably used as a transfer film for etching resist.

In the case of a structure in which the transfer film further has another layer on the side opposite to the temporary support side of the photosensitive layer, the total thickness of the other layers arranged on the side opposite to the temporary support side of the photosensitive layer is the photosensitive layer. The amount is preferably 0.1% to 30%, more preferably 0.1% to 20%, based on the thickness of the sexual layer.

From the viewpoint of suppressing bubble generation during the bonding process described below, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The maximum width of the waviness of the transfer film is preferably 0 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more.

The maximum width of waviness of the transfer film is a value measured by the following procedure.
First, a test sample is prepared by cutting the transfer film in a direction perpendicular to the main surface to a size of 20 cm in length x 20 cm in width. In addition, when the transfer film has a protective film, the protective film is peeled off. Next, the test sample is placed on a stage with a smooth and horizontal surface so that the surface of the temporary support faces the stage. After standing, the surface of the test sample was scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) for a 10 cm square area at the center of the test sample to obtain a three-dimensional surface image. Subtract the minimum concavity height from the maximum convexity height observed in the dimensional surface image. The above operation is performed on 10 test samples, and the arithmetic mean value thereof is defined as the "maximum waviness of the transfer film".

Hereinafter, a transfer film according to the present disclosure will be described by citing an example of a specific embodiment.

The transfer film 20 shown in FIG. 1 includes a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive layer 17, and a protective film 19 in this order.

Note that although the transfer film 20 shown in FIG. 1 has a protective film 19 disposed therein, the protective film 19 does not need to be disposed.

Further, the transfer film 20 shown in FIG. 1 has a form in which a thermoplastic resin layer 13 and an intermediate layer 15 are arranged, but the thermoplastic resin layer 13 or the intermediate layer 15, or the thermoplastic resin layer 13 and the intermediate layer 15, It does not have to be placed.

Each element constituting the transfer film according to the present disclosure will be described below.

[Temporary support]
The transfer film according to the present disclosure includes a temporary support.
The temporary support is a support that supports the transfer layer and is removable.

The temporary support may be a single layer or a laminate of two or more layers.
Examples of temporary supports include those consisting only of a base material; a laminate comprising a base material and a particle-containing layer disposed on one side of the base material; and a base material and both sides of the base material. A laminate including a particle-containing layer disposed in a particle-containing layer is mentioned.

Examples of the base material constituting the temporary support include glass, resin film, and paper. The base material constituting the temporary support is preferably a resin film from the viewpoints of strength, flexibility, and light transmittance.

Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among these, the resin film is preferably a PET film, more preferably a biaxially stretched PET film.

When a particle-containing layer is arranged on one or both surfaces of the base material, the number of particle-containing layers may be one layer, or two or more layers.

The particle-containing layer is formed, for example, by applying a particle-containing layer composition onto a base material and drying it. Moreover, the particle-containing layer can also be arranged by a coextrusion method when forming a resin film. Preferably, the particle-containing layer composition includes a binder polymer and particles. The type of binder polymer is not particularly limited, and can be appropriately selected depending on the purpose, for example. Examples of the binder polymer include acrylic resin, urethane resin, olefin resin, styrene-butadiene resin, ester resin, vinyl chloride resin, and vinylidene chloride resin. When disposing the particle-containing layer by coextrusion, it is preferable to use PET as the binder polymer.

The particle-containing layer may contain one type of binder polymer and particles, or may contain two or more types of particles.

The particles contained in the particle-containing layer are not particularly limited and can be appropriately selected depending on the purpose. The content of particles in the particle-containing layer can be adjusted as appropriate by adjusting the amount of particles added to the composition for particle-containing layer. In this specification, the particles contained in the particle-containing layer are referred to as "additional particles."

Additive particles are to be distinguished from impurities unexpectedly mixed in during the manufacturing process of the temporary support and particles formed during the manufacturing process of the temporary support. The additive particles are preferably particles that do not melt at 200°C.

Whether or not the temporary support is an added particle can be determined, for example, by the following method. Since the additive particles usually have uniformity in shape and distribution, they can be identified by observing them with an optical microscope.

Examples of the additive particles include inorganic particles and organic particles.

Examples of the inorganic particles include particles of inorganic oxides such as silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina).

Examples of organic particles include particles of polymers such as acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene.

When the temporary support has a particle-containing layer, the additive particles contained in the particle-containing layer are preferably particles of an inorganic oxide.

The average particle diameter of the additive particles is not particularly limited, but is, for example, 0.1 μm to 10 μm. The average particle size is measured by cutting a section with a thickness of 100 nm using an ultramicrotome and using a TEM (transmission electron microscope).

In the transfer film according to the present disclosure, the thermal deformation rate of the temporary support is 1.0% or less, preferably 0.5% or less. The lower limit of the thermal deformation rate is not particularly limited, and is preferably 0%. When the thermal deformation rate of the temporary support is 1.0% or less, deformation of the substrate to be bonded to the transfer film is suppressed.

In the present disclosure, the thermal deformation rate is measured by the following method.

On the main surface of the temporary support, a direction parallel to one of the two opposing sides is defined as the A direction, and a direction perpendicular to the A direction is defined as the B direction.
A test piece cut out to have a length of 30 mm in the A direction and 4 mm in the B direction, and a test piece cut out to have a length of 30 mm in the B direction and 4 mm in the A direction are prepared.
The following measurements are performed using two test pieces.
As a measuring device, a thermal expansion coefficient measuring device (product name "TMA450EM", manufactured by TA Instruments) is used.
The measurement conditions are as follows.
Measurement mode: Tensile mode Grip distance: 16mm
Set load: Change from 0.05N to 0.48N at 6.00N/min.
Each test piece is heated from 25°C to 100°C at a heating rate of 20°C/min, the elongation rate of each test piece is measured five times, and the average value is calculated.
Of the two test pieces, the one with the larger average elongation rate is adopted as the thermal deformation rate.

Examples of methods for reducing the thermal deformation rate of the temporary support include a method of increasing the thickness of the temporary support, and a method of increasing the number of particles contained in the temporary support by making the temporary support contain particles. It will be done.

In the transfer film according to the present disclosure, the haze of the temporary support is preferably greater than 2.0% from the viewpoint of suppressing deformation of the substrate to be bonded to the transfer film.

From the above viewpoint, the haze of the temporary support is more preferably 2.5% or more. The upper limit of haze is not particularly limited, and is, for example, 10%.

When forming a pattern using the transfer film according to the present disclosure, it is preferable to peel off the temporary support after the transfer film and the substrate are bonded together and before exposure. If the temporary support is peeled off before exposure, there is no need to consider the influence of the high haze of the temporary support on exposure.

In the present disclosure, haze is measured using a haze meter according to JIS K7136:2000. As the haze meter, for example, the product name "NDH-2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. is used.

Further, in the transfer film according to the present disclosure, from the viewpoint of suppressing deformation of the substrate to be bonded to the transfer film, the total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more contained in the temporary support is 30. Preferably, it is greater than /mm ² .

From the above viewpoint, the total number of particles and aggregates is more preferably 40 particles/mm ² or more. The upper limit of the total number is not particularly limited, and is, for example, 50 pieces/mm ² .

The term "particles" and "agglomerates" as used herein means those having a region in which a difference in polarization from the surrounding region can be observed when the temporary support is observed with a polarizing microscope. Particles and aggregates include, for example, resin carbides formed during the manufacture of the base material and catalysts used in the manufacture of the base material. Further, when providing a particle-containing layer as described above, the additive particles contained in the particle-containing layer also correspond to the above-mentioned particles.

In the present disclosure, the total number of particles and aggregates contained in the temporary support is measured by the following method.

First, the temporary support was observed with a polarizing microscope (product name: "BX60" with "U-POT" filter and "U-AN360" filter inserted to make a simple polarizing microscope, 10x objective lens, manufactured by Olympus). Then, the part where the polarization disturbance occurs is identified as a foreign object (particle or aggregate). The identified foreign matter is observed with an epi-illumination laser microscope (product name: "Confocal Laser Microscope VL2000D", manufactured by Lasertec). Further, the diameter of the foreign object is measured using an optical microscope (product name "BX60", objective lens 100 times, manufactured by Olympus Corporation), and the number of foreign objects with a diameter of 5 μm or more included in the observation area of 1 mm ² is counted. Note that if the foreign object contains voids, the diameter is measured including the voids. If the foreign object is not circular, measure the longest diameter.

When forming a pattern using the transfer film according to the present disclosure, it is preferable to peel off the temporary support after bonding the transfer film and the base material and before exposure. If the temporary support is peeled off before exposure, it is not necessary to consider the influence on exposure due to the large number of particles and aggregates contained in the temporary support.

In addition, in the transfer film according to the present disclosure, from the viewpoint of suppressing deformation of the substrate to be bonded to the transfer film, the temporary support has an optically abnormal area when observed with an epi-illumination laser microscope in an area of 13.5 mm ² It is preferable to include a region in which the total area ratio of is larger than 300 ppm.

From the above viewpoint, it is more preferable that the total area ratio of the optically abnormal region is 350 ppm or more. The upper limit of the total area ratio is not particularly limited, and is, for example, 500 ppm.

In the present disclosure, the area of the optically abnormal region means the area of the optically abnormal region observed in a region up to 2 μm from the center position of the thickness of the temporary support in one or the other direction of the thickness.

In the present disclosure, an optically abnormal region is a region having different optical properties from the main region of the temporary support (resin constituting the temporary support) (specifically, whether the reflectance or refractive index is different from the main region, or a region in which optical phenomena such as scattering and diffraction occur more strongly than in the main region). When the temporary support contains particles, for example, the optically abnormal region includes a light-shielding portion by the particles and an optically abnormal region other than the particles (for example, an abnormal refractive index region having a refractive index different from that of the particles and the main region of the temporary support). ). Examples of the optically abnormal region include a region having a different orientation and/or crystallinity from the main region of the temporary support, an air region, a region of a gas other than air, a cavity region where almost no gas exists, and the like.

In the present disclosure, the total area of the optically abnormal region is measured by the following method.

A polarizing filter (OLS4000-QWP) is inserted above the objective lens of an epi-reflection laser microscope (OLYMPUS OLS-4100). Next, the temporary support cut into 30 mm x 30 mm is horizontally suctioned and fixed onto the stage of a laser microscope using a porous suction plate (65F-HG manufactured by Universal Giken) and a vacuum pump. The suction-fixed temporary support is observed under the conditions of a 50x objective lens and a laser light intensity of 60 nm (laser wavelength is 405 nm). At this time, a region up to 2 μm in each thickness direction from the center position of the temporary support in the thickness direction is defined as a measurement region, and measurement is performed at 200 measurement points in the measurement region of 259 μm×260 μm. Therefore, the total measurement area is 0.259 mm x 0.26 mm x 200 = 13.5 mm ² .

The light amount difference between the pixel with the maximum light amount and the pixel with the minimum light amount in the measured image is divided into 4096 gradations (the value of the maximum light amount is 4095 and the value of the minimum light amount is 0). A histogram (horizontal axis: gradation of light amount (minimum value 0, maximum value 4095), vertical axis: number of pixels) is created as a graph of the light amount distribution of pixels in the image. The measured image is binarized using the gradation that is 400 gradations plus 400 gradations from the larger of the two base values of the created histogram as the threshold, and the areas of pixels with a larger amount of light than the threshold are summed. , the total area is the total area of the optically abnormal region. The ratio of the total area of the optical abnormality region to the measurement area is calculated.

The thickness of the temporary support is preferably 25 μm or more, more preferably 50 μm or more, and even more preferably 75 μm or more, from the viewpoint of suppressing deformation of the substrate to be bonded to the transfer film. The upper limit of the thickness is not particularly limited, and is, for example, 200 μm.

The surface of the temporary support in contact with the transfer layer may be subjected to surface treatment such as ultraviolet irradiation, corona discharge, plasma treatment, etc., from the viewpoint of improving adhesion with the transfer layer. When surface treatment is performed by irradiating ultraviolet rays, the exposure amount is preferably 10 mJ/cm ² to 2000 mJ/cm ² , more preferably 50 mJ/cm ² to 1000 mJ/cm ² .

Examples of light sources for ultraviolet irradiation include light sources that emit light in the wavelength range of 150 nm to 450 nm (for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrode discharge lamps, and light emitting diodes (LEDs). The output and illuminance are not particularly limited.

The transfer layer is preferably in contact with the surface of the temporary support. From the viewpoint of transferring the unevenness of the temporary support to the transfer layer, the surface roughness Rmax of the surface of the temporary support on the transfer layer side is preferably 0.5 μm or less, more preferably 0.01 μm to 0.5 μm. preferable.

The surface roughness Rmax of the surface of the temporary support on the transfer layer side is measured by the following method.

In the present disclosure, the surface roughness Rmax is measured using a three-dimensional optical profiler (New View 7300, manufactured by Zygo).

First, the temporary support is peeled off from the transfer film. Obtain the surface profile of the surface of the temporary support on the transfer layer side. Microscope Application of MetroPro ver. 8.3.2 is used as the measurement/analysis software. Next, a Surface Map screen is displayed using the measurement/analysis software, and histogram data is obtained on the Surface Map screen. The surface roughness Rmax is obtained from the obtained histogram data. Note that the surface roughness Rmax corresponds to the maximum height of the roughness curve at the reference length.

The temporary support may be a recycled product. Examples of recycled products include those made by cleaning used films and the like, turning them into chips, and using the chips as raw materials to make films. A specific example of a recycled product is Toray's Ecouse series.

[Transfer layer]
The transfer film according to the present disclosure includes a transfer layer.

From the viewpoint of ease of peeling of the temporary support, the surface free energy of the transfer layer on the side facing the temporary support is preferably 68.0 mJ/m ² or less, and 50.0 mJ/cm ² to 68. It is more preferably 0 mJ/cm ² , and even more preferably 55.0 mJ/cm ² to 65.0 mJ/cm ² .

In the present disclosure, the surface free energy (unit: mJ/m ² ) of the transfer layer on the side facing the temporary support is calculated by the following method.

On the measurement surface of the transfer layer, the contact angle of two types of liquids, pure water and methylene iodide, was measured using a contact angle meter CA-A model (Kyowa Kaimen Kagaku Co., Ltd.) under an atmosphere of room temperature 25°C and relative humidity 50%. After 20 seconds, 12 µL of the contact angle was dropped using the following method: 12 μL was dropped, and 20 seconds later, measurements were taken at 3 points, and the average value was taken as the contact angle. Using the obtained contact angles of the two types of liquids, the geometric mean method based on Owens-Wendt is used to calculate the dispersion force γ ^d , the polar force γ ^p and the surface energy γ (= γ ^d +γ ^p ) is calculated.

A specific calculation method is shown. The meaning of each symbol is shown below. When γ _SL is the tension at the interface between solid and liquid, the following formula (1) holds true.
γ _SL : Surface free energy of film surface and known liquid γ _S : Surface free energy of film surface γ _L : Known surface free energy of liquid γ _S ^d : Dispersion force component of surface free energy of film surface γ _S ^p : Polar force component of the surface free energy of the film surface γ _L ^d : Dispersion force component of the known surface free energy of the liquid γ _L ^p : Polar force component of the known surface free energy of the liquid γ _SL = γ _S + γ _L −2 ( γ _S ^d・γ _L ^d ) ^1/2 −2 (γ _S ^p・γ _L ^p ) ^1/2 ...Formula (1)
Further, the state when a smooth solid surface and a droplet are in contact with each other at a contact angle (θ) is expressed by the following equation (Young's equation).
γ _S = γ _SL + γ _L cosθ...Formula (2)
By combining these formulas (1) and (2), the following formula is obtained.
(γ _s ^d・γ _L ^d ) ^1/2 + (γ _s ^p・γ _L ^p ) ^1/2 (= γ _L (1+cos θ)/2...Formula (3)

In reality, the contact angle (θ) of two types of liquids, pure water and methylene iodide, the known surface energy γ _L of the liquid, and each component (γ _L ^d , γ _L ^p ) are expressed in equation (3). Substitute and solve the simultaneous equations.
As a result, the surface free energy (γ _S ) on the measurement surface of the transfer layer is calculated.

There are no particular restrictions on the method for adjusting the surface free energy of the side of the transfer layer facing the temporary support within the above range, but a method is to provide an intermediate layer containing a water-soluble resin on the side that comes into contact with the temporary support. can be mentioned.

From the viewpoint of improving the sensitivity of the photosensitive layer, the transfer layer preferably has a water content of 0.1% by mass or more, more preferably 0.15% by mass or more, based on the total amount of the transfer layer. The content is preferably 0.3% by mass or more, and more preferably 0.3% by mass or more. The upper limit of the water content is not particularly limited, and is, for example, 1.0% by mass.
The water content in the transfer layer can be adjusted by the drying method used when forming the transfer layer.

In the present disclosure, the water content in the transfer layer is measured by the following method.

A transfer film cut into a size of 5 mm x 30 mm was used as a sample, and the sample was inserted into a primary trap tube (PAT) and capped. In addition, when a protective film was provided, the sample was prepared by peeling off the protective film, and the sample was inserted immediately after peeling off. Sample preparation was performed at 23° C. and 45% RH. Heating using a thermal desorption device (product name "JTD-505III", manufactured by Japan Analytical Industry Co., Ltd.) and measuring outgas using a gas chromatograph mass spectrometer (product name "GCMS-QP2010", manufactured by Shimadzu Corporation) The water content was measured.

If the developability is good, there will be less residue on the pattern, and if the adhesion to the substrate is good, a thinner pattern can be formed. From the viewpoint of improving developability and adhesion with the substrate, the transfer layer preferably has an iron atom content of 0.01 ppm to 10.0 ppm on a mass basis with respect to the total amount of the transfer layer. It is more preferably from .1 ppm to 10 ppm, and even more preferably from 0.2 ppm to 10 ppm.
The iron content in the transfer layer can be adjusted by the composition of the photosensitive composition.

In the present disclosure, the content of iron atoms in the transfer layer is measured by the following method.

The content of iron atoms is measured by inductively coupled plasma (ICP) emission spectrometry described in JIS K1200-6. As the measuring device, for example, an inductively coupled plasma mass spectrometer (ICP-MS): ICPMS-2030 (manufactured by Shimadzu Corporation) is used.

First, 1.000 g of the transfer layer is weighed out from the transfer film, and the transfer layer is incinerated using an electric furnace. Add 5 mL of a nitric acid aqueous solution (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.; an aqueous solution containing a 1:1 mixture of special grade nitric acid and ultrapure water) to the platinum crucible taken out of the electric furnace to dissolve the ash. Subsequently, 15 ml of ultrapure water is added to obtain an aqueous solution of the ash. The obtained aqueous solution is measured by inductively coupled plasma (ICP) emission spectrometry described in JIS K1200-6, and the content of iron atoms in the transfer layer is calculated.

The transfer layer preferably includes a photosensitive layer in order to form a pattern.

<<Photosensitive layer>>
In a display device equipped with a touch panel such as a capacitive input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor in the viewing section, the wiring of the peripheral wiring part and the lead-out wiring part A conductive layer pattern such as the above is provided inside the touch panel. Generally, to form a patterned layer, for example, a negative photosensitive layer is provided on a substrate using a transfer film or the like, and the photosensitive layer is exposed to light through a mask having a desired pattern. , developing methods are widely used.

The photosensitive layer is preferably a negative photosensitive layer in which the solubility of exposed areas in a developer decreases upon exposure, and the non-exposed areas are removed through development. However, the photosensitive layer is not limited to a negative photosensitive layer, and may be a positive photosensitive layer in which the solubility of the exposed area in a developer is improved by exposure, and the exposed area is removed by development.

The photosensitive layer is obtained, for example, by applying a photosensitive composition and drying it.

When the photosensitive layer is a negative photosensitive layer, the photosensitive layer preferably contains a resin, a polymerizable compound, and a polymerization initiator. Further, when the photosensitive layer is a negative photosensitive layer, as described below, it is also preferable that an alkali-soluble resin (such as Polymer A which is an alkali-soluble resin) is included as part or all of the resin. That is, in one embodiment, the photosensitive layer preferably contains a resin including an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

Such a photosensitive layer (negative photosensitive layer) contains 10% to 90% by weight of a resin, 5% to 70% by weight of a polymerizable compound, and a polymerization initiator, based on the total weight of the photosensitive layer. It is preferable to contain 0.01% to 20% by mass.
Each component will be explained in order below.

<Polymer A (resin)>
When the photosensitive layer is a negative photosensitive layer, the resin contained in the photosensitive layer is also particularly referred to as polymer A.

Examples of the polymer A include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, and combinations of epoxy acrylate resins and acid anhydrides. Examples include acid-modified epoxy acrylate resins obtained by reaction. It is not limited to this.

As the polymer A, (meth)acrylic resin is preferable.

Note that in the present disclosure, (meth)acrylic resin means a resin having a structural unit derived from a (meth)acrylic compound. In the (meth)acrylic resin, the content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, and 60% by mass or more, based on the total mass of the (meth)acrylic resin. More preferably, the amount is % by mass or more.

As the polymer A, a polymer having a structural unit derived from a (meth)acrylic compound and a structural unit derived from a styrene compound is also preferable.

It is preferable that the polymer A is an alkali-soluble resin.

The acid value of the polymer A is preferably 250 mgKOH/g or less, more preferably less than 200 mgKOH/g, and less than 190 mgKOH/g from the viewpoint of better resolution by suppressing swelling of the photosensitive layer by the developer. is even more preferable.

The lower limit of the acid value of Polymer A is not particularly limited. The acid value of the polymer A is preferably 60 mgKOH/g or more, more preferably 80 mgKOH/g or more, and even more preferably 120 mgKOH/g or more, from the viewpoint of better developability.

Note that the acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The acid value of the polymer A may be adjusted depending on the type of structural units constituting the polymer A and the content of the structural units containing acid groups.

The weight average molecular weight of Polymer A is preferably 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferred from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and even more preferably 60,000 or less.

On the other hand, when the weight average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge fusing property and cut chip property when formed into a photosensitive resin laminate. . The weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing property refers to the degree to which the photosensitive layer easily protrudes from the end surface of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree to which chips easily fly when an unexposed film is cut with a cutter. If this chip adheres to the top surface of the photosensitive resin laminate, it will be transferred to a mask in a subsequent exposure step, etc., resulting in defective products.
Note that the photosensitive resin laminate is a laminate obtained by bonding a transfer film and a base material.

The degree of dispersion of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0. . In this disclosure, dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight). In the present disclosure, weight average molecular weight and number average molecular weight are values measured using gel permeation chromatography.

In the photosensitive layer, from the viewpoint of suppressing thickening of the line width and deterioration of resolution when the focal position shifts during exposure, the polymer A contains a structural unit based on a monomer having an aromatic hydrocarbon group. is preferred. Note that such aromatic hydrocarbon groups include, for example, 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, more preferably 85% by mass or less. In addition, when multiple types of polymers A are included, it is preferable that the average value of the content of structural units based on monomers having aromatic hydrocarbon groups falls within the above range.

Monomers having an aromatic hydrocarbon group include, for example, monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoate). acids, styrene dimers, styrene trimers, etc.). Among these, monomers having an aralkyl group or styrene are preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is styrene, the content of the styrene-based structural unit is 20% by mass to 70% by mass based on the total mass of polymer A. It is preferably 25% to 65% by weight, even more preferably 30% to 60% by weight, and particularly preferably 30% to 55% by weight. In addition, when a photosensitive layer contains several types of polymers A, the content rate of the structural unit which has an aromatic hydrocarbon group is calculated|required 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 a substituted or unsubstituted benzyl group is preferred.

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

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride; Examples include vinylbenzyl alcohol. Among them, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is based on the total mass of polymer A. On the other hand, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass.

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

It is preferable that the polymer A containing no structural unit based on a monomer having an aromatic hydrocarbon group is obtained by polymerizing at least one of the first monomers described below, and the first monomer It is more preferable to obtain the monomer by copolymerizing at least one of the monomers and at least one of the second monomers described below.

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

The content of the structural unit based on the first monomer in polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total mass of polymer A. More preferably 15% by mass to 30% by mass.

It is preferable that the content be 5% by mass or more from the viewpoint of expressing good developability and controlling edge fusing property. It is preferable that the content be 50% by mass or less from the viewpoint of high resolution and groove 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 its 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. (meth)acrylates such as tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; acetic acid Examples include esters of vinyl alcohol such as vinyl; and (meth)acrylonitrile. Among these, the second monomer is preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate.

The content of the structural unit based on the second monomer in polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, based on the total mass of polymer A. More preferably 17% by mass to 45% by mass.

When polymer A contains a structural unit based on a monomer having an aralkyl group and/or a structural unit based on a styrene monomer, it suppresses thickening of line width and deterioration of resolution when the focal position shifts during exposure. It is preferable from the viewpoint of For example, a copolymer containing a constitutional unit based on methacrylic acid, a constitutional unit based on benzyl methacrylate, and a constitutional unit based on styrene, a constitutional unit based on methacrylic acid, a constitutional unit based on methyl methacrylate, a constitutional unit based on benzyl methacrylate, and a copolymer containing a constitutional unit based on styrene. Copolymers containing structural units based on the above are preferred.

In one embodiment, the polymer A contains 25% to 55% by mass of structural units based on a monomer having an aromatic hydrocarbon group, and 20% to 35% by mass of structural units based on the first monomer. , a polymer containing 15% by mass to 45% by mass of structural units based on the second monomer. In another embodiment, the weight containing 70% by mass to 90% by mass of structural units based on a monomer having an aromatic hydrocarbon group and 10% by mass to 25% by mass of structural units based on the first monomer. Preferably, it is a combination.

Polymer A may have a linear structure, a branched structure, or an alicyclic structure in its side chain. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or alicyclic structure can be introduced into the side chain of the polymer A. . The group having an alicyclic structure may be monocyclic or polycyclic.

Specific examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, ( Isoamyl meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert-octyl (meth)acrylate etc. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

Specific examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Examples of monomers containing a group having an alicyclic structure in the side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-2-adamantyl; 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-(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-menthanoindene-5- (meth)acrylate yl, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (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 acid Examples include (nor)bornyl acid, isobornyl (meth)acrylate, fentyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.

Among them, monomers containing a group having an alicyclic structure in the side chain include cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fentyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (meth)acrylate More preferred are (nor)bornyl, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate.

The number of polymers A contained in the photosensitive layer may be one or two or more.

When two or more types of polymer A are included, two types of polymer A containing structural units based on monomers having aromatic hydrocarbon groups, or based on monomers having aromatic hydrocarbon groups It is preferable to include a polymer A containing a structural unit and a polymer A not containing a structural unit based on a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of polymer A containing structural units based on monomers having aromatic hydrocarbon groups is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of polymer A. It is preferably at least 80% by mass, more preferably at least 90% by mass.

Furthermore, from the viewpoint of sensitivity and resolution, the photosensitive layer preferably contains an alkali-soluble resin having a crosslinkable group.

The crosslinkable group is preferably a polymerizable group from the viewpoints of developability, sensitivity, and resolution.

The polymerizable group is not particularly limited as long as it participates in a polymerization reaction, and includes, for example, a group having an ethylenically unsaturated group such as a vinyl group, (meth)acryloyl group, styryl group, and maleimide group; and epoxy and a group having a cationic polymerizable group such as a group and an oxetane group.

As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

The alkali-soluble resin having a crosslinkable group is preferably an acrylic resin having an ethylenically unsaturated group, and more preferably an acrylic resin having a structural unit having an ethylenically unsaturated group.

Polymer A is synthesized by adding a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution of the monomer or plural monomers mentioned above diluted with a solvent such as acetone, methyl ethyl ketone, and isopropanol. It is preferable to add an appropriate amount of and heat and stir. In some cases, synthesis may be carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, a solvent may be further added to adjust the concentration to a desired level. As a synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The glass transition temperature Tg of polymer A is preferably 30°C to 135°C. By using Polymer A having a Tg of 135° C. or less, it is possible to suppress thickening of line width and deterioration of resolution when the focal position during exposure is shifted. 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 Polymer A having a Tg of 30° C. or higher from the viewpoint of improving 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.

The photosensitive layer may contain other resins than those mentioned 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, Examples include benzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

As the polymer A, an alkali-soluble resin described in the section of the thermoplastic resin layer below may be used.

The content of polymer A is preferably 10% to 90% by mass, more preferably 30% to 70% by mass, and 40% to 60% by mass, based on the total mass of the photosensitive layer. More preferably, it is expressed in mass %. It is preferable that the content of the polymer A is 90% by mass or less based on the total mass of the photosensitive layer because the development time can be controlled. On the other hand, it is preferable that the content of the polymer A is 10% by mass or more based on the total mass of the photosensitive layer because edge fuse resistance is improved.

<Polymerizable compound>
When the photosensitive layer is a negative photosensitive layer, it is preferable that the photosensitive layer contains a polymerizable compound having a polymerizable group. In the present disclosure, the term "polymerizable compound" refers to a compound that polymerizes under the action of a polymerization initiator, which will be described later, and which is different from the polymer A described above.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it participates in the polymerization reaction, and includes, for example, ethylenically unsaturated groups such as a vinyl group, (meth)acryloyl group, styryl group, and maleimide group. group; and a group having a cationic polymerizable group such as an epoxy group and an oxetane group.

As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and a (meth)acryloyl group is more preferable.

As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferable, since the photosensitivity of the photosensitive layer is better. Compounds having unsaturated groups (polyfunctional ethylenically unsaturated compounds) are more preferred.

In addition, in terms of better resolution and releasability, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and 2 or less. More preferred.

The photosensitive layer is a difunctional or trifunctional ethylenic material having two or three ethylenically unsaturated groups in one molecule, since it has a better balance between the photosensitivity, resolution, and peelability of the photosensitive layer. 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 is preferably 20% by mass or more, more preferably more than 40% by mass, and further preferably 55% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. preferable. The upper limit of the content of the bifunctional ethylenically unsaturated compound is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds may be difunctional ethylenically unsaturated compounds.

Moreover, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.

(Polymerizable compound B1)
It is also preferable that the photosensitive layer 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.

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

Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, naphthalene ring, and anthracene ring; aromatic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; Examples include heterocycles and fused rings thereof, with aromatic hydrocarbon rings being preferred and benzene rings being more preferred. Note that 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 resolution by suppressing swelling of the photosensitive layer by the developer.

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

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 bonded directly or via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents of this publication are incorporated herein.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.
As the 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd. ), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, ethoxylated bisphenol A dimethacrylate (NK ester BPE-500, average repeating number of ethylene oxide chains 10, manufactured by Shin Nakamura Chemical Co., Ltd.) , 2,2-bis(4-(methacryloxidedecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), ethoxylated bisphenol A dimethacrylate (NK ester BPE-1300N, average repetition of ethylene oxide chains) 30, manufactured by Shin Nakamura Chemical Industries, Ltd.), ethoxylated bisphenol A dimethacrylate (NK ester BPE-200, average repeating number of ethylene oxide chains 4, manufactured by Shin Nakamura Chemical Industries, Ltd.), ethoxylated bisphenol A dimethacrylate (NK ester) BPE-100, average repeating number of ethylene oxide chains 2.6, manufactured by Shin Nakamura Chemical Co., Ltd.), and ethoxylated bisphenol A diacrylate (NK ester A-BPE-10, average repeating number of ethylene oxide chains 10, Shin Nakamura) (manufactured by Kagaku Kogyo Co., Ltd.).

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

In general formula (B1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents _C2H4 _. B represents _C3H6 _. n1 and n3 are each independently an integer of 1 to 39, and n1+n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30. The arrangement of the constituent units of -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenol 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, even more preferably 0 to 2, and particularly preferably 0.

The number of polymerizable compounds B1 contained in the photosensitive layer may be one, or two or more.

From the viewpoint of better resolution, 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 photosensitive layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin oozes out from the edge of the transfer member), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

The photosensitive layer may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.
Polymerizable compounds other than polymerizable compound B1 are not particularly limited, and can be appropriately selected from known compounds. For example, compounds that have one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds that do not have an aromatic ring, and trifunctional or higher functional ethylenically unsaturated compounds. can be mentioned.

Examples of monofunctional ethylenically unsaturated compounds 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 bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. .

Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and 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. Commercially available products include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Co., Ltd.).

The content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass or more, more preferably 30% by mass or more based on the total mass of the negative photosensitive layer, from the viewpoint of better resolution and resist removability. It is preferably 40% by mass or more, and more preferably 40% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive composition oozes out from the edge of the transfer member).

The content of the bifunctional ethylenically unsaturated compound is preferably 40% by mass or more, based on the total mass of the polymerizable compound having an ethylenically unsaturated group, from the viewpoint of better resolution and resist removability. It is more preferably at least 80% by mass, and even more preferably at least 80% by mass. The upper limit is preferably 100% by mass or less, more preferably 90% by mass or less, from the viewpoints of transferability and edge fusion (a phenomenon in which the photosensitive composition oozes out from the edges of the transfer film).

Examples of trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth) Examples include acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.

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

In one embodiment, the photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher functional ethylenically unsaturated compound, and the above-mentioned polymerizable compound B1 and two or more trifunctional or higher functional ethylenically unsaturated compounds It is more preferable to include a compound. In this case, the mass ratio of the polymerizable compound B1 and the trifunctional or higher functional ethylenically unsaturated compound is (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher functional ethylenically unsaturated compound) = 1:1 ~5:1 is preferred, 1.2:1 ~ 4:1 is more preferred, and 1.5:1 ~ 3:1 is even more preferred.

Furthermore, in one embodiment, the photosensitive layer preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide-modified compounds of trifunctional or higher-functional ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300 manufactured by Shin Nakamura Chemical Co., Ltd. -1CL, etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd., etc.) ), ethoxylated glycerin triacrylate (A-GLY-9E, etc. 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.) is mentioned.

Furthermore, as the polymerizable compound, a polymerizable compound having an acid group (carboxy group, etc.) may be used. The above acid group may form an acid anhydride group. Examples of the polymerizable compound having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). manufactured by Toagosei Co., Ltd.).

As the polymerizable compound having an acid group, for example, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

The number of polymerizable compounds contained in the photosensitive layer may be one, or two or more.

The content of the polymerizable compound is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 70% by mass, and even more preferably 20% by mass to 70% by mass, based on the total mass of the photosensitive layer.

The molecular weight (weight average molecular weight if it has a molecular weight distribution) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 to 2,200. More preferred.

<Polymerization initiator>
When the photosensitive layer is a negative photosensitive layer, it is also preferable that the photosensitive layer contains a polymerization initiator.

The polymerization initiator is selected depending on the type of polymerization reaction, and includes, for example, a thermal polymerization initiator and a photopolymerization initiator.
The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

It is preferable that the photosensitive layer contains a photopolymerization initiator.
A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators, with radical photopolymerization initiators being preferred.

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

In addition, from the viewpoint of photosensitivity, visibility of exposed areas and non-exposed areas, and resolution, the photosensitive layer uses 2,4,5-triarylimidazole dimer and its derivatives as a photoradical polymerization initiator. It is preferable to include at least one selected from the group consisting of: Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different.

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

As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783 may be used.

Examples of photoradical polymerization initiators 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 (product name: Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (BASF Co., Ltd.), Omnirad651 and 369 (product name: Midori Kagaku Co., Ltd.) Name: IGM Resins manufactured by B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd.) ).

As a commercially available photoradical polymerization initiator, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01 , manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (product name: IRGACURE OXE-02, BASF ), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4 -morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-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 (product Name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Product name: Omnirad 369, manufactured by IGM Resins B.V.) , 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.). (manufactured by B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (product name: Omnirad 651, IGM Resins manufactured by B.V.), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzolyl) phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins B.V.), Oxime ester photopolymerization initiator (product 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 Hampford), 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 Changzhou Strong Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-( O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H -carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.).

A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving actinic rays. The photocationic polymerization initiator is preferably a compound that is sensitive to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited. In addition, even for photocationic polymerization initiators that are not directly sensitive to actinic rays with a wavelength of 300 nm or more, if the compound is sensitive to actinic rays with a wavelength of 300 nm or more and generates acid when used in combination with a sensitizer, the sensitizer can be used as a sensitizer. It can be preferably used in combination with

As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less is preferable. Particularly preferred are photocationic polymerization initiators that are generated. Although the lower limit of pKa is not particularly determined, it is preferably -10.0 or more, for example.

Examples of the cationic photopolymerization initiator include ionic cationic photopolymerization initiators and nonionic cationic photopolymerization initiators.

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 2014-085643A may be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494 may be used. Furthermore, as the oxime sulfonate compound, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.

The photosensitive 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.

The number of polymerization initiators contained in the photosensitive layer may be one, or two or more.

The content of the polymerization initiator (preferably photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more based on the total mass of the photosensitive layer. More preferably, the content is .0% by mass or more. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the negative photosensitive layer.

<Pigment>
The photosensitive layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 nm to 780 nm during color development, from the viewpoint of visibility of exposed areas and unexposed areas, pattern visibility after development, and resolution, and, It is also preferable to include a dye (also referred to as "dye N") whose maximum absorption wavelength changes depending on the acid, base, or radical. When dye N is included, although the detailed mechanism is unknown, adhesion with adjacent layers (for example, intermediate layer) is improved, resulting in better resolution.

In this disclosure, the phrase "the maximum absorption wavelength of a dye changes due to an acid, a base, or a radical" refers to a state in which a dye in a colored state is decolored by an acid, a base, or a radical, and a state in which a dye in a decolored state is decolored by an acid, a base, or a radical. , a base, or a radical, and an aspect in which a dye in a coloring state changes to a coloring state of another hue.

Specifically, the dye N may be a compound that changes from a decolorized state and develops color upon exposure to light, or may be a compound that changes from a color developed state and decolorizes upon exposure. In this case, it may be a dye that changes its coloring or decoloring state when acids, bases, or radicals are generated and act within the photosensitive layer upon exposure; It may also be a dye whose coloring or decoloring state changes as the pH changes (for example, pH). It may also be a dye that changes its coloring or decoloring state when directly stimulated by an acid, base, or radical without being exposed to light.

Among these, from the viewpoint of visibility and resolution of exposed and non-exposed areas, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with radicals.

When the photosensitive layer is a negative type photosensitive layer, from the viewpoint of visibility and resolution of exposed and non-exposed areas, the photosensitive layer contains a dye whose maximum absorption wavelength changes with radicals as the dye N, and It is preferable to include both a photoradical polymerization initiator and a photoradical polymerization initiator.

Furthermore, from the viewpoint of visibility of exposed and unexposed areas, it is preferable that the dye N is a dye that develops color with an acid, a base, or a radical.

As an example of the coloring mechanism of dye N, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive layer, and after exposure, the photoradical polymerization initiator, Examples include embodiments in which radical-reactive dyes, acid-reactive dyes, or base-reactive dyes (for example, leuco dyes) develop color due to radicals, acids, or bases generated from a photocationic polymerization initiator or a photobase generator.

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 nm to 780 nm during color development, more preferably 550 nm to 700 nm, and 550 nm or more. More preferably, the wavelength is 650 nm.

Further, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during 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 nm to 780 nm during color development, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

The maximum absorption wavelength of dye N is determined by the transmission spectrum of a solution containing dye N (liquid temperature 25°C) in the range of 400 to 780 nm under atmospheric conditions using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation). It can be obtained by measuring the wavelength and detecting the wavelength at which the light intensity is minimum (maximum absorption wavelength).

An example of a dye that develops or discolors upon exposure to light is a leuco compound.

Examples of dyes that disappear upon exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

As the dye N, a leuco compound is preferable from the viewpoint of visibility of exposed areas and non-exposed areas.

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons. A leuco compound (diarylmethane dye) having a rhodamine lactam skeleton (a rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco auramine skeleton Examples include leuco compounds (leuco auramine pigments).

Among these, the dye N is preferably a triarylmethane dye or a fluoran dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluoran dye.

The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility of exposed and non-exposed areas. As a result, the lactone ring, sultine 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, and the leuco compound is changed into a ring-closed state. The color can be removed by changing the leuco compound to an open ring state, or the color can be developed by changing the leuco compound to an open ring state. The leuco compound is preferably a compound that has a lactone ring, a sultine ring, or a sultone ring, and develops color when the lactone ring, sultine ring, or sultone ring opens with a radical or an acid. More preferred are compounds that develop color when the lactone ring opens with an acid.

Examples of the dye N include the following dyes and leuco compounds.
Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymol sulfophthalein, xylenol blue, and methyl. Orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria pure blue-naphthalene sulfonate, Victoria pure blue BOH (preserved) Tsuchiya Chemical Co., Ltd.), Oil Blue #603 (Orient Chemical Co., Ltd.), Oil Pink #312 (Orient Chemical Co., Ltd.), Oil Red 5B (Orient Chemical Co., Ltd.), Oil Scarlet #308 (Orient Chemical Co., Ltd.) ), Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylimino naphthoquinone, 2-carboxystearylamino- 4-p-N,N-bis(hydroxyethyl)amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p- Diethylaminophenylimino-5-pyrazolone is mentioned.

Specific examples of leuco compounds among the dyes N include p, p', p''-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malachite green lactone, Benzoylleucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p -Toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-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-diethylamino)-6-methoxy-7-aminofluorane , N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3- (N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6 -Methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl- 2-Methylindol-3-yl) phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethyl Aminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-phthalide, 3-(4-diethylaminophenyl)-3-( 1-ethyl-2-methylindol-3-yl) phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one. .

The dye N is preferably a dye whose maximum absorption wavelength changes with radicals, from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution, and is preferably a dye that develops color due to radicals. It is more preferable that there be.

As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate is preferable.

The number of dyes N contained in the photosensitive layer may be one, or two or more.

The content of the dye N is preferably 0.1% by mass or more based on the total mass of the photosensitive layer from the viewpoint of visibility of exposed areas and non-exposed areas, pattern visibility after development, and resolution. , more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, particularly preferably 0.1% by mass to 1% by mass.

The content of the dye N means the content of the dye when all the dye N contained in the total mass of the photosensitive layer is brought into a colored state. Below, a method for quantifying the content of the dye N will be explained using a dye that develops color due to radicals as an example.
A solution is prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator, Irgacure OXE01 (trade name: BASF Japan Ltd.), is added to each of the obtained solutions, and irradiation with 365 nm light generates radicals, causing all the dyes to become colored. Thereafter, the absorbance of each solution at a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve is created.
Next, the absorbance of the solution in which all the dyes are colored is measured in the same manner as above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive layer, the content of the dye contained in the photosensitive layer is calculated based on a calibration curve.
Note that 3 g of the photosensitive layer is the same as 3 g of the total solid content in the photosensitive composition.

<Thermal crosslinkable compound>
When the photosensitive layer is a negative photosensitive layer, the photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In addition, in this disclosure, the thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.

Examples of thermally crosslinkable compounds include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film.

Blocked isocyanate compounds react with hydroxy groups and carboxy groups, so if the resin and/or polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film decreases. There is a tendency for the function to be enhanced when a film obtained by hardening a negative photosensitive layer is used as a protective film.

Note that 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°C to 160°C, more preferably 130°C to 150°C.

The dissociation temperature of blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of 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 suitably used. However, the differential scanning calorimeter is not limited to this.

Blocking agents with a dissociation temperature of 100 to 160°C include active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds ( Examples include compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime.

Among these, as a blocking agent having a dissociation temperature of 100 to 160°C, for example, from the viewpoint of storage stability, at least one kind selected from oxime compounds is preferable.

The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer target.

A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into isocyanurate and protecting it.

Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is easier to maintain the dissociation temperature in a preferable range than a compound without an oxime structure, and produces less development residue. This is preferable from the viewpoint of ease of use.

The blocked isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and any known polymerizable group can be used, with radically polymerizable groups being preferred.

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

Among these, as the polymerizable group, an ethylenically unsaturated group is preferable, a (meth)acryloyl group is more preferable, and an acryloyl group is even more preferable.

Commercially available products can be used as the blocked isocyanate compound.

Examples of commercially available block isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko), block type Examples include the Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, manufactured by Asahi Kasei Chemicals).

Additionally, a compound having the following structure can also be used as the blocked isocyanate compound.

The number of thermally crosslinkable compounds contained in the photosensitive layer may be one, or two or more.
When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive layer. preferable.

<Surfactant>
The photosensitive layer preferably contains a surfactant from the viewpoint of thickness uniformity.

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.

Examples of the surfactant include hydrocarbon surfactants, fluorine surfactants, and silicone surfactants. From the viewpoint of improving environmental suitability, the surfactant preferably does not contain fluorine atoms. As the surfactant, hydrocarbon surfactants or silicone surfactants are preferred.

Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F -558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Corporation), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Corporation), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Ftergent 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.), U- 120E (Unichem Co., Ltd.) and the like.

In addition, fluorine-based surfactants include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is severed and the fluorine atom evaporates. can also be suitably used. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), An example is DS-21.

Furthermore, 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.

Additionally, block polymers can also be used as the fluorosurfactant.

In addition, 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, propyleneoxy groups). A fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.

Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (manufactured by DIC Corporation).

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

Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether , polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, and the like.

Specific examples of hydrocarbon surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (and above). , manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-1105, Examples include D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), etc. .

Silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and terminals, and structural units with hydrophilic groups in the side chains and siloxane bonds in the side chains. Polymers having structural units having groups can be mentioned.

Among these, the silicone surfactant is preferably a polymer having a constitutional unit having a hydrophilic group in the side chain and a constitutional unit having a siloxane bond-containing group in the side chain. The polymer may be a random copolymer or a block copolymer.

Examples of the structural unit having a hydrophilic group in the side chain include structural units based on the following monomers.

R ⁴ is a hydrogen atom or a methyl group,
R ⁵ is a hydrogen atom or a methyl group,
n is an integer from 1 to 4,
m is an integer from 1 to 100.

Examples of the structural unit having a siloxane bond-containing group in the side chain include structural units based on the following monomers.

R is each independently an alkyl group having 1 to 3 carbon atoms,
R ¹ is a hydrogen atom or a methyl group,
L ¹ is a divalent organic group or a single bond.

R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 10 carbon atoms,
R ³ is an alkyl group having 1 to 4 carbon atoms,
n is an integer from 5 to 50.

Specific examples of silicone surfactants include:
EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (manufactured by DIC Corporation),
DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above, Toray Silicone SH8400) 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-22-4515, KF-6004, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP- 120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Silicone Co., Ltd.),
F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials),
BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK 377, BYK378, BYK323 (manufactured by BYK Chemie)
etc.

Furthermore, as the surfactant, nonionic surfactants are preferred.

The number of surfactants contained in the photosensitive layer may be one type or two or more types.

When the photosensitive layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, and 0.01% by mass to 1% by mass, based on the total mass of the photosensitive layer. 0.0% by weight is more preferable, and 0.05% by weight to 0.80% by weight is even more preferable.

<Other additives>
In addition to the above-mentioned components, the photosensitive layer may contain known additives as necessary.
Examples of additives include radical polymerization inhibitors, chain transfer agents, sensitizers, plasticizers, heterocyclic compounds (triazole, etc.), benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), and Examples include purine bases (adenine, etc.).

Each additive contained in the photosensitive layer may be one type or two or more types.

The photosensitive layer may contain a radical polymerization inhibitor.

Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenothiazine, phenoxazine, or 4-methoxyphenol is preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, and the like. Nitrosophenylhydroxyamine aluminum salt is preferred in order not to impair the sensitivity of the photosensitive layer.

When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, and 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer. 0.0% by weight is more preferable, and 0.02% by weight to 2.0% by weight is even more preferable. The content of the polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and 0.01% by mass, based on the total mass of the polymerizable compound. More preferably, the amount is from % by mass to 1.0% by mass.

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

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 include carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. As the carboxybenzotriazole, for example, commercially available products such as CBT-1 (trade name: Johoku Kagaku Kogyo Co., Ltd.) can be used.

The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, and 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer. is more preferable. When the content is 0.01% by mass or more, the storage stability of the photosensitive layer is better. On the other hand, when the content is 3% by mass or less, sensitivity can be maintained and dye decolorization can be suppressed more effectively.

The photosensitive layer may contain a sensitizer.

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

The number of sensitizers contained in the photosensitive layer may be one, or two or more.

When the photosensitive layer contains a sensitizer, the content of the sensitizer can be selected as appropriate depending on the purpose. It is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the sexual layer.

The photosensitive layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.

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

The photosensitive layer also contains metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents. It may further contain known additives such as.

The additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-085643, and the contents of this publication are incorporated herein.

The thickness of the photosensitive layer is generally 0.1 μm to 300 μm, preferably 0.2 μm to 100 μm, more preferably 0.5 μm to 50 μm, even more preferably 0.5 μm to 15 μm, and 0.5 μm to 10 μm. is particularly preferred, and 0.5 μm to 8 μm is most preferred. This improves the developability of the photosensitive layer and improves the resolution.

In one embodiment, the thickness is preferably 0.5 μm to 5 μm, more preferably 0.5 μm to 4 μm, and even more preferably 0.5 μm to 3 μm.

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

<Impurities etc.>
The photosensitive layer may contain a predetermined amount of impurities.

Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to have the following content.

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

Methods for keeping impurities within the above range include selecting materials with a low content of impurities as raw materials for the composition, preventing contamination of impurities during the preparation of the photosensitive layer, and removing them by washing. . By such a method, the amount of impurities can be kept within the above range.

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

The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer may be small. preferable. The content of these compounds relative to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.

The lower limit of the content is preferably 10 ppb, more preferably 100 ppb, based on the total mass of the photosensitive layer. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measuring method.

From the viewpoint of improving the sensitivity of the photosensitive layer, the water content of the photosensitive layer is preferably 0.1% by mass or more, and preferably 0.15% by mass or more, based on the total amount of the photosensitive layer. is more preferable, and even more preferably 0.3% by mass or more. The upper limit of the water content is not particularly limited, and is, for example, 1.0% by mass.

The water content in the photosensitive layer is measured in the same manner as the water content in the transfer layer.

If the photosensitive layer has good developability, it will hardly leave residue on the pattern, and if it has good adhesion to the substrate, it will be possible to form a thinner pattern. From the viewpoint of improving developability and adhesion with the substrate, the content of iron atoms in the transfer layer is preferably 0.01 ppm to 10.0 ppm on a mass basis with respect to the total amount of the photosensitive layer. It is more preferably from .1 ppm to 10 ppm, and even more preferably from 0.2 ppm to 10 ppm.

The content of iron atoms in the photosensitive layer is measured in the same manner as the content of iron atoms in the transfer layer.

<Pigment>
The photosensitive layer may be a colored resin layer containing a pigment.

In order to protect the liquid crystal display window of recent electronic devices, a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc., is sometimes attached to the liquid crystal display window of recent electronic devices. be. A colored resin layer may be used to form such a light-blocking 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 these, when forming a black pattern, a black pigment is preferably selected as the pigment.

As the black pigment, any known black pigment (such as an organic pigment or an inorganic pigment) can be appropriately selected as long as it does not impair the effects of the present disclosure. Among them, from the viewpoint of optical density, preferred examples of the black pigment include carbon black, titanium oxide, titanium carbide, iron oxide, and graphite, with carbon black being particularly preferred. From the viewpoint of surface resistance, carbon black whose surface is at least partially coated with resin is preferable as carbon black.

From the viewpoint of dispersion stability, the number average particle size of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm.

Here, the particle size refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope and the area is the same as the area of the pigment particle, and the number average particle size is the average value obtained by determining the above particle size for 100 arbitrary particles and averaging the 100 determined particle sizes.

As for the white pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of JP-A No. 2005-007765 can be used. Specifically, among white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable as inorganic pigments, and titanium oxide or zinc oxide is more preferable. Preferably, titanium oxide is more preferable. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.

Furthermore, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or two or more treatments may be performed. This suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, and the like.

From the viewpoint of reducing the thickness of the photosensitive layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and both alumina treatment and zirconia treatment are particularly preferred.

Furthermore, when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, it is also preferable that the photosensitive layer further contains a chromatic pigment other than the black pigment and the white pigment. When a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, in terms of better dispersibility.

Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter referred to as C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), and Monolight. - Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Splatter (C.I. Pigment・Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C. I. Pigment Red 122, C. I. Pigment Red 149, C. I. Pigment Red 168, C. I. Pigment Red 177, C. I. Pigment Red 180, C. I. Pigment Red 192, C. I. Pigment Red 215, C. I. Pigment Green 7, C. I. Pigment Blue 15:1, C. I. Pigment Blue 15:4, C. I. Pigment Blue 22, C. I. Pigment Blue 60, C. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Among them, C. I. Pigment Red 177 is preferred.

When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, based on the total mass of the photosensitive layer. It is more preferably more than 35% by mass, and particularly preferably 10% by mass or more and 35% by mass or less.

When the photosensitive layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of pigments other than black pigments is preferably 30% by mass or less, and 1% by mass to 20% by mass based on the black pigment. It is more preferably 3% by mass to 15% by mass.

Note that when the photosensitive layer contains a black pigment and is formed from a photosensitive composition, the black pigment (preferably carbon black) is introduced into the photosensitive composition in the form of a pigment dispersion. It is preferable that

The dispersion liquid may be prepared by adding a mixture obtained by pre-mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture using a dispersion machine. The pigment dispersant may be selected depending on the pigment and the solvent, and for example, commercially available dispersants can be used. Note that the vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion, and is liquid, and includes 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).

Examples of dispersants include urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acids. Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups, and Oil-based dispersants such as their salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Examples include water-soluble resins such as water-soluble polymer compounds, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide adducts, phosphate ester systems, and the like. The aspect of the dispersant may be selected from the items described in paragraphs [0021] to [0065] of JP-A-2021-012355.

Preferred dispersants include, for example, basic polymer type dispersants. Examples of the basic polymer type dispersant include a polymer containing a nitrogen atom. Nitrogen atoms may be included in the main chain of the polymer. Nitrogen atoms may be included in the side chains of the polymer. Nitrogen atoms may be included in the main chain and side chains of the polymer. The basic polymer type dispersant is preferably a polymer containing a nitrogen atom in a side chain. Since the surface of carbon black is generally acidic, when carbon black is used as a pigment, a basic polymer type dispersant is particularly preferred as the dispersant.

Examples of the polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in a side chain) include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing polymer. Examples include polymers containing at least one atomic group selected from the group consisting of heterocyclic groups. For example, a polymer containing a quaternary ammonium base is preferred. The atomic group is preferably introduced into the side chain of the polymer. For example, a polymer containing at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group in its side chain. Coalescence is preferred, and polymers containing a quaternary ammonium base in the side chain are more preferred. Examples of the counter ion of the quaternary ammonium cation in the quaternary ammonium base include carboxylic acid ions. Examples of carboxylic acid ions include aliphatic carboxylic acid ions and aromatic carboxylic acid ions.

The polymer containing a nitrogen atom (preferably a polymer containing a nitrogen atom in a side chain) is preferably a polymer containing a structural unit derived from styrene and a structural unit derived from a maleimide derivative. More preferably, it is a copolymer with a maleimide derivative. A maleimide derivative has a structure in which at least one hydrogen atom of maleimide is substituted with a substituent. As a maleimide derivative, for example, at least one atomic group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic group is used. Examples include maleimide derivatives containing. The maleimide derivative is preferably a maleimide derivative containing a quaternary ammonium base.

The dispersant may be a commercially available dispersant, such as BYK-2012 (BYK-2012).
Japan Co., Ltd.).

The photosensitive layer may contain a dispersion aid (also referred to as a pigment dispersion aid) in addition to the pigment. The dispersion aid may be selected from known dispersion aids.

Examples of the dispersion aid include compounds having organic dye residues. Examples of organic pigments include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, and benzimidazo pigments. Ron pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. Examples include pigments. The compound having an organic dye residue may have an acidic substituent, a basic substituent, or a neutral substituent. Examples of acidic substituents include sulfo groups, carboxy groups, and phosphoric acid groups. Examples of the basic substituent include a sulfonamide group and an amino group. Examples of neutral substituents include phenyl groups and phthalimidoalkyl groups. The aspect of the dispersion aid may be selected from the items described in paragraphs [0067] to [0084] of JP-A-2021-012355.

Preferred dispersion aids include, for example, compounds having phthalocyanine residues. Specifically, the dispersion aid is preferably a phthalocyanine pigment derivative or a salt thereof having an acidic substituent, and at least one acidic substituent selected from the group consisting of a sulfo group, a carboxy group, and a phosphoric acid group. A phthalocyanine pigment derivative having a sulfo group or a salt thereof is more preferable, and a phthalocyanine pigment derivative having a sulfo group or a salt thereof is even more preferable. Phthalocyanine pigment derivatives are described, for example, in JP 2007-226161A, WO 2016/163351, JP 2017-165820, and Patent No. 5753266. These publications are incorporated herein by reference.

The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, roll mill, attritor, super mill, dissolver, homomixer, and sand mill. Furthermore, it may be finely pulverized by mechanical grinding using frictional force. Regarding the dispersing machine and fine pulverization, reference can be made to the description in "Encyclopedia of Pigments" (written by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pages 438 and 310).

＜＜Middle layer＞＞
The transfer layer preferably includes an intermediate layer between the temporary support and the photosensitive layer.

By arranging the intermediate layer, it is possible to suppress mixing of components during coating of a plurality of layer-forming compositions and during storage after coating.

The intermediate layer is preferably a water-soluble resin layer containing a water-soluble resin.
Further, as the intermediate layer, an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in JP-A-5-072724, can also be used. It is preferable that the intermediate layer is an oxygen barrier layer because sensitivity during exposure is improved, time load on the exposure machine is reduced, and productivity is improved.

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

Hereinafter, each component that the intermediate layer may contain will be explained.

It is preferable that the intermediate layer contains resin.

It is preferable that the above resin contains a water-soluble resin as part or all of it.

Examples of resins that can be used as water-soluble resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Examples include resins such as coalescence.

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

When the water-soluble resin is a copolymer of (meth)acrylic acid/vinyl compound, each composition ratio (mol%) is preferably 90/10 to 20/80, and 80/20 to 30/70, for example. 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. Further, 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 degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

In addition, in order to further improve the interlayer mixing suppressing ability of the intermediate layer, the resin contained in the intermediate layer is the same as the resin contained in the layer disposed on one side of the intermediate layer and the resin contained in the layer disposed on the other side of the intermediate layer. It is preferable that the resin is different from the resin contained in the. For example, if the photosensitive layer contains polymer A and the thermoplastic resin layer contains thermoplastic resin (alkali-soluble resin), the intermediate layer contains polymer A and thermoplastic resin (alkali-soluble resin). It is preferable that the resin is different from the soluble resin.

The water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of further improving oxygen barrier properties and interlayer mixing suppression ability.

The number of water-soluble resins contained in the intermediate layer may be one type, or two or more types.

The content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more based on the total mass of the water-soluble resin layer (intermediate layer) in order to further improve oxygen barrier properties and ability to suppress interlayer mixing. , more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more. The upper limit is not particularly limited, but is preferably 99.9% by mass or less, more preferably 99.8% by mass or less.

The intermediate layer may contain known additives such as surfactants, if necessary.

The number of surfactants contained in the intermediate layer may be one, or two or more.
The surfactant preferably includes at least one selected from the group consisting of nonionic surfactants, fluorine surfactants, and silicone surfactants.

It is preferable that the surfactant contains a silicone surfactant from the viewpoint of the releasability, resolution, oxygen blocking ability, defect suppression property, etc. of the temporary support.

Also, silicone surfactants are preferred from the viewpoint of improving the adhesion between the intermediate layer and adjacent layers (photosensitive layer, thermoplastic resin, etc.) (hereinafter also referred to as "interlayer adhesion").
From the viewpoint of releasability, resolution, oxygen blocking ability, defect suppression ability, interlayer adhesion, etc. of the temporary support, the content of the silicone surfactant is 60% by mass based on the total mass of the surfactant. It is preferably at least 80% by mass, preferably at least 95% by mass, and may be 100% by mass.
Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers having an organic group introduced into at least one of a side chain and a terminal.

From the viewpoint of releasability, resolution, oxygen blocking ability, defect suppression ability, interlayer adhesion, etc. of the temporary support, the content of the surfactant is 0.1% by mass to 0.1% by mass based on the total mass of the intermediate layer. It is preferably 10% by weight, more preferably 0.5% to 7% by weight, and even more preferably 1% to 5% by weight.

The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not reduced and the ability to suppress interlayer mixing is excellent. Furthermore, it is also possible to suppress an increase in the time required to remove the intermediate layer during development.

<<Thermoplastic resin layer>>
The transfer layer preferably includes a thermoplastic resin layer between the temporary support and the intermediate layer. By including the thermoplastic resin layer in the transfer film, the followability to the substrate in the step of bonding the transfer film and the substrate is improved, and it is possible to suppress the inclusion of air bubbles between the substrate and the transfer film. As a result, adhesion between the thermoplastic resin layer and the layer adjacent to it (eg, temporary support) can be ensured.

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

<Alkali-soluble resin (thermoplastic resin)>
The thermoplastic resin is preferably an alkali-soluble resin.

Examples of alkali-soluble resins 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. , polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

As the alkali-soluble resin, acrylic resin is preferred from the viewpoint of developability and adhesion with adjacent layers.

Here, the acrylic resin is at least one selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic esters, and structural units derived from (meth)acrylic acid amide. It means a resin having one type of structural unit.

As for acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic amide is the total content of the acrylic resin. It is preferable that the amount is 50% by mass or more based on the mass.

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

Moreover, it is preferable that the alkali-soluble resin contains at least one selected from the group consisting of structural units derived from styrene and structural units derived from styrene derivatives. Specific examples of styrene derivatives include vinyltoluene, p-methylstyrene, and p-chlorostyrene.

The total content of structural units derived from styrene and structural units derived from styrene derivatives in the alkali-soluble resin is preferably 5% by mass to 60% by mass, and 10% by mass to 50% by mass, based on the total mass of the alkali-soluble resin. % is more preferable, and 15% to 40% by weight is even more preferable.

In addition, the alkali-soluble resin has a mass ratio of the content of structural units derived from (meth)acrylic acid ester to the total content of structural units derived from styrene and styrene derivatives from 0.3 to 2.5. It is preferably from 0.5 to 2.05, even more preferably from 0.7 to 1.75.

Furthermore, the alkali-soluble resin is preferably a polymer having acid groups.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with a carboxy group being preferred.

From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin with an acid value of 60 mgKOH/g or more, and even more preferably a carboxyl group-containing acrylic resin with 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, even more 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.

For example, among the polymers described in paragraph 0025 of JP-A-2011-095716, an alkali-soluble resin that is a carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more, and the alkali-soluble resin described in paragraphs 0033 to 0052 of JP-A-2010-237589. A carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more among the polymers of Examples include resin.

The copolymerization ratio of structural units having a carboxyl group in the above carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and 12% by mass, more preferably 10% by mass to 40% by mass, based on the total mass of the acrylic resin. More preferably, the amount is from % by mass to 30% by mass.

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 with an adjacent layer.

The alkali-soluble resin may have a reactive group. The reactive group may be any group that is capable of addition polymerization, and includes ethylenically unsaturated groups; polycondensable groups such as hydroxy groups and carboxy groups; and polyaddition reactive groups such as epoxy groups and (block) isocyanate groups. 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 number of alkali-soluble resins contained in the thermoplastic resin layer may be one type or two or more types.

From the viewpoint of developability and adhesion with adjacent layers, 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. It is preferably 40 to 80% by weight, more preferably 50 to 75% by weight.

<Pigment>
The thermoplastic resin layer contains a dye (also simply referred to as "dye B") whose maximum absorption wavelength is 450 nm or more in the wavelength range of 400 to 780 nm during color development, and whose maximum absorption wavelength changes with acid, base, or radical. It is preferable.

The preferred embodiments of dye B are the same as the preferred embodiments of dye N described above, except for the points described below.

From the viewpoint of visibility and resolution of exposed and non-exposed areas, dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and more preferably a dye whose maximum absorption wavelength changes with acid. .

From the viewpoint of visibility and resolution in exposed and non-exposed areas, the thermoplastic resin layer contains both a dye as dye B whose maximum absorption wavelength changes depending on an acid, and a compound that generates an acid when exposed to light, which will be described later. It is preferable to include.

The number of dyes B contained in the thermoplastic resin layer may be one, or two or more.

The content of dye B is preferably 0.2% by mass or more, and 0.2% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of exposed areas and non-exposed areas. It is more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass 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 brought into a colored state. Below, a method for quantifying the content of dye B will be explained using a dye that develops color due to radicals as an example.
A solution is prepared by dissolving 0.001 g and 0.01 g of the dye in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator, Irgacure OXE01 (trade name, BASF Japan Ltd.), is added to each of the obtained solutions, and irradiation with 365 nm light generates radicals to bring all the dyes into a colored state. Thereafter, the absorbance of each solution at a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve is created.
Next, the absorbance of the solution in which all the dyes are colored is measured in the same manner 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 dye contained in the thermoplastic resin layer is calculated based on a calibration curve.
Note that 3 g of the thermoplastic resin layer is the same as 3 g of the solid content of the composition for forming a thermoplastic resin layer.

<Compounds that generate acids, bases, or radicals when exposed to 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 when exposed to light.

The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.

As 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 the photocationic polymerization initiators that may be included in the photosensitive layer described above, and the preferred embodiments are the same except for the points described below.

From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoint of properties, it is more preferable to include 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 radical photopolymerization initiator include the radical photopolymerization initiator that the above-mentioned photosensitive layer may contain, and the preferred embodiments are also the same.

(Photobase generator)
The thermoplastic resin composition may also include a photobase generator.

The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2, 6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4 -morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl -4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

The number of compounds C contained in the thermoplastic resin layer may be one type, or two or more types.

The content of compound C is preferably 0.1% by mass to 10% by mass, and 0.5% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed areas and non-exposed areas. More preferably, the amount is from % by mass to 5% by mass.

<Plasticizer>
The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion with adjacent layers, and developability.

The plasticizer preferably has a smaller molecular weight (weight average molecular weight if it is an oligomer or polymer and has a molecular weight distribution) than the 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 exhibits plasticity by being compatible with the alkali-soluble resin, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and 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.

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

Examples of the (meth)acrylate compound used as a plasticizer include the (meth)acrylate compound described above as a polymerizable compound contained in the photosensitive layer.

In the transfer film, when the thermoplastic resin layer and the photosensitive layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the negative photosensitive layer contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, thereby suppressing component diffusion between the layers and improving storage stability.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesion between the thermoplastic resin layer and an adjacent layer, it is important that the (meth)acrylate compound does not polymerize even in the exposed area after exposure. preferable.

In addition, from the viewpoints of resolution of the thermoplastic resin layer, adhesion with adjacent layers, and developability, the (meth)acrylate compound used as a plasticizer should contain two or more (meth) A polyfunctional (meth)acrylate compound having an acryloyl group is preferred.

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

The number of plasticizers contained in the thermoplastic resin layer may be one type, or two or more types.

The content of the plasticizer is 1% by mass to 70% by mass based on the total mass of the thermoplastic resin layer, from the viewpoint of resolution of the thermoplastic resin layer, adhesion with adjacent layers, and developability. It is preferably 10% by mass to 60% by mass, more preferably 20% by mass to 50% by mass.

<Sensitizer>
The thermoplastic resin layer may contain a sensitizer.

The sensitizer is not particularly limited, and includes the sensitizers that may be included in the above-mentioned negative photosensitive layer.

The number of sensitizers contained in the thermoplastic resin layer may be one type or two or more types.

The content of the sensitizer can be selected as appropriate depending on the purpose, but from the viewpoint of improving sensitivity to light sources and visibility of exposed and non-exposed areas, the content of the sensitizer should be 0.01% based on the total mass of the thermoplastic resin layer. It is preferably from 0.05% to 1% by weight, more preferably from 0.05% to 1% by weight.

<Additives, etc.>
In addition to the above-mentioned components, the thermoplastic resin layer may also contain known additives such as surfactants, if necessary.

Furthermore, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A No. 2014-085643, and the contents of this publication are incorporated herein.

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

<<Protective film>>
The transfer film may have a protective film.

As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. It will be done.

Furthermore, a resin film made of the same material as the above-mentioned temporary support may be used as the protective film.

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

The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, even more preferably 5 μm to 40 μm, and particularly preferably 15 μm 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 being relatively inexpensive.

Further, in the protective film, it is preferable that the number of fish eyes with a diameter of 80 μm or more contained in the protective film is 5 or less/m ² .

In addition, "fish eyes" refers to foreign matter, undissolved matter, oxidized deterioration products, etc. of materials when manufacturing films by methods such as heat-melting, kneading, extrusion, biaxial stretching, and casting methods. was captured in the film.

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, and even more preferably 5 particles/mm ² or less.

Thereby, defects caused by the transfer of unevenness caused by particles contained in the protective film to the photosensitive layer or the conductive layer can be suppressed.

From the viewpoint of imparting windability, 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 0.03 μm. The above is more preferable. On the other hand, it is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

The protective film may be a recycled product. Examples of recycled products include those that have been washed and made into chips from used films, and made into films using these as materials. A specific example of recycled products is Toray Industries' Ecouse series.

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

<<Transfer film manufacturing method>>
The method for producing the transfer film according to the present disclosure is not particularly limited, and any known method can be used.
As a method for manufacturing the above-mentioned transfer film 20, for example, a composition for forming a thermoplastic resin layer is applied to the surface of the temporary support 11 to form a coating film, and this coating film is further dried to form a thermoplastic resin layer. a step of forming an intermediate layer 15 by applying an intermediate layer forming composition to the surface of the thermoplastic resin layer 13 to form a coating film, and further drying this coating film to form an intermediate layer 15; The method includes the steps of applying a photosensitive composition to the surface of the photosensitive layer 15 to form a coating film, and further drying the coating film to form the photosensitive layer 17.

The transfer film 20 is manufactured by pressing the protective film 19 onto the photosensitive layer 17 of the laminate manufactured by the above manufacturing method.

The method for manufacturing a transfer film according to the present disclosure includes the step of providing a protective film 19 in contact with the surface of the photosensitive layer 17 opposite to the side on which the temporary support 11 is provided. It is preferable to produce a transfer film 20 comprising a thermoplastic resin layer 13, an intermediate layer 15, a photosensitive layer 17, and a protective film 19. The thermoplastic resin layer 13, the intermediate layer 15, and the photosensitive layer 17 correspond to the transfer layer 12.

After manufacturing the transfer film 20 using the above manufacturing method, the transfer film 20 may be wound up to create and store a roll-shaped transfer film. The transfer film in the form of a roll can be provided as it is for the step of bonding it to a substrate using a roll-to-roll method, which will be described later.

The method for manufacturing the transfer film 20 described above is a method in which the photosensitive layer 17 and the intermediate layer 15 are formed on the protective film 19, and then the thermoplastic resin layer 13 is formed on the surface of the intermediate layer 15. Good too.

<Method for forming thermoplastic resin layer>
The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and any known method can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer onto a temporary support and drying it if necessary.

The composition for forming a thermoplastic resin layer preferably contains the various components that form the thermoplastic resin layer described above and a solvent. In addition, in the composition for forming a thermoplastic resin layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the thermoplastic resin layer described above. be.

The solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent, and any known solvent can be used. Examples of the solvent include those similar to those contained in the photosensitive composition described below, and preferred embodiments are also the same.

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

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.) may be used. Can be mentioned.

<Method for forming intermediate layer>
The composition for forming an intermediate layer preferably contains the various components for forming the intermediate layer described above and a solvent. In addition, in the intermediate layer forming composition, the preferred range of the content of each component relative to the total solid content of the intermediate layer forming composition is the same as the preferred range of the content of each component relative to the total mass of the intermediate layer described above. be.

The solvent is not particularly limited as long as it is capable of dissolving or dispersing the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents; A mixed solvent with a solvent is more preferable.

Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.

The number of solvents contained in the intermediate layer forming composition may be one, or two or more.

The content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass based on 100 parts by mass of the total solid content of the intermediate layer forming composition. Parts to 900 parts by mass are more preferred.

The method for forming the intermediate layer is not particularly limited as long as it is a method that can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). .

<Method for forming photosensitive layer>
A coating method using a photosensitive composition containing the components constituting the photosensitive layer (e.g., polymer A, a polymerizable compound, a polymerization initiator, etc.) and a solvent is advantageous in terms of productivity. It is desirable that the

Specifically, the method for producing a transfer film according to the present disclosure includes coating a photosensitive composition on an intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to make it photosensitive. A method of forming layers is preferred. Note that the amount of remaining solvent is adjusted by drying the coating film.

The photosensitive composition preferably contains the various components that form the photosensitive layer described above and a solvent. In the photosensitive composition, the preferred range of the content of each component relative to the total solid content of the photosensitive composition is the same as the preferred range of the content of each component relative to the total mass of the photosensitive layer described above.

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

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

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

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

As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvents described in paragraph 0014 of JP2018-177889 may be used, and the contents of these are herein incorporated by reference. be incorporated into.

The number of solvents contained in the photosensitive composition may be one, or two or more.

The content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, more preferably 100 parts by mass to 1200 parts by mass, and further preferably 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition. preferable.

Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (ie, slit coating).

As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying are preferred.

The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Further, the upper limit thereof is preferably 130°C or less, more preferably 120°C or less. Drying can also be carried out by continuously changing the temperature.

Moreover, the drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. Further, the upper limit thereof is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

Furthermore, the transfer film according to the present disclosure can be manufactured by laminating a protective film to the photosensitive layer.

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

Examples of the device for laminating the protective film to the photosensitive layer include known laminators such as a vacuum laminator and an auto-cut laminator.

The laminator is preferably equipped with any heatable roller such as a rubber roller, and is capable of applying pressure and heating.

The transfer film according to the present disclosure can be applied to various uses.
The transfer film according to the present disclosure can be used, for example, as an electrode protective film, an insulating film, a flattening film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an antireflection film, an etching resist, and Applicable to plated parts.

More specifically, the transfer film according to the present disclosure can be used as a protective film or insulating film for touch panel electrodes, a protective film or insulating film for printed wiring boards, a protective film or insulating film for TFT substrates, a color filter, and an overcoat film for color filters. It can be applied to etching resists for forming wiring, plating resists for forming wiring, and plating resists for forming flexible printed wiring boards.

[Pattern formation method]
The pattern forming method according to the present disclosure includes:
A step of preparing a transfer film including a temporary support and a transfer layer disposed on the temporary support (preparation step);
A step of bonding the transfer film and the substrate so that the surface of the transfer film opposite to the surface of the temporary support is in contact with the substrate (bonding step);
a step of peeling off the temporary support to obtain a laminate (temporary support peeling step);
A step of exposing the laminate to light in a pattern (exposure step);
A step of developing the exposed laminate to form a pattern,
The temporary support preferably has a thermal deformation rate of 1.0% or less.

Each step will be explained below.

[Preparation process]
In the preparation step, a transfer film including a temporary support and a transfer layer disposed on the temporary support is prepared. A preferred embodiment of the transfer film is as described above.

[Lamination process]
In the bonding step, the transfer film and the substrate are bonded together such that the surface of the transfer film opposite to the surface of the temporary support is in contact with the substrate.
Note that when the transfer film includes a protective film, the protective film is peeled off before being bonded to the substrate.

The transfer film is preferably bonded to the substrate by stacking the transfer layer on the substrate and applying pressure and heat using means such as a roll. For bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further improve productivity can be used.

The lamination temperature is preferably 70°C to 130°C.

<Substrate>
As a substrate used for forming a pattern according to the present disclosure, a known substrate can be used. The substrate may be a substrate having a conductive layer, or may be a substrate having a conductive layer on the surface of the base material.

The substrate may have any layer other than the conductive layer as necessary.

Examples of the base material constituting the substrate include glass, silicon, and resin film.

When using glass as the base material, the base material is preferably transparent. Further, the refractive index of the base material is preferably 1.50 to 1.52.

Examples of transparent glass substrates include tempered glass represented by Corning's Gorilla Glass. Furthermore, as the transparent glass substrate, materials described in JP-A No. 2010-86684, JP-A No. 2010-152809, and JP-A No. 2010-257492 may be used.

When using a resin film as the base material, the base material is preferably a resin film with low optical distortion and/or high transparency. Such resin films include, for example, polyethylene terephthalate (PET) films, polyethylene naphthalate films, polycarbonate films, triacetylcellulose films, and cycloolefin polymer films.

When manufacturing using a roll-to-roll method, the base material is preferably a resin film. Moreover, when manufacturing circuit wiring for a touch panel by a roll-to-roll method, it is preferable that the base material is a resin sheet.

The thickness of the base material is preferably 5 μm to 200 μm, more preferably 10 μm 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 in terms of conductivity and fine line formation. It is preferable that there be.

Furthermore, only one conductive layer or two or more conductive layers may be disposed on the base material. When two or more conductive layers are arranged, it is preferable to have conductive layers made of different materials.

A preferred embodiment of the conductive layer is described, for example, in paragraph [0141] of International Publication No. 2018/155193, the content of which is incorporated herein.

The conductive layer is preferably a metal layer.

The metal layer is a layer containing metal, and the metal is not particularly limited, and any known metal can be used. Preferably, the metal layer is a conductive layer.

Examples of the main components (so-called main metals) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. Note that the term "main metal" refers to the metal with the largest content among the metals contained in the metal layer.

The thickness of the conductive layer is not particularly limited, and is preferably 50 nm or more, more preferably 100 nm or more. The upper limit is preferably 2 μm or less.

The method of forming the conductive layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion in which fine metal particles are dispersed and sintering a coating film, a sputtering method, and a vapor deposition method.

[Temporary support peeling process]
In the temporary support peeling step, the temporary support is peeled off to obtain a laminate. In the pattern forming method according to the present disclosure, since the temporary support is peeled off in advance, foreign matter contained in the temporary support does not affect the exposure in the exposure step.

The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.
[Exposure process]
In the exposure step, the laminate obtained in the peeling step is exposed in a pattern.

The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. It is preferable that at least a part of the pattern (preferably the electrode pattern of the touch panel and/or the lead-out wiring part) includes a thin line with a width of 20 μm or less, and more preferably a thin line with a width of 10 μm or less. The display quality of a display device (for example, a touch panel) equipped with an input device having circuit wiring manufactured by the circuit wiring manufacturing method can be improved, and the area occupied by the lead wiring can be reduced.

The light source used for exposure is not particularly limited as long as it irradiates light with a wavelength that can expose the photosensitive layer (for example, 365 nm or 405 nm), and can be appropriately selected and used. Examples of the light source include an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

The exposure amount is preferably 5 mJ/cm ² to 200 mJ/cm ² , more preferably 10 mJ/cm ² to 100 mJ/cm ² .

In the exposure step, the mask and the photosensitive layer may be brought into contact with each other for exposure, or the mask and the photosensitive layer may be brought into close proximity without contacting each other for exposure.

The exposure method is contact exposure method in case of contact exposure method, proximity exposure method in case of non-contact exposure method, projection exposure method using lens system or mirror system, or direct exposure method using exposure laser etc. can be selected and used as appropriate. In the case of a lens-based or mirror-based projection exposure method, an exposure machine having an appropriate lens numerical aperture (NA) can be used depending on the required resolving power and depth of focus. In the case of a direct exposure method, the photosensitive layer may be directly exposed to light, or the photosensitive layer may be subjected to reduction projection exposure through a lens. Moreover, exposure may be performed not only under the atmosphere but also under reduced pressure or vacuum. Alternatively, exposure may be performed with a liquid such as water interposed between the light source and the photosensitive layer.

Examples of masks include quartz masks, soda lime glass masks, and film masks. Among these, quartz masks are preferred because they have excellent dimensional accuracy, and film masks are preferred because they can be easily made large. As the base material for the film mask, a polyester film is preferred, and a polyethylene terephthalate film is more preferred.
A specific example of the base material of the film mask is XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).

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

[Development process]
In the development step, the exposed laminate is developed to form a pattern.

Development can be performed using a developer.

The developing solution is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxy. and choline (2-hydroxyethyltrimethylammonium hydroxide).

Examples of development methods include paddle development, shower development, spin development, and dip development.

Suitable developers include, for example, the developer described in paragraph [0194] of WO 2015/093271, and examples of development methods that are suitably used include, for example, the developer described in paragraph [0194] of WO 2015/093271. Examples include the development method described in [0195].

[Post-exposure process and post-bake process]
The pattern forming method according to the present disclosure may include a step of exposing the pattern obtained by the developing step (post-exposure step) and/or a step of heating (post-bake step).

When both a post-exposure step and a post-bake step are included, it is preferable to perform post-bake after post-exposure.

The exposure amount of post-exposure is preferably 100 mJ/cm ² to 5000 mJ/cm ² , more preferably 200 mJ/cm ² to 3000 mJ/cm ² .

The post-bake temperature is preferably 80°C to 250°C, more preferably 90°C to 160°C.

The post-bake time is preferably 1 minute to 180 minutes, more preferably 10 minutes to 60 minutes.

[Circuit wiring manufacturing method]
In the first aspect of the method for manufacturing circuit wiring according to the present disclosure,
A step of preparing a transfer film including a temporary support and a transfer layer disposed on the temporary support (preparation step);
A step of bonding the transfer film and the substrate so that the surface of the transfer film opposite to the surface of the temporary support is in contact with the substrate (bonding step);
a step of peeling off the temporary support to obtain a laminate (temporary support peeling step);
A step of exposing the laminate to light in a pattern (exposure step);
A step of developing the exposed laminate to form a pattern (developing step);
A process of plating an area of the substrate where no pattern is placed (plating process);
A step of peeling off the pattern (pattern peeling step),
The temporary support preferably has a thermal deformation rate of 1.0% or less.
The preparation process, the bonding process, the temporary support peeling process, and the exposure process are the same as the pattern forming method described above, so their explanation will be omitted.

A conductor pattern is formed when plating is performed on an area where no pattern is placed. Generally, it is called a semi-additive method.

[Plating process]
In the plating process, plating is performed on areas of the substrate where no pattern is placed.

As the plating method, known methods can be applied, such as electroplating and electroless plating. Preferably, the plating is electroplating.

Examples of the metal included in the plating include known metals.
Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals.
Among these, it is preferable that the plating contains copper or an alloy thereof, since the conductivity of the conductive pattern is more excellent. Further, from the viewpoint of improving the conductivity of the conductive pattern, it is preferable that the plating layer contains copper as a main component.

Components of the plating solution used in electroplating include, for example, water-soluble copper salts. As the water-soluble copper salt, water-soluble copper salts commonly used as components of plating solutions can be used. The water-soluble copper salt is preferably at least one selected from the group consisting of, for example, an inorganic copper salt, an alkanesulfonic acid copper salt, an alkanolsulfonic acid copper salt, and an organic acid copper salt. Examples of inorganic copper salts include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of copper alkanesulfonate include copper methanesulfonate and copper propanesulfonate. Examples of copper alkanolsulfonate salts include copper isethionate and copper propanolsulfonate. Examples of organic acid copper salts include copper acetate, copper citrate, and copper tartrate.

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

The electroplating method and conditions are not limited. For example, a conductor pattern can be formed by supplying the laminate after the development process to a plating tank in which a plating solution is added. In electroplating, a conductor pattern can be formed by, for example, controlling the current density and the transport speed of the transparent base material.

The temperature of the plating solution used for electroplating is preferably 70°C or lower, more preferably 10°C to 40°C. The current density in electroplating is preferably 0.1 A/dm ² to 100 A/dm ² , more preferably 0.5 A/dm ² to 20 A/dm ² . The productivity of conductor patterns can be improved by increasing the current density. By lowering the current density, the uniformity of the thickness of the conductor pattern can be improved.

[Pattern peeling process]
The pattern peeling process is a process of peeling off the pattern.
Examples of methods for removing the remaining pattern include a method of removing it by chemical treatment, and a method of removing it using a stripping liquid is preferable.
As a method for removing the remaining pattern, for example, a known method such as a spray method, a shower method, and a paddle method using a stripping solution may be used.

Examples of the stripping solution include a stripping solution in which an alkaline compound is dissolved in at least one selected from the group consisting of water, dimethyl sulfoxide, and N-methylpyrrolidone.

Examples of alkaline compounds (compounds that exhibit alkalinity when dissolved in water) include alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, as well as primary amine compounds, secondary amine compounds, and tertiary amine compounds. and alkaline organic compounds such as quaternary ammonium salt compounds. As the alkaline organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferred.

A method for removing the pattern is to immerse the substrate with the remaining resist pattern in a stirring stripping solution at a temperature of 30°C to 80°C (preferably 50°C to 80°C) for 1 minute to 30 minutes. can be mentioned.
It is also preferable that the stripping liquid does not dissolve the conductive layer.

The pH of the stripping solution during the stripping treatment is preferably 11 or higher, more preferably 12 or higher, and even more preferably 13 or higher. The upper limit is preferably 14 or less, more preferably 13.8 or less. The pH can be measured using a known pH meter according to JIS Z8802-1984. The pH measurement temperature is 25°C.

The temperature of the stripping solution during the stripping process is preferably higher than the temperature of the developer during the development process. Specifically, the value obtained by subtracting the temperature of the developer from the temperature of the stripping solution (temperature of the stripping solution - temperature of the developer) is preferably 10°C or higher, more preferably 20°C or higher. preferable. The upper limit is preferably 100°C or less, more preferably 80°C or less.

It is preferable that the pH of the stripping solution used in the stripping process is higher than the pH of the developer used in the development process. Specifically, the value obtained by subtracting the pH of the developer from the pH of the stripping solution (pH of the stripping solution - pH of the developer) is preferably 1 or more, more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.

After removing the pattern with a remover, it is also preferable to perform a rinsing process to remove the remover remaining on the substrate. Water or the like can be used for rinsing.
After stripping and/or rinsing the pattern using a stripping liquid, a drying process may be performed to remove excess liquid from the substrate.

In a second aspect of the method for manufacturing circuit wiring according to the present disclosure, the bonding step, the peeling step, the exposure step, and the step of etching the substrate in a region where a pattern is not arranged (etching step) are provided. , and a step of peeling off the pattern (pattern peeling step).

[Etching process]
In the etching process, the pattern formed from the photosensitive layer is used as an etching resist to perform etching on the substrate.

As the etching treatment method, known methods can be applied, such as the method described in paragraphs 0209 to 0210 of JP2017-120435A, and the method described in paragraphs 0048 to 0054 of JP2010-152155A. Examples include a wet etching method using immersion 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 depending on the object to be etched.

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, and an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid; Mention may be made of mixed aqueous solutions with salts selected from potassium permanganate. The acidic component may be a combination of multiple acidic components.

Examples of the alkaline etching solution include an aqueous solution of an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide), and alkaline components and salts. (for example, potassium permanganate). The alkaline component may be a combination of a plurality of alkaline components.

After the etching process, it is also preferable to perform a rinsing process to remove the etching solution remaining on the substrate before proceeding to the next step. Water or the like can be used for rinsing.
After the etching process and/or the rinsing process, a drying process may be performed to remove excess liquid from the substrate.

[Pattern peeling process]
The pattern peeling process in the second aspect can be performed in the same manner as the pattern peeling process in the first aspect.

[Other processes]
The method for manufacturing circuit wiring according to the present disclosure may include any steps (other steps) other than the steps described above. Examples include, but are not limited to, the following steps.

In addition, examples of the exposure step, development step, and other steps applicable to the method for manufacturing circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A No. 2006-23696.

<Step of reducing visible light reflectance>
The method for manufacturing circuit wiring may include the step of performing a process of reducing the visible light reflectance of part or all of the conductive layer included in the substrate.

An example of the treatment for reducing visible light reflectance is oxidation treatment. When the substrate includes a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.

The treatment for reducing visible light reflectance is described in paragraphs 0017 to 0025 of JP 2014-150118, and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315. , the contents of these publications are incorporated herein.

<Process of forming an insulating film, process of forming a new conductive layer on the surface of the insulating film>
It is also preferable that the method for manufacturing the circuit wiring includes the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. Through the above steps, it is possible to form a second electrode pattern that is insulated from the first electrode pattern.

The step of forming the insulating film is not particularly limited, and includes known methods for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.

The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer with a desired pattern may be formed by photolithography using a conductive photosensitive material.

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

[Applications of circuit wiring]
The circuit wiring manufactured by the circuit wiring manufacturing method can be applied to various devices. Examples of the device including circuit wiring manufactured by the above manufacturing method include an input device, preferably a touch panel, and more preferably a capacitive touch panel. Furthermore, the input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[Manufacturing method of printed wiring board]
The transfer film of the present disclosure can be used for manufacturing printed wiring boards. The method for manufacturing a printed wiring board includes the step of subjecting the substrate having the resist pattern to at least one selected from the group consisting of etching treatment and plating treatment. Here, the etching treatment or plating treatment of the substrate can be performed on the surface of the substrate by a known method using a developed resist pattern as a mask.
Further, before the etching treatment or the plating treatment, a residual film removal process may be performed using resin etching using a chemical solution containing potassium permanganate or the like, resin ashing using plasma, or the like.

Examples of the etching solution used in the etching process include a cupric chloride solution, a ferric chloride solution, and an alkaline etching solution. Examples of plating include copper plating, solder plating, nickel plating, and gold plating.

After performing the etching treatment or the plating treatment, the resist pattern can be peeled off using an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used for development, for example. As this strong alkaline aqueous solution, for example, a 1% to 10% by mass aqueous sodium hydroxide solution and a 1% to 10% by mass potassium hydroxide aqueous solution are used. Furthermore, examples of the peeling method include a dipping method and a spray method. Note that the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board, and may have small-diameter through holes.

When plating is performed on a substrate that includes an insulating layer and a conductor layer formed on the insulating layer, it is necessary to remove the conductor layer other than the resist pattern. This removal method includes, for example, a method in which the resist pattern is peeled off and then lightly etched; plating is followed by solder plating, and then the resist pattern is peeled off to mask the wiring part with solder, and then the wiring part is masked with solder. One example is a method of processing using an etching solution that can etch only the portions of the conductor layer that are not etched.

Embodiments of the present invention will be described in more detail with reference to Examples below. The materials, amounts used, proportions, processing details, and processing procedures shown in the following examples can be changed as appropriate without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below.

<Preparation of photosensitive composition>
The components used to prepare the photosensitive composition are as follows.
[Polymer A]
- Alkali-soluble resin with crosslinkable group 1: Styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA)/methacrylic acid-glycidyl methacrylate (GMA-MAA) = 47.7/1.3/19 /32 (mass ratio), Mw: 20,000, acid value: 124 mgKOH/g, glass transition temperature: 76°C, solid content: 30% by mass, weight average molecular weight: 20,000
・Alkali-soluble resin 2 having a crosslinkable group: styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA)/methacrylic acid-glycidyl methacrylate (GMA-MAA) = 34/15/19/32 (mass) ratio), Mw: 20,000, acid value: 124 mgKOH/g, glass transition temperature: 77°C, solid content: 30% by mass, weight average molecular weight: 20,000
・Alkali-soluble resin 3 having a crosslinkable group: styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA)/methacrylic acid-glycidyl methacrylate (GMA-MAA) = 22/27/19/32 (mass) ratio), Mw: 20,000, acid value: 124 mgKOH/g, glass transition temperature: 78°C, solid content: 30% by mass, weight average molecular weight: 20,000
Note that "methacrylic acid-glycidyl methacrylate" refers to a structural unit obtained by reacting the carboxy group of a structural unit derived from methacrylic acid with the epoxy group of glycidyl methacrylate.

[Polymerizable compound]
・BPE-500: Product name "NK Ester BPE-500", ethoxylated bisphenol A dimethacrylate, average repeating number of ethylene oxide chains 10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ・BPE-100: Product name "NK Ester BPE-100" ”, Ethoxylated bisphenol A dimethacrylate, average repeating number of ethylene oxide chains 2.6, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Product name “Aronix M-270”, polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. , the above BPE-500 and BPE-100 correspond to polymerizable compound B1.

[Polymerization initiator]
・B-CIM: Product name “B-CIM” (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Kurogane Kasei Co., Ltd.)

[Sensitizer]
・EAB-F: Product name "EAB-F", 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Boeki Co., Ltd.

[Polymerization inhibitor]
・Phenothiazine (manufactured by Fujifilm Wako Pure Chemical Industries)

〔Antioxidant〕
・Phenidone 1% MEK solution: Methyl ethyl ketone solution containing 1% by mass of phenidone, manufactured by Tokyo Kasei Kogyo Co., Ltd.

[Chain transfer agent]
・Compound A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[Pigment]
・LCV: Leuco crystal violet, manufactured by Tokyo Kasei Kogyo Co., Ltd., a pigment that develops color due to radicals ・Malachite green: Malachite green oxalate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

〔anti-rust〕
・CBT-1: Product name “CBT-1”, carboxybenzotriazole, manufactured by Johoku Kagaku Kogyo Co., Ltd.

[Surfactant]
・F-552: Product name "Megafac F-552", manufactured by DIC Corporation

〔solvent〕
・MMPGAc: 1-methoxy-2-propyl acetate ・MEK: Methyl ethyl ketone ・MFG: Propylene glycol monomethyl ether

The above components were mixed in the amounts (parts by mass) listed in Table 1 to prepare a photosensitive composition.

<Preparation of composition for forming intermediate layer>
The components used to prepare the intermediate layer forming composition are as follows.

[Water-soluble resin]
・PVA: Polyvinyl alcohol ・PVP: Polyvinylpyrrolidone ・HPMC: Hydroxypropyl methylcellulose

[Surfactant]
・F-444: Product name "Megafac F-444", manufactured by DIC Corporation

〔solvent〕
・Methanol・Pure water

The above components were mixed in the amounts (parts by mass) listed in Table 1 to prepare a composition for forming an intermediate layer.

<Preparation of composition for forming thermoplastic resin layer>
The components used to prepare the composition for forming a thermoplastic resin layer are as follows.

〔Thermoplastic resin〕
- Alkali-soluble resin B1: benzyl methacrylate (BzMA)/methacrylic acid (MAA)/acrylic acid (AA) = 78/14.5/7.5 (mass ratio), Mw: 12,500, acid value: 187 mgKOH/ g, glass transition temperature: 75°C, solid content: 30% by mass

[Polymerizable compound]
・A-DCP: Product name "NK ester A-DCP", tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・8UX-015A: Product name "8UX-015A", UV-curable urethane acrylate, TO-2349 manufactured by Taisei Fine Chemical Co., Ltd.: Product name "Aronix TO-2349" manufactured by Toagosei Co., Ltd.

〔solvent〕
・MEK: Methyl ethyl ketone

In Table 1, "B/A" means the ratio of the total mass of polymerizable compound B1 to the total mass of polymer A.

<Preparation of temporary support>
Temporary supports 1 to 6, which are biaxially stretched PET films shown in Table 2, were prepared.

For each temporary support, the thickness, thermal deformation rate, haze, surface energy, surface roughness Rmax, the total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more, and the total area ratio of the optically abnormal region were measured. The measurement method is as follows.

(thickness)
It was calculated as the average value of five arbitrary points measured by SEM cross-sectional observation.

(thermal deformation rate)
On the main surface of the temporary support, a direction parallel to one of the two opposing sides was defined as the A direction, and a direction perpendicular to the A direction was defined as the B direction.
A test piece cut out to have a length of 30 mm in the A direction and 4 mm in the B direction, and a test piece cut out to have a length of 30 mm in the B direction and 4 mm in the A direction were prepared.
The following measurements were performed using two test pieces.
As a measuring device, a thermal expansion coefficient measuring device (product name "TMA450EM", manufactured by TA Instruments) was used.
The measurement conditions are as follows.
Measurement mode: Tensile mode Grip distance: 16mm
Set load: Changed from 0.05N to 0.48N at 6.00N/min.
Each test piece was heated from 25°C to 100°C at a heating rate of 20°C/min, and the elongation rate of each test piece was measured five times, and the average value was calculated.
Of the two test pieces, the one with the larger average elongation rate was adopted as the thermal deformation rate.

(Haze)
It was measured using a haze meter according to JIS K7136:2000.

(Surface roughness Rmax)
The temporary support was peeled off from the transfer film. Obtain the surface profile of the surface of the temporary support on the transfer layer side. Microscope Application of MetroPro ver. 8.3.2 was used as the measurement/analysis software. Next, a Surface Map screen was displayed using the measurement/analysis software, and histogram data was obtained on the Surface Map screen. The surface roughness Rmax was obtained from the obtained histogram data.

(Total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more)
Observe the temporary support with a polarizing microscope (product name: "BX60" with "U-POT" filter and "U-AN360" filter inserted to make a simple polarizing microscope, 10x objective lens, manufactured by Olympus), The portion where the polarization disturbance occurred was identified as a foreign object (particle or aggregate). The identified foreign matter was observed with an epi-illumination laser microscope (product name: "Confocal Laser Microscope VL2000D", manufactured by Lasertec), and the total area ratio of the optically abnormal region, which will be described later, was measured. In addition, the diameter of foreign particles was measured using an optical microscope (product name "BX60", objective lens 100 times, manufactured by Olympus Corporation), and the number of foreign particles with a diameter of 5 μm or more included in an observation area of 1 mm ² was counted.

(Total area ratio of optical abnormal area)
A polarizing filter (OLS4000-QWP) was inserted above the objective lens of an epi-reflection laser microscope (OLS-4100 manufactured by Olympus). Next, the temporary support cut into 30 mm x 30 mm was horizontally suctioned and fixed on the stage of a laser microscope using a porous suction plate (65F-HG manufactured by Universal Giken) and a vacuum pump. The suction-fixed temporary support was observed at a laser beam intensity of 60 (laser wavelength: 405 nm) with a 50-fold objective lens. At this time, a region of 2 μm in the center of the temporary support in the thickness direction was set as the measurement region, and measurements were performed at 200 measurement points in the measurement region of 259 μm×260 μm.

The light amount difference between the pixel with the maximum light amount and the pixel with the minimum light amount in the measured image is divided into 4096 gradations (the value of the maximum light amount is 4095 and the value of the minimum light amount is 0). A histogram (horizontal axis: gradation of light amount (minimum value 0, maximum value 4095), vertical axis: number of pixels) was created, which is a graph of the light amount distribution of pixels in the image. The measured image is binarized using the gradation that is 400 gradations plus 400 gradations from the larger of the two base values of the created histogram as the threshold, and the areas of pixels with a larger amount of light than the threshold are summed. , the total area was taken as the total area of the optically abnormal region. The ratio of the total area of the optically abnormal region to the measured area was calculated.

<Preparation of transfer film>
[Example 1]
The composition for forming an intermediate layer was applied onto the temporary support 1 using a slit-shaped nozzle so that the thickness after drying would be the thickness of the intermediate layer shown in Table 1. The coating film of the composition for forming an intermediate layer was dried at 90° C. for 120 seconds to form an intermediate layer. A photosensitive composition was applied onto the intermediate layer using a slit-shaped nozzle so that the thickness after drying would be the thickness of the photosensitive layer shown in Table 1. The coating film of the photosensitive composition was dried at 80° C. for 120 seconds to form a photosensitive layer. That is, an intermediate layer and a photosensitive layer were formed as a transfer layer 1 on a temporary support 1. Thereby, a transfer film having the temporary support 1, the intermediate layer, and the photosensitive layer in this order was obtained.

The surface free energy of the transfer layer 1 on the side facing the temporary support 1 was 60.1 mJ/m ² .
The content of water in the transfer layer 1 was 0.1% by mass based on the total amount of the transfer layer 1.
The content of iron atoms in the transfer layer 1 was 0.01 ppm based on the total amount of the transfer layer 1.
The content of water in the photosensitive layer was 0.1% by mass based on the total amount of the photosensitive layer.
The content of iron atoms in the photosensitive layer was 0.01 ppm based on the total amount of the photosensitive layer.

[Example 2 to Example 5, Comparative Example 1]
A transfer film was obtained in the same manner as in Example 1, except that Temporary Support 1 was changed to Temporary Supports 2 to 6.

The surface free energy of the transfer layer 1 on the side facing each of the temporary supports 2 to 6 was 60.1 mJ/m ² .

[Example 6]
The composition for forming an intermediate layer was applied onto the temporary support 2 using a slit-shaped nozzle so that the thickness after drying would be the thickness of the intermediate layer shown in Table 1. The coating film of the composition for forming an intermediate layer was dried at 90° C. for 120 seconds to form an intermediate layer. A composition for a thermoplastic resin layer was applied onto the intermediate layer using a slit-shaped nozzle so that the thickness after drying would be the thickness of the thermoplastic resin layer shown in Table 1. The coating film of the composition for a thermoplastic resin layer was dried at 100° C. for 120 seconds to form a thermoplastic resin layer. A photosensitive composition was applied onto the thermoplastic resin layer using a slit-shaped nozzle so that the thickness after drying would be the thickness of the photosensitive layer shown in Table 1. The coating film of the photosensitive composition was dried at 80° C. for 120 seconds to form a photosensitive layer. That is, a thermoplastic resin layer, an intermediate layer, and a photosensitive layer were formed as a transfer layer 2 on a temporary support 2. Thereby, a transfer film having the temporary support 2, the thermoplastic resin layer, the intermediate layer, and the photosensitive layer in this order was obtained.

The surface free energy of the transfer layer 2 on the side facing the temporary support 2 was 60.1 mJ/m ² .
The content of water in the transfer layer 2 was 0.1% by mass based on the total amount of the transfer layer 2.
The content of iron atoms in the transfer layer 2 was 0.01 ppm based on the total amount of the transfer layer 2.
The content of water in the photosensitive layer was 0.1% by mass based on the total amount of the photosensitive layer.
The content of iron atoms in the photosensitive layer was 0.01 ppm based on the total amount of the photosensitive layer.

Using the transfer films obtained in Examples and Comparative Examples, substrate deformability, reticulation, and patterning properties were evaluated. The evaluation results are shown in Tables 2 and 3.

[Example 7 to Example 15]
A transfer film was obtained in the same manner as in Example 1, except that the transfer layer and temporary support were changed to those listed in Tables 2 and 3.

In Example 7, the surface free energy of the transfer layer 1 on the side facing the temporary support 6 was 60.1 mJ/m ² .
In Examples 8 and 12, the surface free energy of the transfer layer 3 on the side facing each temporary support was 60.1 mJ/m ² .
In Examples 9 and 13, the surface free energy of the transfer layer 4 on the side facing each temporary support was 60.1 mJ/m ² .
In Examples 10 and 14, the surface free energy of the transfer layer 5 on the side facing each temporary support was 60.1 mJ/m ² .
In Examples 11 and 15, the surface free energy of the transfer layer 6 on the side facing each temporary support was 60.1 mJ/m ² .

The content of water in transfer layers 3 to 6 was 0.1% by mass based on the total amount of each of transfer layers 3 to 6.
The content of iron atoms in the transfer layers 3 to 6 was 0.01 ppm based on the total amount of each of the transfer layers 3 to 6.
The water content in the photosensitive layers of transfer layers 3 to 6 was 0.1% by mass based on the total amount of the photosensitive layers.
The content of iron atoms in the photosensitive layers of transfer layers 3 to 6 was 0.01 ppm based on the total amount of the photosensitive layers.

<Substrate deformability>
Using a vacuum laminator (product name "MVR-250T", manufactured by MC Co., Ltd.), the transfer film and the substrate (product name "Metal Royal", manufactured by Toray Advanced Materials Korea) are exposed to light. They were bonded together so that the sexual layer was in contact with the substrate. Note that the transfer film was attached to both sides of the substrate. The bonding process was carried out under the conditions of a conveyance speed of 1 m/min, a degree of vacuum of 50 Pa, and a lamination temperature of 100°C. A laminate was obtained in which the temporary support, the transfer layer (intermediate layer/photosensitive layer), the substrate, the transfer layer (photosensitive layer/intermediate layer), and the temporary support were laminated in this order.
In the obtained laminate, one temporary support was peeled off. The peeled laminate was placed with the surface from which the temporary support was peeled as the top surface, and the amount of deformation of the substrate was measured.
The distance in the vertical direction between the center of the board and the end of the board was defined as the amount of deformation of the board. The evaluation criteria are as follows.
A: The amount of deformation is 1 cm or less.
B: The amount of deformation is more than 1 cm and less than 3 cm.
C: The amount of deformation is more than 3 cm and less than 5 cm.
D: The amount of deformation is more than 5 cm.

<Reticulation>
Similar to the evaluation of substrate deformability, a laminate was obtained in which the temporary support, transfer layer (intermediate layer/photosensitive layer), substrate, transfer layer (photosensitive layer/intermediate layer), and temporary support were laminated in this order. Ta.
In the obtained laminate, one temporary support was peeled off under an environment of a temperature of 23 degrees Celsius and a humidity of 50%. The surface of the transfer layer after peeling was visually observed to determine whether reticulation (wrinkles) had occurred. The evaluation criteria are as follows.
A: Reticulation has not occurred.
B: Reticulation is occurring.

<Patternability>
Using a vacuum laminator (product name "MVR-250T", manufactured by MC Co., Ltd.), the transfer film and the substrate (product name "Metal Royal", manufactured by Toray Advanced Materials Korea)) are They were bonded together so that the photosensitive layer was in contact with the substrate. Note that the transfer film was attached to one side of the substrate. The bonding process was carried out under the conditions of a conveyance speed of 1 m/min, a degree of vacuum of 50 Pa, and a lamination temperature of 100°C. A laminate was obtained in which the temporary support, the transfer layer (intermediate layer/photosensitive layer), and the substrate were laminated in this order.
In the obtained laminate, the temporary support was peeled off (peeling step). After the peeling step, ultraviolet rays were irradiated from the transfer layer side through a photomask at an exposure dose of 50 mJ/cm ² (exposure step). The photomask used for exposure had a line-and-space pattern in which the width ratio (duty ratio) of the transmitting area and the light-blocking area was 1:1, and the line width (and space width) was 15 μm. . After the exposure step, shower development was performed for 30 seconds using a 1.0% by mass aqueous sodium carbonate solution at a liquid temperature of 25° C. (development step). After the development process, the formed pattern was observed with an optical microscope to check for defects in the pattern (for example, disconnections, omissions, defects, etc.). The evaluation criteria are as follows.
A: There is no pattern defect.
B: There is a pattern defect.

The evaluation results are shown in Tables 2 and 3.

As shown in Tables 2 and 3, Examples 1 to 15 include a temporary support and a transfer layer disposed on the temporary support, and the temporary support has a thermal deformation rate of 1. It was found that since it was 0% or less, deformation of the substrate used in the transfer process was suppressed.
On the other hand, in Comparative Example 1, the thermal deformation rate of the temporary support was more than 1.0%, indicating that the substrate was deformed.

In Example 2, since the surface roughness Rmax of the surface of the temporary support on the transfer layer side was 0.5 μm or less, it was found that the patterning property was excellent compared to Example 3.

<Example 101: Production of flexible printed wiring board>
A copper layer with a thickness of 300 nm was provided on both sides of a polyimide base material (Kapton 100H, manufactured by Toray Industries, Inc.) with a thickness of 25 μm by a vapor deposition method to prepare a polyimide base material with a copper layer.

<Exposure method 1>
The transfer film of Example 1 was laminated on the above-mentioned copper layer-coated polyimide base material under the laminating conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 1.0 m/min, so that the copper layer and the photosensitive layer were in contact with each other. Both sides were laminated to produce a laminate for evaluation.
Next, the temporary supports on both sides were peeled off at an angle of 180°.
Next, using a photomask having a pattern with a predetermined line width (μm)/space width (μm), the intermediate layer was brought into contact with the mask to simultaneously expose both sides. For exposure, a high-pressure mercury lamp with i-line (365 nm) as the main exposure wavelength was used. The exposure amount was arbitrarily set so that the top shape of each pattern coincided with the mask opening. Shower development was performed on both sides with a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 30° C., followed by washing with water to obtain a laminate in which a predetermined pattern was formed on the copper layers on both sides.
The above laminate was subjected to acid degreasing, water washing, and sulfuric acid dipping in this order, and copper plating was performed using a copper sulfate plating solution at 1 A/dm ² until the plating thickness reached 15 μm. After washing with water and drying, the resist was removed using a 3.0 mass% sodium hydroxide aqueous solution at 50°C, and the seed layer was removed using an etching solution (containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide). It was removed with an aqueous solution (28° C.) and washed with water to produce a flexible printed wiring board. It was confirmed that the manufactured flexible printed wiring board operated normally.

<Exposure method 2>
The transfer film of Example 1 was laminated on both sides of a polyimide substrate with a copper layer so that the copper layer and the photosensitive layer were in contact with each other under the laminating conditions of a roll temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 1.0 m/min. A laminate for evaluation was produced.
Next, one side of the temporary support was peeled off at an angle of 180°, and the peeled side was exposed to light.
Exposure was carried out using a projection exposure machine equipped with a high-pressure mercury lamp, and reduced projection exposure was performed using an i-line (365 nm) through a mask. A mask having a pattern with a predetermined line width (μm)/space width (μm) was used. Further, the exposure amount was arbitrarily set so that the top shape of each pattern coincided with the mask opening.
Next, the temporary support of the transfer film on the side opposite to the exposed side was peeled off at an angle of 180°, and the peeled side was exposed under the same conditions as the first exposed side.
Shower development was performed on both sides with a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 30° C., followed by washing with water to obtain a laminate in which a predetermined pattern was formed on the copper layers on both sides.
The above laminate was subjected to acid degreasing, water washing, and sulfuric acid dipping in this order, and copper plating was performed using a copper sulfate plating solution at 1 A/dm ² until the plating thickness reached 15 μm. After washing with water and drying, the resist was removed using a 3.0 mass% sodium hydroxide aqueous solution at 50°C, and the seed layer was removed using an etching solution (containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide). It was removed with an aqueous solution (28° C.) and washed with water to produce a flexible printed wiring board. It was confirmed that the manufactured flexible printed wiring board operated normally.

[Examples 102 to 115]
Flexible printed wiring boards were produced in the same manner as in Example 101, except that the transfer films of Examples 2 to 15 were used. It was confirmed that the flexible printed wiring boards manufactured by either exposure method 1 or exposure method 2 operated normally.

The disclosures of Japanese Patent Application No. 2022-106641 filed on June 30, 2022 and Japanese Patent Application No. 2023-000740 filed on January 5, 2023 are incorporated by reference in their entirety. Incorporated herein. In addition, all documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference. , incorporated herein by reference.

Claims

comprising a temporary support and a transfer layer disposed on the temporary support,
The temporary support is a transfer film having a thermal deformation rate of 1.0% or less.
The transfer film according to claim 1, wherein the transfer layer has a surface free energy of 68.0 mJ/m 2 or less on the side facing the temporary support.
The transfer layer is in contact with the surface of the temporary support,
The transfer film according to claim 1 or 2, wherein the surface roughness Rmax of the transfer layer side surface of the temporary support is 0.5 μm or less.
The transfer film according to claim 1 or 2, wherein the transfer layer includes a photosensitive layer.
The transfer film according to claim 4, wherein the transfer layer includes an intermediate layer between the temporary support and the photosensitive layer.
The transfer film according to claim 5, wherein the transfer layer includes a thermoplastic resin layer between the temporary support and the intermediate layer.
The transfer film according to claim 1 or 2, wherein the temporary support has a haze of greater than 2.0%.
The transfer film according to claim 1 or 2, wherein the total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more contained in the temporary support is more than 30 pieces/mm 2 .
The transfer film according to claim 1 or 2, wherein the temporary support includes an area where the total area ratio of the optically abnormal area is larger than 300 ppm when observed in an area of 13.5 mm 2 with an epi-reflection laser microscope. .
The transfer film according to claim 1 or 2, wherein the temporary support has a thickness of 25 μm or more.
The transfer film according to claim 4, wherein the photosensitive layer contains an alkali-soluble resin having an acid value of 80 mgKOH/g to 250 mgKOH/g.
The transfer film according to claim 4, wherein the photosensitive layer contains an alkali-soluble resin having a crosslinkable group.
The photosensitive layer is made of an alkali whose mass ratio of the content of (meth)acrylic acid ester-derived structural units to the total content of styrene-derived structural units and styrene derivative-derived structural units is 0.3 to 2.5. The transfer film according to claim 4, comprising a soluble resin.
The transfer film according to claim 1 or 2, wherein the transfer layer has a water content of 0.1% by mass or more based on the total amount of the transfer layer.
The transfer film according to claim 4, wherein the photosensitive layer has a water content of 0.1% by mass or more based on the total amount of the photosensitive layer.
The transfer film according to claim 1 or 2, wherein the transfer layer has an iron atom content of 0.01 ppm to 10.0 ppm on a mass basis based on the total amount of the transfer layer.
The transfer film according to claim 4, wherein the photosensitive layer has an iron atom content of 0.01 ppm to 10.0 ppm on a mass basis based on the total amount of the photosensitive layer.
preparing a transfer film including a temporary support and a transfer layer disposed on the temporary support;
bonding the transfer film and the substrate so that the surface of the transfer film opposite to the surface of the temporary support is in contact with the substrate;
Peeling off the temporary support to obtain a laminate;
a step of exposing the laminate to light in a pattern;
Developing the exposed laminate to form a pattern,
The method for forming a pattern, wherein the temporary support has a thermal deformation rate of 1.0% or less.
preparing a transfer film including a temporary support and a transfer layer disposed on the temporary support;
bonding the transfer film and the substrate so that the surface of the transfer film opposite to the surface of the temporary support is in contact with the substrate;
Peeling off the temporary support to obtain a laminate;
a step of exposing the laminate to light in a pattern;
Developing the exposed laminate to form a pattern;
plating an area of the substrate where the pattern is not arranged;
peeling off the pattern;
The method for manufacturing circuit wiring, wherein the temporary support has a thermal deformation rate of 1.0% or less.