TW202311872A - Method for producing laminate having conductor pattern, transfer film - Google Patents

Abstract

The present invention provides a method for producing a laminate having a conductor pattern that is capable of producing a conductor pattern having a desired shape even under a condition that cleaning treatment applied with an acidic solution is implemented on a photoresist pattern before electroplating treatment is implemented, and a transfer film. A method for producing a laminate having a conductor pattern comprises, in sequence: a laminating step, in which a transfer film is laminated on a substrate in such a manner that a surface of the transfer film that is opposite to a pseudo support is put in contact with a metal layer of the substrate of which a surface includes the metal layer; an exposure step, in which a photosensitive composition layer is subjected to pattern exposure; a development step, in which developing treatment is implemented to form a photoresist pattern; a heating step, in which the photoresist pattern is subjected to heating; a cleaning step, in which an acidic solution is applied to clean the photoresist pattern that has been heated; an electroplating step, in which electroplating treatment is implemented; a stripping step, in which the photoresist pattern is peeled off; and a removing step, in which a metal layer that is exposed in the stripping step is removed to form a conductor pattern on the substrate. The photosensitive composition layer includes a thermal cross-linking agent.

Description

Manufacturing method of laminate with conductive pattern, transfer film

The present invention relates to a method for manufacturing a laminate with a conductor pattern and a transfer film.

The method of arranging a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing is widely used because the number of steps required to obtain a predetermined pattern is small.

Patent Document 1 discloses a method of laminating a photosensitive resin layer containing predetermined components on a support, transferring the photosensitive resin layer onto a substrate, and forming a photoresist by exposure treatment and development treatment. pattern, and then perform electroplating treatment to manufacture a circuit board.

[Patent Document 1] Japanese Patent Laid-Open No. 2016-139154

Recently, further miniaturization of the shape of the conductor pattern is required, and the demand for shape control is further increased. The inventors of the present invention referred to the method described in Patent Document 1, performed a cleaning process with an acidic solution to remove dirt on the photoresist pattern before the plating process, and performed the plating process. As a result, they found that the conductive pattern obtained The shape is deformed from the desired shape, and improvement is required.

An object of the present invention is to provide a method for producing a laminate having a conductive pattern capable of producing a desired shape of the conductive pattern even when the photoresist pattern is cleaned with an acidic solution before the plating process. Moreover, the subject of this invention is providing the transfer film.

As a result of intensive studies on the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems can be solved by the following configurations.

(1) A method of manufacturing a laminate having a conductor pattern, which sequentially comprises: In the pasting step, the surface of the transfer film having the dummy support and the negative photosensitive composition layer on the side opposite to the dummy support is in contact with the metal layer of the substrate having a metal layer on the surface. The printed film is bonded to the substrate; Exposure step, pattern exposure of the photosensitive composition layer; A development step, performing a development treatment on the exposed photosensitive composition layer to form a photoresist pattern; a heating step, heating the photoresist pattern; a cleaning step of cleaning the heated photoresist pattern with an acidic solution; An electroplating step, performing electroplating treatment on the metal layer located in the area where the photoresist pattern is not arranged; a stripping step, stripping the photoresist pattern; and a removal step of removing the metal layer exposed by the lift-off step and forming a conductor pattern on the substrate, Between the bonding step and the exposure step or between the exposure step and the development step, there is further a dummy support peeling step for peeling off the dummy support, The photosensitive composition layer contains a thermal crosslinking agent. (2) The method of manufacturing a laminate having a conductor pattern as described in (1), wherein The modulus of elasticity of the surface of the photoresist pattern heated in the heating step opposite to the substrate side is 5.0 GPa or more. (3) The method of manufacturing a laminate having a conductor pattern as described in (1) or (2), wherein Let the elastic modulus of the surface of the photoresist pattern heated by the heating step on the side opposite to the substrate side be the elastic modulus X, When the elastic modulus near the substrate side of the photoresist pattern heated by the heating step is defined as the elastic modulus Y, Satisfy X/Y≤1.2. (4) The method of manufacturing a laminate having a conductor pattern according to any one of (1) to (3), wherein The photosensitive composition layer contains a polymerizable compound and a polymerization initiator. (5) The method of manufacturing a laminate having a conductor pattern as described in (4), wherein The polymerizable compound has an alkylene oxide modified bisphenol structure. (6) The method for producing a laminate having a conductor pattern as described in any one of (1) to (5), wherein The thermal crosslinking agent contains blocked isocyanate compounds. (7) The method for producing a laminate having a conductor pattern according to any one of (1) to (6), wherein The haze of the pseudo-support is 1.0% or less. (8) The method of manufacturing a laminate having a conductor pattern as described in any one of (1) to (7), wherein The thickness of the pseudo-support is 50 μm or less. (9) The method of manufacturing a laminate having a conductor pattern according to any one of (1) to (8), wherein The transfer film has an intermediate layer between the dummy support and the photosensitive composition layer. (10) The method of manufacturing a laminate having a conductor pattern as described in (9), wherein The middle layer is a water-soluble resin layer. (11) The method for producing a laminate having a conductor pattern according to any one of (1) to (10), wherein The exposure step is a step of performing pattern exposure through a photomask. (12) The method for producing a laminate having a conductor pattern as described in any one of (1) to (10), wherein The exposing step is a step of pattern-exposing the photosensitive composition layer through a lens using active light on which the image of the mask is projected. (13) The method of manufacturing a laminate having a conductor pattern according to any one of (1) to (10), wherein There is a pseudo-support stripping step between the bonding step and the exposure step, The exposing step is a step of pattern-exposing the photosensitive composition layer by bringing the exposed surface of the dummy support into contact with a photomask. (14) A transfer film having a pseudo-support and a negative photosensitive composition layer, wherein The photosensitive composition layer contains a thermal crosslinking agent, The haze of the pseudo-support is 1.0% or less. (15) The transfer film as described in (14), wherein The thickness of the pseudo-support is 50 μm or less. (16) The transfer film as described in (14) or (15), wherein The photosensitive composition layer contains a polymerizable compound and a polymerization initiator. (17) The transfer film as described in (16), wherein The polymerizable compound has an alkylene oxide modified bisphenol structure. (18) The transfer film according to any one of (14) to (17), which has an intermediate layer between the dummy support and the photosensitive composition layer. (19) The transfer film as described in (18), wherein The middle layer is a water-soluble resin layer. [Invention effect]

According to the present invention, it is possible to provide a method for manufacturing a laminate having a conductor pattern capable of producing a desired shape of the conductor pattern even when the photoresist pattern is cleaned with an acidic solution before the plating process. Moreover, according to this invention, a transfer film can be provided.

Hereinafter, the present invention will be described in detail. The description of the constituent requirements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

The meaning of each description in this specification is shown below. In this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In this specification, among the numerical ranges described step by step, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other stages. In addition, in the numerical range described in this specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in an Example.

In this specification, the term "step" not only includes an independent step, but also includes in this term as long as the intended purpose of the step can be achieved even if it cannot be clearly distinguished from other steps.

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

In this specification, unless otherwise specified, TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both are trade names manufactured by TOSOH CORPORATION) are used as columns for weight average molecular weight (Mw) and number average molecular weight (Mn). Using THF (tetrahydrofuran) as an eluent, using a differential refractometer as a detector, and using polystyrene as a standard substance, and measuring with a gel permeation chromatography (GPC) analysis device, the polystyrene-converted standard substance is used. value. In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution means a weight average molecular weight (Mw). In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectroscopic analyzer. In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm. In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

In this specification, "(meth)acryl group" is a concept that includes both acryl group and methacryl group, and "(meth)acryloxy" includes both acryloxy and methacryloxy. Based on these two concepts.

In addition, in this specification, "alkali solubility" means that the solubility with respect to 100 g of 1 mass % aqueous solutions of sodium carbonate at 22 degreeC is 0.1 g or more.

In this specification, "water solubility" means that the solubility with respect to 100 g of water of pH7.0 whose liquid temperature is 22 degreeC is 0.1 g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the above-mentioned solubility conditions.

In this specification, the "solid content" of a composition refers to the components forming the composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), it refers to all components except the solvent. Moreover, if it is a component which forms a composition layer, a liquid component is also considered a solid component.

As a characteristic point of the manufacturing method of the laminated body which has a conductor pattern of this invention, the point that a photosensitive composition layer contains a thermal crosslinking agent can be mentioned. As a result of studying the causes of the above-mentioned problems in the prior art, the present inventors have found that when the photoresist pattern is cleaned with an acidic solution, the photoresist pattern is peeled off or disassembled, and as a result, the desired shape cannot be obtained. conductor pattern. Therefore, it has been found that by including a thermal crosslinking agent in the photosensitive composition layer and performing heat treatment after the development treatment to crosslink the photoresist pattern, the resistance to acidic solutions is improved, and as a result, a desired shape can be obtained. conductor pattern.

<Manufacturing method of laminate with conductor pattern> The manufacturing method of the laminated body with the conductor pattern of the present invention comprises in sequence: In the pasting step, the surface of the transfer film having the dummy support and the negative photosensitive composition layer on the side opposite to the dummy support is in contact with the metal layer of the substrate having a metal layer on the surface. The printed film is bonded to the substrate; Exposure step, pattern exposure of the photosensitive composition layer; A development step, performing a development treatment on the exposed photosensitive composition layer to form a photoresist pattern; a heating step, heating the photoresist pattern; a cleaning step of cleaning the heated photoresist pattern with an acidic solution; An electroplating step, performing electroplating treatment on the metal layer located in the area where the photoresist pattern is not arranged; a stripping step, stripping the photoresist pattern; and a removal step of removing the metal layer exposed by the lift-off step and forming a conductor pattern on the substrate, Between the bonding step and the exposure step or between the exposure step and the development step, there is further a dummy support peeling step for peeling off the dummy support. Hereinafter, each step will be described in detail.

[Fitting procedure] The bonding step is to transfer the transfer film in such a way that the surface of the transfer film opposite to the dummy support side is in contact with the metal layer of the substrate having a metal layer on the surface of the transfer film having the dummy branch body and the negative photosensitive composition layer. The step of laminating the printing film and the substrate. By implementing this step, a substrate with a photosensitive composition layer having a substrate, a metal layer, a photosensitive composition layer, and a dummy support in this order can be obtained.

The configuration of the transfer film will be described in detail later.

A substrate having a metal layer on its surface (substrate with a metal layer) has a substrate and a metal layer arranged on the surface of the substrate. Examples of the substrate include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, and the substrates described in paragraph [0140] of International Publication No. 2018/155193 are preferred. As the material of the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

The metal layer is a layer containing metal, and the metal is not particularly limited, and known metals can be used. It is preferable that the metal layer is a conductive layer. Examples of the main component (so-called main metal) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. In addition, the "main component" refers to the metal with the largest content among the metals contained in the metal layer.

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

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

One or more metal layers may be disposed on the substrate. When two or more metal layers are arranged, the two or more metal layers may be the same or different from each other, and metal layers of different materials are preferred.

In the above lamination, it is preferable to bring the photosensitive composition layer side (the surface opposite to the dummy support side) of the transfer film into contact with the metal layer on the substrate to be pressure-bonded. The method of the pressure bonding is not particularly limited, and known transfer methods and lamination methods can be used. Among them, it is preferable to overlay the surface of the photosensitive composition layer on the substrate having the metal layer, and to perform pressurization and heating with a roller or the like. A known laminator, such as a vacuum laminator and an automatic cutting laminator, can be used for bonding. Although it does not specifically limit as lamination temperature, For example, 70-130 degreeC is preferable.

[Exposure steps] The exposing step is a step of pattern-exposing the photosensitive composition layer. "Pattern exposure" means exposure in a patterned form, and refers to exposure in a form in which exposed parts and unexposed parts exist. The positional relationship between the exposed part (exposed area) and the unexposed part (unexposed area) in pattern exposure can be adjusted suitably. Exposure is preferably performed from the photosensitive composition layer side.

Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, and mask exposure or projection exposure is preferred. That is, as an exposure process, the process of performing pattern exposure through a photomask is preferable. In addition, as the exposure step, a step of pattern-exposing the photosensitive composition layer through a lens using active light rays onto which an image of a photomask is projected is also preferable.

When the dummy support peeling step described later is performed between the bonding step and the exposure step, the exposure step is preferably an exposure step in which the surface exposed by peeling the dummy support is brought into contact with a photomask to perform pattern exposure. In other words, the exposure step of pattern-exposing the photosensitive composition layer by bringing the exposed surface of the layered body from which the dummy support has been peeled, which is exposed by peeling off the dummy support, into contact with a photomask is preferable. In addition, as the above-mentioned exposed surface, when the transfer film has a three-layer structure of a dummy support, an intermediate layer, and a photosensitive composition layer, the surface of the intermediate layer corresponds to this. If this exposure step is adopted, a higher-definition photoresist pattern can be obtained, and a higher-definition conductor pattern can be finally obtained. When performing the dummy support peeling step described later, it is preferable to employ such an exposure step between the bonding step and the exposure step. In addition, when the dummy support peeling step described later is performed between the exposure step and the development step, as the exposure step, the layer of the transfer film and the transfer film obtained in the lamination step are made to have the substrate. It is preferable to perform an exposure step in which the surface on the opposite side of one side is in contact with a photomask to perform pattern exposure.

In the exposure step of pattern exposure, a curing reaction of components contained in the photosensitive composition layer can occur in the exposed region (region corresponding to the opening of the photomask) of the photosensitive composition layer. By performing a developing step after exposure, non-exposed regions of the photosensitive composition layer are removed to form a pattern.

It is also preferable that the method of the present invention has a mask stripping step of peeling off the photomask used in the exposure step between the exposure step and the development step. As a mask peeling process, a well-known peeling process is mentioned, for example.

As a light source for pattern exposure, any light source in a wavelength range capable of curing at least the photosensitive composition layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Among them, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. In addition, the dominant wavelength is the wavelength with the greatest intensity.

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

Preferable 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, and these contents are incorporated in this specification.

[Pseudo-support stripping step] The dummy support stripping step is performed between the bonding step and the exposure step or between the exposure step and the development step. Among them, it is preferable to have a dummy support peeling step between the bonding step and the exposing step. The dummy support peeling step is a step of peeling the dummy support from the laminate of the transfer film and the metal layer-attached substrate. As the method of peeling off the pseudo-support, for example, known peeling methods can be mentioned. Specifically, there may be mentioned the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589.

[Development procedure] The developing step is a step of performing developing treatment on the exposed photosensitive composition layer to form a photoresist pattern. The image development of the said photosensitive composition layer can be performed using a developing solution. As a developing solution, an alkaline aqueous solution is preferable. Examples of basic compounds that may be contained in an alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide Ammonium, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide and Choline (2-Hydroxyethyltrimethylammonium Hydroxide).

As for the liquid temperature of the developer at the time of developing processing, 10-50 degreeC is preferable, 15-40 degreeC is more preferable, 20-35 degreeC is still more preferable. The pH of the developer at the time of developing is preferably 9 or higher, more preferably 10 or higher, and still more preferably 11 or higher. The upper limit is preferably 14 or less, more preferably less than 13. pH can be measured by the method based on JIS Z8802-1984 using a well-known pH meter. The measurement temperature of pH was set at 25°C.

The content of water in the developer is preferably at least 50% by mass and less than 100% by mass, more preferably at least 90% by mass and less than 100% by mass, based on the total mass of the developer. In the developer, the content of the basic compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developer.

As a system of image development, systems, such as spin-on-dip image development, shower image development, spin image development, and immersion image development, are mentioned, for example.

As a developing solution preferably used in this specification, for example, the developing solution described in paragraph [0194] of International Publication No. 2015/093271 can be mentioned. As a developing method preferably used, for example, the international The development method described in paragraph [0195] of Publication No. 2015/093271.

It is also preferable to perform a rinsing process for removing the developer remaining on the metal layer-attached substrate after the development and before transferring to the next step. Water or the like can be used for the rinsing treatment. After the development and/or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the metal layer.

The position and size of the photoresist pattern formed on the substrate with the metal layer are not particularly limited, but a thin line shape is preferred. Specifically, the line width of the photoresist pattern is preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is often 1.0 μm or more.

[Heating step] The heating step is a step of heating the photoresist pattern. By carrying out this step, a crosslinked structure is formed in the resist pattern by a thermal crosslinking agent described later, and resistance against cleaning with an acidic solution to be performed in a cleaning step described later can be imparted to the resist pattern. The heating temperature is not particularly limited, but is preferably 100 to 200°C, more preferably 120 to 150°C. The heating time is not particularly limited, but is preferably 10 to 60 minutes, more preferably 20 to 40 minutes.

The modulus of elasticity of the surface of the photoresist pattern heated by the heating step opposite to the substrate side is not particularly limited, but from the viewpoint of better effects of the present invention, it is preferably 5.0 GPa or more, 5.5 GPa The above is better. The upper limit is not particularly limited, but it is often 7.0 GPa or less. The measuring method of the above elastic modulus is as follows. The modulus of elasticity was measured using an atomic force microscope (AFM). The specific procedure is as follows. Measurements are performed in QNM mode using an atomic force microscope (for example, AFM Dimension Icon manufactured by Bruker Corporation). As a probe, for example, RTESPA-150 (150 KHz, 5 N/m) is used. Measure a total of 5 fields of view with a 1 μm square per field of view, and measure a total of 50 points of force curve (force curve) at 10 points per field of view. Using the Hertz contact theory, the slope of the force curve of the return stroke (Area from 20% to 90% of the maximum load) Calculate the modulus of elasticity. In addition, specific examples of calibration of the AFM probe are as follows. The force curve of the quartz substrate was measured in advance, and the warpage sensitivity was calculated from the slope of the force curve. The spring constant is calculated by measuring the thermal fluctuation of the probe. For example, the spring constant is calculated using the Thermal Tune method included in the software of the AFM manufactured by Bruker. Measure the shape of the tip curvature correction sample (RM-12M: Ti Roughness Sample), for example, use the image analysis mode (Tip Qualification) attached to the AFM software manufactured by Bruker to calculate the curvature of the tip.

Let the elastic modulus of the surface of the photoresist pattern heated by the heating step opposite to the substrate side be elastic modulus X, and let the elastic modulus near the substrate side of the photoresist pattern heated by the heating step be When it is the modulus of elasticity Y, X/Y is not particularly limited, but is preferably 1.20 or less, more preferably 1.10 or less, from the viewpoint of more excellent effects of the present invention. The lower limit is not particularly limited, but is preferably 1.05 or higher. As a method for measuring the above-mentioned elastic modulus X, a method based on the above-mentioned atomic force microscope (AFM) can be mentioned. The method of measuring the above elastic modulus Y is as follows. Along the thickness direction, use a microtome to cut the photoresist pattern, so that the vertical section of the photoresist pattern is exposed, and measure the overall thickness of the vertical section from the substrate relative to the photoresist pattern by the same method as the above-mentioned elastic modulus X. The elastic modulus at any one of the height positions of 0 to 20% is taken as the above-mentioned elastic modulus Y. That is, the vicinity of the substrate side of the photoresist pattern refers to a range of height positions of 0 to 20% of the entire thickness of the photoresist pattern from the substrate in the vertical cross section of the photoresist pattern.

[Cleaning procedure] The cleaning step is a step of cleaning the photoresist pattern heated in the heating step with an acidic solution. The acidic solution is not particularly limited as long as it contains an acid. Examples of the acid in the acidic solution include sulfuric acid, nitric acid, hydrogen chloride, phosphoric acid, hydrofluoric acid, sulfonylic acid, and oxalic acid. The concentration of the acid in the acidic solution is not particularly limited, but the concentration of the acid component is preferably 5 to 30% by mass, more preferably 10 to 20% by mass, based on the total mass of the acidic solution.

It is preferable that the acidic solution contains a solvent. As a solvent, water and an organic solvent are mentioned. Examples of the organic solvent include alcohol-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, and hydrocarbon-based solvents.

The method of cleaning the photoresist pattern with an acidic solution is not particularly limited, as long as the photoresist pattern can be contacted with the acidic solution. For example, the method of supplying an acidic solution on a photoresist pattern, and the method of dipping a photoresist pattern in an acidic solution are mentioned. The contact time between the photoresist pattern and the acidic solution is not particularly limited, but is preferably 1-20 minutes, more preferably 3-10 minutes. The liquid temperature of the acidic solution when the photoresist pattern is brought into contact with the acidic solution is preferably 25 to 50°C, more preferably 30 to 40°C.

[Plating steps] The electroplating step is a step of electroplating the metal layer in the area where the photoresist pattern is not arranged. By implementing this step, an electroplating layer can be formed on the metal layer in the area where the photoresist pattern is not arranged.

As a method of electroplating treatment, an electrolytic plating method and an electroless plating method are mentioned, for example, The electrolytic plating method is preferable from a viewpoint of productivity. If the electroplating step is performed, an electroplating layer having the same pattern shape as that of the region (opening of the photoresist pattern) on which the photoresist pattern is not disposed on the substrate with the metal layer can be obtained.

As a metal contained in a plating layer, a well-known metal is mentioned, for example. Specifically, metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals are mentioned. Among these, it is preferable that the electroplating layer contains copper or an alloy thereof from the viewpoint that the conductivity of the conductor pattern is more excellent. Moreover, it is preferable that the electroplating layer contains copper as a main component from a viewpoint of the electroconductivity of a conductor pattern being more excellent.

The thickness of the plating layer is preferably at least 0.1 μm, more preferably at least 1 μm. The upper limit is preferably 20 μm or less.

[Peel off procedure] The stripping step is a step of stripping the photoresist pattern. The method of stripping the residual photoresist pattern is not particularly limited, and the method of removing it by chemical treatment is mentioned, and the method of removing it by using a stripping solution is preferred. Moreover, it can also remove by well-known methods, such as a spray method, a shower method, and a spin-on-dip method, using a stripping liquid.

As the stripping liquid, for example, a stripping liquid obtained by dissolving an inorganic base component or an organic base component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof is mentioned. As an inorganic base component, sodium hydroxide and potassium hydroxide are mentioned, for example. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. As the basic organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferable. It is also preferable that the stripping solution does not dissolve the metal layer.

As the stripping method of the photoresist pattern, it is possible to immerse the substrate with the remaining photoresist pattern in the stripping solution having a liquid temperature of preferably 30 to 80° C., more preferably 50 to 80° C., for 1 to 30 minutes. method.

The pH of the stripping liquid at the time of the stripping treatment is preferably 11 or higher, more preferably 12 or higher, and still more preferably 13 or higher. The upper limit is preferably 14 or less, more preferably 13.8 or less. pH can be measured by the method based on JIS Z8802-1984 using a well-known pH meter. The measurement temperature of pH was set at 25°C. It is preferable that the liquid temperature of the stripping liquid during the peeling treatment is higher than the liquid temperature of the developing solution during the development treatment. Specifically, the value obtained by subtracting the liquid temperature of the developer from the liquid temperature of the stripping liquid (liquid temperature of the stripping liquid - liquid temperature of the developer) is preferably 10°C or higher, more preferably 20°C or higher. . The upper limit is preferably 100°C or lower, more preferably 80°C or lower. It is preferable that the pH of the stripping solution when performing the stripping treatment is higher than the pH of the developing solution when performing the developing treatment. 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 stripping the photoresist pattern with the stripping solution, it is also preferable to perform a rinse process for removing the stripping solution remaining on the substrate. Water or the like can be used for the rinsing treatment. After the stripping and/or rinsing process of the photoresist pattern by the stripping liquid, a drying process for removing excess liquid from the substrate may be performed.

[removal steps] The removing step is a step of removing the metal layer exposed by the stripping step and forming a conductor pattern on the substrate. In the removal step, etching treatment of the metal layer located in the non-pattern formation region (in other words, the region not protected by the plating layer) is performed using the plating layer formed by the plating step as an etching resist.

The method of removing a part of the metal layer is not particularly limited, and it is preferable to use a known etching solution. Examples of known etching solutions include ferric chloride solution, copper chloride solution, ammonia-alkali solution, sulfuric acid-hydrogen peroxide mixed solution, phosphoric acid-hydrogen peroxide mixed solution, and the like.

When the removing step is performed, the metal layer exposed on the surface is removed from the substrate, and the plated layer (conductor pattern) having a pattern shape remains, so that a laminate having a conductor pattern can be obtained.

The upper limit of the line width of the formed conductor pattern is preferably 8 μm or less, more preferably 6 μm or less. The lower limit is not particularly limited, but it is often 1 μm or more.

[additional steps] The manufacturing method of the laminated body which has a conductor pattern may include arbitrary steps (other steps) other than the above-mentioned steps. For example, the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. 2019/022089, and the step of forming on an insulating film described in paragraph [0172] of International Publication No. 2019/022089 can be mentioned. Steps of new metal layer, etc., but not limited to these steps.

-Steps to reduce reflectance of visible light- The manufacturing method of the laminated body which has a conductor pattern may include the process of performing the process of reducing the reflectance of a part or all of the visible light of some or all of the several metal layers which a base material has. Oxidation treatment can be mentioned as a treatment for lowering the reflectance of visible light. When the substrate has a metal layer containing copper, the copper is oxidized to become copper oxide and the metal layer is blackened, thereby reducing the visible light reflectance of the metal layer. Regarding the treatment of reducing the reflectance of visible light, it is described in paragraphs [0017] to [0025] of Japanese Patent Application Laid-Open No. 2014-150118 and paragraphs [0041], [0042], and [0048] of Japanese Patent Application Laid-Open No. 2013-206315. ] paragraphs and [0058] paragraphs, the contents recorded in these publications are incorporated into this specification.

-Step of forming an insulating film, and step of forming a new metal layer on the surface of the insulating film- It is also preferable that the method of manufacturing a laminate having a conductor pattern includes the step of forming an insulating film on the surface of the circuit wiring and the step of forming a new metal layer on the surface of the insulating film. Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed. The step of forming an insulating film is not particularly limited, and a known method for forming a permanent film can be used. In addition, an insulating film having a desired pattern can also be formed by photolithography using an insulating photosensitive material.

It is also preferable to use a substrate having a plurality of metal layers on both surfaces of the substrate in the method of manufacturing a laminate having a conductive pattern, and to sequentially or simultaneously form circuits on the metal layers formed on both surfaces of the substrate. With such a configuration, the circuit wiring for a touch panel in which the first conductor pattern is formed on one surface of the base material and the second conductor pattern is formed on the other surface can be formed. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material in a roll-to-roll system.

<Applications of laminates with conductor patterns> The method for manufacturing a laminate with a conductor pattern can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and dimming films; the manufacture of printed wiring boards and semiconductor packages; the manufacture of semiconductor chips or packages Manufacture of columns and pins for interconnection; manufacture of metal masks; manufacture of tape-shaped substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding: tape-and-roll automatic bonding), etc. Moreover, an electrostatic capacity type touch panel is mentioned as said touch panel. The manufacturing method of the laminated body of this invention can be used for the formation of the conductive film in a touch panel, or peripheral circuit wiring. The touch panel described above can be applied to display devices such as organic EL (electro-luminescence: electroluminescence) display devices and liquid crystal display devices, for example.

＜Transfer Film＞ The transfer film used in the method for producing a laminate having a conductive pattern of the present invention has a dummy support and a negative photosensitive composition layer, and the photosensitive composition layer contains a thermal crosslinking agent. The transfer film may have other layers besides the dummy support and the photosensitive composition layer. As another layer, the intermediate|middle layer mentioned later is mentioned, for example. Moreover, the transfer film may have other members (for example, a protective film etc.) mentioned later.

As an embodiment of the transfer film, for example, the following constitution (1) or (2) can be mentioned, and constitution (2) is preferable. (1) "pseudo-support/photosensitive composition layer/protective film" (2) "pseudo-support/intermediate layer/photosensitive composition layer/protective film" It is preferable that the transfer film has an intermediate layer.

From the viewpoint of suppressing generation of air bubbles in the bonding step, the maximum width of the ripples of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. In addition, the lower limit of the maximum width of the corrugation is 0 μm or more, preferably 0.1 μm or more, more preferably 1 μm or more. The maximum width of the ripples of the transfer film is a value measured by the following procedure. First, the transfer film was cut into a size of 20 cm in length x 20 cm in width in a direction perpendicular to the main surface to prepare a test sample. In addition, when the transfer film has a protective film, the protective film is peeled off. Next, on a workbench with a smooth surface and a horizontal surface, the above-mentioned test sample was left still so that the surface of the dummy support faced the workbench. After standing still, scan the surface of the test sample with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) to obtain a three-dimensional surface image of the center of the test sample within a 10 cm square area. From the obtained three-dimensional surface image The height of the largest convexity minus the height of the lowest concave. The above-mentioned operation was performed on 10 test samples, and the arithmetic mean thereof was defined as the "maximum waviness width of the transfer film".

In the photosensitive composition layer of the transfer film, when there are further composition layers on the surface of the photosensitive composition layer opposite to the dummy support, the total thickness of the other composition layers is relative to the photosensitive composition layer. The total thickness of the layers is preferably 0.1 to 30%, more preferably 0.1 to 20%.

From the viewpoint of better adhesion, the transmittance of light having a wavelength of 365 nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.

An example of embodiment of the transfer film will be described. The transfer film 10 shown in FIG. 1 has a dummy support 11 , a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15 , and a protective film 19 in this order. Although the transfer film 10 shown in FIG. 1 has the intermediate layer 13 and the protective film 19, it does not need to have the intermediate layer 13 and the protective film 19. In FIG. 1 , each layer (for example, a photosensitive composition layer, an intermediate layer, etc.) that can be disposed on the dummy support 11 other than the protective film 19 is also referred to as a “composition layer”.

Hereinafter, with regard to the transfer film, each member and each component will be described in detail.

[pseudo-support] The transfer film has a pseudo-support. The member of the pseudo support system supporting the photosensitive composition layer is finally removed by peeling treatment.

The pseudo-support may be any of a single-layer structure and a multi-layer structure. As the pseudo-support, a thin film is preferable, and a resin thin film is more preferable. Also, as a pseudo-support, a film that is flexible and does not undergo significant deformation, shrinkage or elongation under pressure or under pressure and heat is also preferred, and a film without deformation such as wrinkles and scratches is also preferred. better. Examples of films include polyethylene terephthalate films (for example, biaxially stretched polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films , polyimide film and polycarbonate film, polyethylene terephthalate film is preferred.

From the viewpoint of enabling pattern exposure through the dummy support, it is preferable that the dummy support has high transparency, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more. It is preferable that the haze of the dummy support is small from the viewpoint of the pattern formability at the time of pattern exposure through the dummy support and the transparency of the dummy support. Specifically, the haze value of the pseudo-support is preferably 2.0% or less, more preferably 1.0% or less, and still more preferably 0.5% or less. The lower limit is not particularly limited, and 0.1% or more can be mentioned. It is preferable that the number of fine particles, foreign matter, and defects contained in the dummy support is small from the viewpoint of the pattern formation property at the time of pattern exposure through the dummy support and the transparency of the dummy support. The number of particles, foreign substances, and defects with a diameter of 1 μm or more in the pseudo-support is preferably 50 pieces/10mm2 ^or less, more preferably 10 pieces/10mm2 ^or less, more preferably 3 pieces/10mm2 ^or less, and 0 pieces /10mm ² is especially good.

The thickness of the pseudo-support is more preferably 5 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, further preferably 50 μm or less, particularly preferably 20 μm or less, and most preferably 16 μm or less from the viewpoint of ease of handling and versatility. The thickness of the pseudo-support was calculated as an average value of arbitrary five points measured by cross-sectional observation with SEM (Scanning Electron Microscope).

From the viewpoint of handleability, the pseudo-support may have a layer (lubricant layer) containing fine particles on one or both surfaces of the pseudo-support. The fine particles contained in the lubricant layer preferably have a diameter of 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

From the viewpoint of improving the adhesiveness between the dummy support and the photosensitive composition layer, the surface of the dummy support that is in contact with the photosensitive composition layer may be subjected to a surface modification treatment. Examples of the surface modification treatment include treatment using UV irradiation, corona discharge, and plasma. The exposure amount in UV irradiation is preferably 10 to 2000 mJ/cm ² , more preferably 50 to 1000 mJ/cm ² . As long as the exposure amount is within the above-mentioned range, the lamp output and the illuminance are not particularly limited. Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and luminescent lamps that emit light in the 150-450 nm wavelength band. Diodes (LEDs).

Examples of pseudo supports include biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and biaxially stretched polyethylene terephthalate film with a thickness of 9 μm. Stretched polyethylene terephthalate film. In addition, as the pseudo-support, for example, paragraphs [0017] to [0018] of JP-A 2014-085643, paragraphs [0019]-[0026] of JP-A 2016-027363, international publications Paragraphs [0041] to [0057] of No. 2012/081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370 are incorporated into this specification. Examples of commercially available pseudo-supports include registered trademark LUMIRROR 16KS40 and registered trademark LUMIRROR 16FB40 (the above are manufactured by TORAY INDUSTRIES, INC.); Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (the above are Toyobo Co., Ltd. manufacture).

[Photosensitive composition layer] The transfer film has a negative photosensitive composition layer. Hereinafter, each component contained in the photosensitive composition layer is demonstrated in order. In addition, below, it demonstrates starting from the thermal crosslinking agent which is one of the characteristic points of this invention.

(thermal crosslinking agent) The photosensitive composition layer contains a thermal crosslinking agent. Examples of the thermal crosslinking agent include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. The blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group. Therefore, for example, when the resin and/or polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the formed film will decrease, which will make the negative photosensitive composition The tendency to enhance the function when the film formed by hardening the material layer is used as a protective film. In addition, the blocked isocyanate compound means "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 100-160°C, more preferably 130-150°C. The dissociation temperature of blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of blocked isocyanate when it is analyzed and measured by DSC (Differential scanning calorimetry) using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments Inc. (model number: DSC6200) can be preferably used. However, the differential scanning calorimeter is not limited to this.

As an end-capping agent with a dissociation temperature of 100 to 160° C., active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, Di2-ethylhexyl malonate, etc.), oxime compounds (formaldoxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime, etc. have -C (=N-OH ) - the compound of the structure represented). Among them, as a blocking agent having a dissociation temperature of 100 to 160° C., for example, from the viewpoint of storage stability, at least one selected from oxime compounds is preferable.

For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesive force with the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among blocked isocyanate compounds having an isocyanurate structure, compared with compounds not having an oxime structure, it is easier to set the dissociation temperature in a preferable range, and it is easier to reduce developing residues. A compound having an oxime structure using an oxime compound as a blocking agent is preferred.

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

As a blocked isocyanate compound, a commercial item can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (the above are manufactured by SHOWA DENKO K.K.) , End-capped Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, Duranate (registered trademark) SBB-70P, etc., manufactured by ASAHI KASEI CORPORATION). Moreover, the compound of the following structures can also be used as a blocked isocyanate compound.

[chemical formula 1]

One type of thermal crosslinking agent may be used alone, or two or more types may be used. The content of the thermal crosslinking agent in the photosensitive composition layer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the photosensitive composition layer.

(resin) The photosensitive composition layer may contain resin. Resin A which is alkali-soluble resin is mentioned as resin contained in the photosensitive composition layer. From the standpoint of better resolution by suppressing the swelling of the negative photosensitive composition layer caused by the developer, the acid value of resin A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g , less than 190 mgKOH/g is further preferred. The lower limit of the acid value of resin A is not particularly limited, but from the viewpoint of better developability, it is more preferably 120 mgKOH/g or more, further preferably 150 mgKOH/g or more, and particularly preferably 170 mgKOH/g or more. In addition, the acid value (mgKOH/g) refers to the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of resin A should just be adjusted by the kind of the structural unit which comprises resin A, and content of the structural unit containing an acid group mentioned later.

The weight average molecular weight of the resin A is not particularly limited, and is preferably 5,000-500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably at most 100,000, further preferably at most 60,000. On the other hand, when the weight average molecular weight is 5,000 or more, it is comparatively advantageous from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge melting and chipping properties when it is set as a negative photosensitive resin laminate. good. The weight average molecular weight is more preferably at least 10,000, further preferably at least 20,000, and particularly preferably at least 30,000. The edge melting property refers to the ease with which the negative photosensitive composition layer protrudes from the end surface of the roll when the transfer film is wound up in a roll shape as a negative photosensitive resin laminate. The chipping property refers to the ease of scattering of chips when the unexposed film is cut with a cutter. If this swarf adheres to the upper surface and the like of the negative photosensitive resin laminate, it will be transferred to the mask in the subsequent exposure step and the like to cause a defective product. The degree of dispersion of the resin A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0. In the present 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.

It is preferable that the glass transition temperature Tg of resin A is 30-135 degreeC. By using the resin A which has Tg of 135 degreeC or less, deterioration of the line width thickness and resolution at the time of focus position shift at the time of exposure can be suppressed. From this viewpoint, the Tg of the alkali-soluble polymer is more preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower. Moreover, it is preferable to use the resin A which has Tg of 30 degreeC or more from a viewpoint of edge melting resistance improvement. From this viewpoint, the Tg of the resin A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, most preferably 70°C or higher.

-Constituent unit derived from a monomer having an aromatic hydrocarbon group- Also, from the viewpoint of suppressing deterioration of line width and resolution when the focal position shifts during exposure, it is preferable that the resin A contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Moreover, as such an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example. The content of the structural unit derived from the monomer having an aromatic hydrocarbon group in the resin A is preferably 20% by mass or more, more preferably 30% by mass or more, based on all the structural units of the resin A. The upper limit is not particularly limited, but is preferably at most 95% by mass, more preferably at most 85% by mass. Moreover, when plural types of resin A are contained, it is preferable that the average value of content of the structural unit derived from the monomer which has an aromatic hydrocarbon group exists in the said range.

As monomers having an aromatic hydrocarbon group, for example, monomers having an aralkyl group, styrene and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butoxystyrene , Acetyloxystyrene, styrene dimer and styrene trimer, etc.). Among them, monomers having aralkyl groups or styrene are preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural units derived from styrene is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and 20% to all the structural units of resin A. -60 mass % is more preferable, and 25-55 mass % is especially preferable. Moreover, when the photosensitive composition layer contains several types of alkali-soluble polymers, the content rate of the structural unit derived from the monomer which has an aromatic hydrocarbon group was calculated|required as a weight average.

Examples of the aralkyl group include a phenylalkyl group which may have a substituent, and a benzyl group which may have a substituent is preferred.

Examples of the monomer containing a phenylalkyl group which may have a substituent include phenylethyl (meth)acrylate and the like.

Examples of monomers containing benzyl groups which may have substituents include benzyl (meth)acrylates such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinylbenzyl chloride; Vinyl monomers having a benzyl group, such as vinyl benzyl alcohol, are preferably (meth)acrylates having a benzyl group, and more preferably benzyl (meth)acrylate. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of the constituent units derived from benzyl (meth)acrylate is preferably 10 to 90% by mass relative to all the constituent units of the resin A, 15 to 85% by mass is more preferable.

-Constituent unit derived from a monomer having a carboxyl group- Resin A may have a structural unit derived from a monomer having a carboxyl group. Examples of monomers having carboxyl groups include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid. Acid half ester. Among these, (meth)acrylic acid is preferable. The content of the structural unit derived from a monomer having a carboxyl group in the resin A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass, relative to all the structural units of the resin A. better. From the viewpoint of expressing favorable developability, controlling edge melting properties, etc., it is preferable to make the said content into 5 mass % or more. From the viewpoint of the high resolution of the photoresist pattern and the bead shape, and further from the viewpoint of the chemical resistance of the photoresist pattern, the above-mentioned content is preferably 50% by mass or less.

-Non-acidic constituent unit- Resin A may contain a non-acidic structural unit derived from a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the aforementioned monomers (non-acidic monomers) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl, (meth)acrylate isobutyl, (meth)acrylate tertiary butyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate 2-hydroxypropyl, (Meth)acrylates such as cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; (meth)acrylonitrile, etc. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferable, and methyl (meth)acrylate is more preferable. The content of the structural units derived from non-acidic monomers in the resin A is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and still more preferably 2 to 40% by mass, based on all the structural units of the resin A. better.

Resin A may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. In this specification, "main chain" means the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and "side chain" means an atomic group branched from the main 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 an alicyclic structure can be introduced into the side chain of the alkali-soluble polymer . 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, secondary butyl (meth)acrylate, Tertiary butyl (meth)acrylate, isopentyl (meth)acrylate, tertiary pentyl (meth)acrylate, secondary pentyl (meth)acrylate, 2-octyl (meth)acrylate, ( 3-octyl methacrylate and tertiary octyl (meth)acrylate, etc. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl methacrylate are preferred, and isopropyl methacrylate or tertiary butyl methacrylate is better. Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Moreover, (meth)acrylate which has an alicyclic hydrocarbon group with 5-20 carbon atoms is mentioned. As more specific examples, (meth)acrylate (bicyclo[2.2.1]heptyl-2)ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl Alkyl ester, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-(meth)acrylate -Ethyl adamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester Alkyl esters, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (methyl ) 2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methanoinden-5 (meth)acrylate -yl ester, octahydro-4,7-inden-1-ylmethyl (meth)acrylate, 1-menthol (meth)acrylate, tricyclodecane (meth)acrylate, ( Meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[ 4.1.0] Heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenzyl (meth)acrylate, 2,2,5-tris(meth)acrylate Methyl cyclohexyl ester and cyclohexyl (meth)acrylate, etc. Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate-1 - adamantyl ester, 2-adamantyl (meth)acrylate, fenzyl (meth)acrylate, 1-menthol (meth)acrylate or tricyclodecane (meth)acrylate as Preferably, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate or (methyl) ) tricyclodecane acrylate is more preferred.

-Constituent unit having a polymerizable group- Resin A may have a polymeric group, and may contain the structural unit which has a polymeric group. As the polymerizable group, a radical polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. Moreover, when resin A has an ethylenically unsaturated group, it is preferable that resin A contains the structural unit which has an ethylenically unsaturated group in a side chain. As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable.

As a structural unit having a polymerizable group, a structural unit represented by formula (P) is preferable.

[chemical formula 2]

In the formula (P), R ^P represents a hydrogen atom or a methyl group. ^LP represents a divalent linking group. P represents a polymerizable group.

R ^P represents a hydrogen atom or a methyl group. As R ^P , a hydrogen atom is preferable.

^LP represents a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N -, divalent hydrocarbon groups, and combinations thereof. 2-valent base. R ^N represents a substituent. As said hydrocarbon group, an alkylene group, a cycloalkylene group, and an arylylene group are mentioned, for example. The above-mentioned alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 2-8, and still more preferably 3-5. The above-mentioned alkylene group may have a heteroatom, and the methylene group in the above-mentioned alkylene group may be substituted with a heteroatom. As the above-mentioned hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is preferable, and an oxygen atom is more preferable. The above-mentioned cycloalkylene group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is preferably from 3 to 20, more preferably from 5 to 10, and still more preferably from 6 to 8. The aforementioned aryl group may be either monocyclic or polycyclic. The number of carbon atoms in the arylylene group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. A phenylene group is preferable as the above-mentioned arylylene group. The above-mentioned cycloalkylene group and the above-mentioned arylylene group may have a hetero atom as a ring member atom. As the above-mentioned hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is preferable, and an oxygen atom is more preferable. The above-mentioned hydrocarbon group may further have a substituent. Examples of the above-mentioned substituents include halogen atoms (for example, fluorine atoms, etc.), hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, and alkenyl groups, with hydroxyl groups being preferred. As L ^P , an alkylene group which may have a heteroatom is preferable.

P represents a polymerizable group. The aforementioned polymerizable group is as described above.

As an example of the structural unit which has a polymeric group, what is shown below is mentioned, However, It is not limited to these.

[chemical formula 3]

In the above constituent units, Rx represents a hydrogen atom or a methyl group. In addition, in the above structural units, Ry represents a hydrogen atom or a methyl group.

Resin A may contain one type of structural unit having a polymerizable group alone, or may contain two or more types. When the resin A contains a structural unit having a polymerizable group, from the viewpoint that the effects of the present invention are more excellent, the content of the structural unit having a polymerizable group relative to all the structural units of the resin A is preferably 5 to 70% by mass. Preferably, 10-50 mass % is more preferable, 20-40 mass % is still more preferable. Also, from the viewpoint of more excellent effect of the present invention, the content of the structural unit having a polymerizable group in the resin A is preferably 5 to 70 mol %, 10 to 60 mol % with respect to all the structural units of the resin A. Mole% is more preferable, and 20-50 mole% is still more preferable.

As a method for introducing a polymerizable group into the resin A, there may be mentioned a method in which compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinylidene compounds, aldehyde compounds, methylol compounds, and carboxylic anhydrides are mixed with Functional groups such as hydroxyl group, carboxyl group, primary amino group, secondary amino group, acetoacetyl group and sulfo group can be reacted. As a preferable example of the method of introducing a polymerizable group into the resin A, the following method can be mentioned: after synthesizing a polymer having a carboxyl group by a polymerization reaction, making glycidyl (meth)acrylate, etc. The (meth)acrylate having an epoxy group reacts with a part of the carboxyl groups of the obtained polymer to introduce a (meth)acryloxy group into the polymer. As another method, the following method can be mentioned: After synthesizing a polymer having a hydroxyl group by a polymerization reaction, the (meth)acrylate having an isocyanate group is reacted with a part of the hydroxyl group of the obtained polymer by a polymer reaction. reaction to introduce (meth)acryloyloxy groups into the polymer. By this method, the resin A which has a (meth)acryloxy group in a side chain can be obtained. The above polymerization reaction is preferably carried out at a temperature of 70-100°C, more preferably at a temperature of 80-90°C. As the polymerization initiator used in the above-mentioned polymerization reaction, an azo initiator is preferable, for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. The above polymer reaction is preferably carried out at a temperature of 80-110°C. In the above polymer reaction, it is better to use catalysts such as ammonium salts.

Resin A may be used individually by 1 type, and may use 2 or more types. When two or more are used, two resins A containing constituent units derived from monomers having aromatic hydrocarbon groups are used in combination, or resin A containing constituent units derived from monomers having aromatic hydrocarbon groups is used in combination with resin A not containing constituent units derived from Resin A which is a constituent unit of a monomer having an aromatic hydrocarbon group is preferable. In the latter case, the proportion of resin A containing constituent units derived from monomers having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass relative to the total mass of resin A. It is more preferable that it is more than mass %, and it is especially preferable that it is more than 90 mass %.

Resin A can be synthesized by using free radical polymerization initiators such as peroxide-based polymerization initiators (for example, benzoyl peroxide) and azo-based polymerization initiators (for example, azobisisobutyronitrile). It is performed by polymerizing the above-mentioned single or plural monomers.

The content of the resin A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive composition layer. good. It is preferable to make content of resin A into 90 mass % or less from a viewpoint of developing time control. On the other hand, it is preferable to make content of resin A into 10 mass % or more from a viewpoint of edge melting resistance improvement.

The photosensitive composition layer may contain other resins than the above-mentioned resin A. Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, poly Silicone resins, polyethyleneimines, polyallylamines and polyalkylene glycols.

(polymeric compound) The photosensitive composition layer may contain a polymerizable compound having a polymerizable group. As a polymeric compound, an ethylenically unsaturated compound is preferable. In addition, in this specification, a "polymerizable compound" means the compound different from the said resin A which polymerizes by the action of the polymerization initiator mentioned later.

The polymerizable group possessed by the polymerizable compound may be any group as long as it participates in the polymerization reaction, and examples thereof include vinyl, acryl, methacryl, styryl, and maleimide groups. Groups with ethylenically unsaturated groups such as epoxy groups and oxetanyl groups with cationic polymerizable groups, preferably groups with ethylenically unsaturated groups, acryl or methacryl groups for better.

As the ethylenically unsaturated group which the ethylenically unsaturated compound has, a vinyl group, an acryl group, a methacryl group, a styryl group, a maleimide group, etc. are mentioned. As the ethylenically unsaturated group, an acryl group or a methacryl group is preferable. The polymerizable group possessed by the polymerizable compound other than the ethylenically unsaturated compound is not particularly limited as long as it participates in the polymerization reaction. The base of the polymeric base. Hereinafter, ethylenically unsaturated compounds will be described.

The ethylenically unsaturated compound is preferably a compound (polyfunctional ethylenically unsaturated compound) having two or more ethylenically unsaturated groups in one molecule from the viewpoint of better photosensitivity. Also, from the standpoint of better resolving properties and exfoliation properties, 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. Less than one is further preferred.

From the standpoint of a better balance between photosensitivity, resolving power, and peelability of the photosensitive composition layer, bifunctional or trifunctional ethylenically unsaturated groups having 2 or 3 ethylenically unsaturated groups in one molecule Compounds are preferred, and bifunctional ethylenically unsaturated compounds containing two ethylenically unsaturated groups in one molecule are more preferred. From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and still more preferably 55% by mass or more. good. The upper limit is not particularly limited, and may be 100% by mass. That is, all polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Also, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryl group as a polymerizable group is preferable.

-polymerizable compound B1- It is also preferable that the photosensitive composition layer contains the polymerizable compound B1 which has an aromatic ring and 2 ethylenically unsaturated groups as a polymerizable compound.

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

Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, aromatic rings such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings. As the heterocyclic ring and such condensed rings, an aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable. In addition, the above-mentioned aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

It is preferable that polymerizable compound B1 has a bisphenol structure from a viewpoint of improving resolution by suppressing the swelling of the photosensitive composition layer by a developing solution. As the bisphenol structure, for example, the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl) phenyl)methane) and bisphenol B structure from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), bisphenol A structure is better.

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

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is better. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy) yl)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2, 2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methyl Acryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadeca Ethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane ( BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) and Ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.).

The polymerizable compound B1 may be used alone or in combination of 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 composition layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive resin bleeds from the end of the transfer member), 70% by mass or less is more preferable, and more preferably 60% by mass or less .

As the polymerizable compound, a polymerizable compound having an alkylene oxide-modified bisphenol structure is preferable, and a compound represented by the following general formula (B1) (also corresponding to the aforementioned polymerizable compound B1) is more preferable.

[chemical formula 4]

In the general formula (B1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents C ₂ H ₄ . B represents C ₃ H ₆ . n1 and n3 are each independently an integer of 1-39, and n1+n3 is an integer of 2-40. n2 and n4 are each independently an integer of 0-29, and n2+n4 is an integer of 0-30. The arrangement of the constituent units of -(AO)- and -(BO)- may be random or block. Also, in the case of a block, any of -(AO)- and -(BO)- may be on the bisphenyl side. In one aspect, n1+n2+n3+n4 is preferably 2-20, more preferably 2-16, and further preferably 4-12. Also, n2+n4 is preferably 0-10, more preferably 0-4, still more preferably 0-2, and particularly preferably 0.

The photosensitive composition layer may contain other polymerizable compounds other than the aforementioned polymerizable compounds. Other polymerizable compounds are not particularly limited, and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds. compound.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethylsuccinate, polyethylene glycol Alcohol Mono(meth)acrylate, Polypropylene Glycol Mono(meth)acrylate and Phenoxyethyl(meth)acrylate.

Examples of bifunctional ethylenically unsaturated compounds not having an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and urethane di(meth)acrylate. base) acrylate and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol Dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 , 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol dimethacrylate (4G, 9G, 14G, and 23G, etc., Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) M-220 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-240 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-270 (manufactured by TOAGOSEI 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. Acrylate. Examples of the urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Examples of commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co. , Ltd. manufacturing).

Examples of ethylenically unsaturated compounds having a trifunctional or higher function include diperythritol (tri/tetra/penta/hexa)(meth)acrylate, neopentylthritol (tri/tetra)(meth)acrylic acid ester, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate Meth)acrylate, glycerol tri(meth)acrylate and their alkylene oxide modified substances. Among them, "(three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates. The concept of acrylate, "(three/tetra) (meth)acrylate" includes the concepts of tri(meth)acrylate and tetra(meth)acrylate. In one aspect, it is also preferable that the photosensitive composition layer includes the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and preferably includes the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. Saturated compounds are more preferred. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound is (total mass of the polymerizable compound B1: (total mass of the trifunctional or higher ethylenically unsaturated compound)=1:1 -5:1 is preferable, 1.2:1-4:1 is more preferable, and 1.5:1-3:1 is still more preferable. Moreover, in one aspect, it is preferable that the photosensitive composition layer contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. , Shin-Nakamura Chemical Co., Ltd., A-9300-1CL, etc.), ethoxylated trimethylolpropane trimethacrylate (SR454, SR499, SR502, etc., manufactured by TOMOE Engineering Co., Ltd. ), 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., DAICEL- EBECRYL (registered trademark) 135, etc. manufactured by ALLNEX LTD.), ethoxylated glycerin trimethacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) TO -2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

Moreover, as a polymeric compound, the polymeric compound which has an acidic group (carboxyl group etc.) can be used. The above-mentioned acid groups may form acid anhydride groups. 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 (manufactured by TOAGOSEI CO., LTD. registered trademark) M-510 (manufactured by TOAGOSEI CO.,LTD.). As the polymerizable compound having an acid group, for example, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 can be used.

The molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably from 200 to 3000, more preferably from 280 to 2200, and still more preferably from 300 to 2200.

A polymeric compound may be used individually by 1 type, and may use 2 or more types together. The content of the polymerizable compound is preferably from 0 to 70% by mass, more preferably from 10 to 70% by mass, and still more preferably from 20 to 60% by mass, relative to the total mass of the photosensitive composition layer.

(polymerization initiator) The photosensitive composition layer may contain a polymerization initiator. As the polymerization initiator, for example, known polymerization initiators can be used depending on the form of the polymerization reaction. Specifically, thermal polymerization initiators and photopolymerization initiators are mentioned. The polymerization initiator may be any of a radical polymerization initiator and a cationic polymerization initiator.

It is preferable that the photosensitive composition layer contains a photoinitiator. The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving active rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. As a photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, A photoradical polymerization initiator is preferable.

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

In addition, from the viewpoint of photosensitivity, visibility of exposed parts and non-exposed parts, and resolution, the photosensitive composition layer contains a compound selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof. At least one of these groups is preferred as a photoradical polymerization initiator. In addition, 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-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-bis(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, those described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064]-[0081] of JP-A-2015-014783 can be used. The polymerization initiator.

Examples of photoradical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl base) anisyl, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 ( Trade name: Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (BASF Corporation), Omnirad651 and 369 (trade name: IGM Resins B.V. company) and 2,2'-bis (2- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

As a commercially available photoradical polymerization initiator, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) ( Trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone- 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF Corporation), IRGACURE OXE-03 (manufactured by BASF Corporation), IRGACURE OXE-04 (manufactured by BASF Corporation), 2-(dimethylamine yl)-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 (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropane -1-Kone (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2 -Diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester-based photopolymerization initiator (trade name Name: Lunar 6, manufactured by DKSH Japan K.K.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl) -4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime ) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2- Furylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.) and 3- Cyclohexyl-1-(6-(2-(benzoyloxyimino)octyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2- (O-Benzoxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.).

Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving active light. As the photocationic polymerization initiator, a compound that reacts to active light with a wavelength of 300nm or more, preferably 300nm-450nm to generate acid is preferred, but its chemical structure is not limited. Also, as for the photocationic polymerization initiator that is not directly responsive to active light with a wavelength of 300 nm or more, as long as it is a compound that generates an acid in response to active light with a wavelength of 300 nm or more by using in combination with a sensitizer, it can also be used with a sensitizer. Sensitive agents are preferably used in combination. As a photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferred, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferred, and a photocationic polymerization initiator that generates an acid with a pKa of 2 or less An acidic photocationic polymerization initiator is further preferred. The lower limit of pKa is not particularly specified, but is preferably -10.0 or more, for example.

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned. As an ionic photocationic polymerization initiator, an onium salt compound, such as a diaryl iodonium salt and a triaryl permeicium salt, and a quaternary ammonium salt are mentioned, for example. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs [0114] to [0133] of JP-A-2014-085643 can be used.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-three wells, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The compounds described in paragraphs [0083] to [0088] of JP-A No. 2011-221494 can be used as the trichloromethyl-s-three wells, the diazomethane compound, and the imide sulfonate compound. Also, as the oxime sulfonate compound, compounds described in paragraphs [0084] to [0088] of International Publication No. 2018/179640 can be used.

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

One kind of polymerization initiator may be used alone, or two or more kinds may be used. The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the photosensitive composition layer, It is still more preferable that it is 1.0 mass % or more. The upper limit is not particularly limited, but is preferably at most 20% by mass, more preferably at most 15% by mass, and still more preferably at most 10% by mass, based on the total mass of the photosensitive composition layer.

(sensitizer) It is preferable that the photosensitive composition layer contains a sensitizer. The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone (xanthone) compounds, thioxanthone (thioxanthone) compounds, Pyridone compounds, pyridazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (eg, 1,2,4-triazole), stilbene compounds, distyrylbenzene , styrylbenzene (styrylbenzene), three well compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds. In addition, the compounds listed above also include derivatives of the above compounds. Among them, as sensitizers, dialkylaminobenzophenone compounds, anthracene compounds, distyrylbenzene compounds or styrylpyridine compounds are preferred, anthracene compounds, distyrylbenzene compounds or styryl A pyridine compound is more preferable, and an anthracene derivative, a distyrylbenzene derivative, or a styrylpyridine derivative is still more preferable.

One kind of sensitizer may be used alone, or two or more kinds may be used. When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to the light source and increasing the hardening speed by balancing the polymerization speed and chain transfer, relatively The total mass of the photosensitive composition layer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass.

(pigment) From the viewpoint of the visibility of the exposed portion and the non-exposed portion, the visibility of the pattern after development, and the resolution, the photosensitive composition layer includes a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm during color development. A dye whose absorption wavelength is changed by acid, alkali or free radical (also referred to as "dye N") is also preferable. When the dye N is contained, although the detailed mechanism is not clear, the adhesiveness with the adjacent layer (for example, a water-soluble resin layer) improves, and resolution becomes more excellent.

In this specification, "the maximum absorption wavelength of a pigment is changed by acid, alkali or free radical" may refer to a state in which a pigment in a colored state is decolorized by an acid, alkali or free radical, or a pigment in a decolorized state. Either of the state in which the color is developed by acid, alkali or free radicals, and the state in which the pigment in the color-developed state changes to a color-developed state of another hue. Specifically, the dye N may be a compound that develops color by changing from a decolorized state by exposure, or may be a compound that decolorizes by changing from a color-developed state by exposure. In this case, it may be a dye that generates an acid, an alkali, or a free radical in the photosensitive composition layer by exposure, and these act to change the state of color development or decolorization, or the photosensitive composition layer. A pigment whose internal state (such as pH) is changed by acid, alkali or free radicals, thereby changing the state of color development or decolorization. In addition, it may be a pigment that undergoes a change in the state of color development or decolorization by directly being stimulated by an acid, an alkali, or a free radical without exposure to light.

Among them, from the viewpoint of the visibility and resolution of the exposed part and the non-exposed part, dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, and the maximum absorption wavelength is generated by free radicals. Varying pigments are more preferred. When the photosensitive composition layer is a negative photosensitive composition layer, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part, the negative photosensitive composition layer contains a maximum absorption wavelength that is generated by free radicals. The changed dye is preferable as both the dye N and the photoradical polymerization initiator. Moreover, it is preferable that dye N is a dye which develops color by acid, alkali, or a radical from the viewpoint of the visibility of an exposure part and a non-exposure part.

As an example of the color development mechanism of the dye N, a radical reactive dye, an acid reactive dye or an alkali reactive dye (such as a leuco dye) can be mentioned by adding a photoradical polymerization initiator to the photosensitive composition layer. , photocationic polymerization initiator (photoacid generator) or photobase generator and free radicals, acids or bases generated by photoradical polymerization initiators, photocationic polymerization initiators or photobase generators after exposure And the appearance of color.

From the viewpoint of the visibility of the exposed part and the non-exposed part, the maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development of the dye N is preferably 550 nm or more, more preferably 550 to 700 nm, and 550 to 650 nm. Further better. In addition, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm for color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of pigment N was measured by using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in the atmospheric environment in the wavelength range of 400nm to 780nm. The intensity is obtained at an extremely small wavelength (maximum absorption wavelength).

As a coloring matter which develops or decolorizes by exposure, a colorless compound is mentioned, for example. Examples of dyes that decolorize by exposure include colorless compounds, diarylmethane-based dyes, Kuchiguchi-based dyes, Kuchiyamaguchi-based dyes, iminonaphthoquinone-based dyes, and azomethine-based dyes. and anthraquinone pigments. As the dye N, a colorless compound is preferable from the viewpoint of the visibility of the exposed portion and the non-exposed portion.

As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane dye), a colorless compound having a spiropyran skeleton (spiropyran dye), and a colorless compound having a fluorescent yellow parent skeleton ( Fluorescent yellow parent system pigment), colorless compound with diarylmethane skeleton (diarylmethane pigment), colorless compound with rhodamine lactam skeleton (rhodamine lactamide pigment), indolyl A colorless compound with a phthalide skeleton (indolylphthalide pigment) and a colorless compound with a colorless aureamine skeleton (colorless aureamine pigment). Among them, triarylmethane-based pigments or fluorescent yellow parent system pigments are preferred, and colorless compounds (triphenylmethane-based pigments) with triphenylmethane skeletons or fluorescent yellow parent system pigments are more preferred.

As a colorless compound, it is preferable to have a lactone ring, a sultone ring, or a sultone ring from the viewpoint of the visibility of an exposed part and a non-exposed part. Thereby, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with the free radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator Decolorize a colorless compound by closing its ring, or develop a color by opening its ring. As a colorless compound, a compound having a lactone ring, a sultone ring or a sultone ring and the lactone ring, a sultone ring or a sultone ring is colored by free radicals or acid ring opening is preferable , a compound that has a lactone ring and the lactone ring is opened by free radicals or acid to develop color is more preferred.

Examples of the dye N include the following dyes and leuco compounds. Among dyes N, specific examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, and quinaldine. quinaldine red, rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red , Congo red, benzopurpurine 4B, α-naphthyl red, nile blue 2B, nile blue A, methyl violet, malachite green, parafuchsin , victoria pure blue (manufactured by Orient Chemical Industries Co., Ltd.), Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industries Co., Ltd.), oil scarlet (oil scarlet) #308 (manufactured by Orient Chemical Industries Co., Ltd.), oil red OG (manufactured by Orient Chemical Industries Co., Ltd.), oil red RR (manufactured by Orient Chemical Industries Co., Ltd.), oil green #502 (manufactured by Orient Chemical Industries Co., Ltd.), spilon red (manufactured by Orient Chemical Industries Co., Ltd.), BEH special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresyl violet, cresyl red, rhodamine B, rhodamine 6G, sulforhodamine B, aurethamine, 4-p-diethylaminophenylimino Naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino -Phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p Diethylaminophenylimino-5-pyrazolone.

Among the dye N, specific examples of the colorless compound include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy) , crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoride Bright yellow precursor, 2-anilino-3-methyl-6-(N-ethyl-p-toluidyl) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N, N-diethylamino)-5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6- Methyl-7-anilino fluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilino fluorescent yellow precursor, 3-(N,N-diethyl Amino)-6-methyl-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-chloro fluorescent yellow precursor, 3-(N ,N-diethylamino)-6-methoxy-7-aminofluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorescence Yellow precursor, 3-(N,N-diethylamino)-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow precursor, 3-(N,N-diethylamino)-7,8-benzofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorescent Yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-stibamido fluorescent yellow precursor, 3-piperidinyl-6-methyl-7-anilino fluorescent yellow Parent, 3-pyrrolidinyl-6-methyl-7-anilinofluorescent yellow parent, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide (phthalide) , 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylamine Phthalactone, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide lactone, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenyl Amino) spiroisobenzofuran-1 (3H), 9'-[9H]koushankou star-3-one.

From the viewpoint of the visibility of the exposed area and the non-exposed area, the visibility of the pattern after development, and the resolution, the pigment N is preferably a pigment whose maximum absorption wavelength is changed by free radicals. The pigment of color is better. As the dye N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate are preferable.

One kind of dye N may be used alone, or two or more kinds may be used. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, the visibility of the pattern after development, and the resolution, the content of the pigment N is preferably 0.1% by mass or more with respect to the total mass of the photosensitive composition layer, and 0.1 to 0.1% by mass. 10 mass % is more preferable, 0.1-5 mass % is further more preferable, and 0.1-1 mass % is especially preferable.

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 composition layer is in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by radicals as an example. A solution in which 0.001 g and 0.01 g of a pigment were dissolved in 100 mL of methyl ethyl ketone was prepared. A photoradical polymerization initiator (trade name, Irgacure OXE01, manufactured by BASF Japan Ltd.) was added to each of the obtained solutions, and light with a wavelength of 365 nm was irradiated to generate radicals to bring all the pigments into a color-developed state. Then, under an atmospheric environment, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve was prepared. Next, except having dissolved 3 g of photosensitive composition layers in methyl ethyl ketone instead of a dye, the absorbance of the solution which color-developed all dyes was measured by the method similar to the above. Based on the calibration curve, the content of the pigment contained in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer. In addition, the photosensitive composition layer 3g is the same as the total solid content 3g in the photosensitive composition.

(pigment) The photosensitive composition layer may contain a pigment. When the photosensitive composition layer contains a pigment, the photosensitive composition layer corresponds to a colored resin layer. In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the back peripheral portion of a transparent glass substrate or the like is attached to a liquid crystal display window of an electronic device in order to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer can be used. As a pigment, what is necessary is just to select suitably according to a desired hue, For example, black pigment, a white pigment, and color pigments other than black and white are mentioned. When forming a black pattern, a black pigment is preferable as a pigment.

As a black pigment, a well-known black pigment (for example, an organic pigment, an inorganic pigment, etc.) is mentioned, for example. Among these, carbon black, titanium oxide, titanium carbide, iron oxide, or graphite are preferred as the black pigment, and carbon black is more preferred, from the viewpoint of optical density. As the carbon black, a surface-modified carbon black in which at least a part of the surface is covered with a resin is preferable from the viewpoint of surface resistance.

From the viewpoint of dispersion stability, the particle diameter (number average particle diameter) of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. "Particle size" refers to the diameter of a circle when the area of the pigment particle is calculated from a photographic image of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered. In addition, the "number average particle diameter" means the average value obtained by obtaining the said particle diameter for arbitrary 100 particles, and averaging the obtained 100 particle diameters.

Examples of white pigments include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of JP-A-2005-007765. As the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate are preferred, titanium oxide or zinc oxide is more preferred, titanium oxide is further preferred , rutile-type or anatase-type titanium oxide is particularly preferred, and rutile-type titanium oxide is most preferred. In addition, the surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or organic matter, or two or more of these treatments may be performed. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance and delustering properties can be improved. From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, it is preferable to perform at least one of alumina treatment and zirconia treatment as the surface treatment on the surface of titanium oxide, and to perform alumina treatment and zirconium dioxide treatment are both better.

When the photosensitive composition layer is a colored resin layer, it is also preferable that the photosensitive composition layer contains color pigments other than black pigments and white pigments from the viewpoint of transferability. The particle size (number average particle size) of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. The lower limit is preferably at least 10 nm. Examples of color pigments include Victoria Pure Blue BO (Color Index (Color Index) (hereinafter, also referred to as "C.I.") 42595), auretamine (C.I. 41000), fat black (fat black) HB (C.I. 26150 ), monolight yellow GT (C.I. Pigment Yellow 12), permanent yellow GR (C.I. Pigment Yellow 17), permanent yellow HR (C.I. Pigment Yellow 83), permanent carmine (permanent carmine) FBB (C.I. Pigment Red 146), Hestaperm Red (hostaperm red) ESB (C.I. Pigment Violet 19), Permanent Ruby (permanent ruby) FBH (C.I. Pigment Red 11), Fastel Pink (pastel pink) B Supura (C.I. Pigment Red 81), monastral fast blue (C.I. Pigment Blue 15), Monolette Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Violet 23, and C.I. Pigment Red 177 are preferred.

One kind of pigment may be used alone, or two or more kinds may be used. The pigment content is preferably more than 3% by mass and not more than 40% by mass relative to the total mass of the photosensitive composition layer, more preferably more than 3% by mass and not more than 35% by mass, more preferably more than 5% by mass and not more than 35% by mass. More preferably, 10 to 35% by mass is particularly preferred.

When the photosensitive composition layer contains pigments other than black pigments (for example, white pigments and color pigments, etc.), the content of pigments other than black pigments is preferably 30% by mass or less relative to the total mass of black pigments, 1 -20 mass % is more preferable, and 3-15 mass % is still more preferable.

When the photosensitive composition layer contains a black pigment, it is preferred that the black pigment (preferably carbon black) be introduced into the photosensitive composition in the form of a pigment dispersion. The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing with a disperser. What is necessary is just to select a pigment dispersant according to a pigment and a solvent, For example, a commercially available dispersant can be used. "Vehicle" refers to the part of the medium that disperses the pigment when preparing the pigment dispersion. The above-mentioned vehicle is liquid and contains a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. In addition, fine pulverization can also be carried out by mechanical grinding using frictional force. Examples of the disperser and fine pulverization include the descriptions in "Paint Dictionary" (by Kunizo Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310).

(other additives) The photosensitive composition layer may contain known additives as needed in addition to the above components. Examples of additives include radical polymerization inhibitors, antioxidants (for example, phenidone, etc.), rust inhibitors (for example, benzotriazoles and carboxybenzotriazoles, etc.), sensitizers, interface Active agents, plasticizers, heterocyclic compounds (eg, triazoles, etc.), pyridines (eg, isonicotinamide, etc.), and purine bases (eg, adenine, etc.). In addition, examples of other additives include metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic precipitation inhibitors and paragraphs [0165] to [0184] of JP-A-2014-085643, the contents of which are incorporated in this specification. Each additive may be used alone or in combination of two or more.

The photosensitive composition 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 them, phenothiazine, phenanthamide, or 4-methoxyphenol is preferred. Examples of other radical polymerization inhibitors include naphthylamine, copper (I) chloride, N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, and the like. In order not to impair the sensitivity of the photosensitive composition layer, it is preferable to use N-nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor. The content of the radical polymerization inhibitor is preferably from 0.005 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, and still more preferably from 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

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

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di -2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N,N - Di-2-ethylhexyl)aminoethylenylcarboxybenzotriazole and the like. As carboxybenzotriazoles, commercial items such as CBT-1 (JOHOKU CHEMICAL CO., LTD., brand name) can be used, for example.

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

Examples of the surfactant include those described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable. Examples of commercially available fluorine-based surfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F- 144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, 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 (the above are manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (the above Manufactured for Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (the above are AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (the above are manufactured by OMNOVA Solutions Inc.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F , 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by Neos Corporation), U-120E (manufactured by UNICHEM CO., LTD.), etc. Also, as the fluorine-based surfactant, an acrylic compound having a molecular structure including a functional group containing a fluorine atom is preferably used, and when heat is applied, the functional group containing a fluorine atom is cut off, thereby Fluorine atoms evaporate. Examples of such fluorine-based surfactants include the MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as MEGAFACE DS- twenty one. Furthermore, 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 as the fluorine-based surfactant. In addition, a blocked polymer can also be used as the fluorine-based surfactant. Also, as a fluorine-based surfactant, a fluorine-containing polymer compound comprising a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a structure unit derived from a (meth)acrylate compound having two A constituent unit of the (meth)acrylate compound of the above (preferably 5 or more) alkoxyl groups (preferably ethoxyl groups, propoxyl groups). Moreover, as a fluorine-type surfactant, the fluorine-containing polymer which has a group containing an ethylenically unsaturated bond in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K (the above are manufactured by DIC Corporation) and the like.

From the viewpoint of improving environmental suitability, fluorine-based surfactants are derived from compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). The surfactant of the alternative material is preferred. As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerin ethoxylate, etc.) base compounds, 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, etc. Specific examples include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, HYDROPALAT WE 3323 (manufactured by BASF Corporation), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation). Manufactured), Solsperse 20000 (manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-1105, D-6112, D-6112- W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd. above), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd. above), etc.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.

Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and 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 (manufactured by Dow Corning Toray Co.,Ltd. X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, 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 (the above are Shin-Etsu Silicone Co., Ltd. (manufactured), F-4440, TSF-4300, TSF-4445, TSF -4460、TSF-4452（以上為Momentive Performance Materials Inc.製造）、BYK300、BYK306、BYK307、BYK310、BYK320、BYK323、BYK325、BYK330、BYK313、BYK315N、BYK331、BYK333、BYK345、BYK347、BYK348、BYK349、BYK370 , BYK377, BYK378 (the above are manufactured by BYK Chemie), etc.

Surfactants may be used alone or in combination of two or more. When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.80% by mass relative to the total mass of the photosensitive composition layer. for further improvement.

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

The layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and 0.5 to 8 μm for the best. Thereby, the developability of a photosensitive composition layer can be improved, and resolution can be improved. Moreover, in one aspect, 0.5-5 μm is preferable, 0.5-4 μm is more preferable, and 0.5-3 μm is still more preferable.

(impurities, etc.) The photosensitive composition layer may contain impurities. Examples of impurities include metal impurities or ions thereof, halide ions, residual organic solvents, and residual monomers.

Examples of metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions and halide ions. Among them, from the viewpoint of easy mixing, sodium ions, potassium ions, and halide ions are preferably contained in the following contents. The metal impurities are compounds different from the above-mentioned particles (for example, metal oxide particles) that may be contained in the transfer film.

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

As a method of adjusting the content of impurities, for example, a method of selecting a material with a low content of impurities as a raw material of the photosensitive composition layer, a method of preventing impurities from entering the photosensitive composition layer, and a method of washing and removing them are mentioned. The content of impurities can be quantified by known methods such as ICP emission spectrometry, atomic absorption spectrometry, and ion chromatography, for example.

Examples of residual organic solvents include benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethyl Acetamide and hexane. The content of the residual organic solvent is preferably at most 100 mass ppm with respect to the total mass of the photosensitive composition layer, more preferably at most 20 mass ppm, still more preferably at most 4 mass ppm. The lower limit is preferably at least 10 mass ppb with respect to the total mass of the photosensitive composition layer, more preferably at least 100 mass ppb. As a method of adjusting content of a residual organic solvent, the method of adjusting the drying process conditions in the manufacturing method of the transfer film mentioned later is mentioned. Moreover, content of a residual organic solvent can be quantified by a well-known method, such as a gas chromatography analysis, for example.

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

[middle layer] The transfer film preferably has an intermediate layer between the dummy support and the photosensitive composition layer. Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-072724. As an intermediate layer, an oxygen barrier layer is preferable from the standpoint of improving the sensitivity at the time of exposure and reducing the time load of the exposure machine to improve productivity, and exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (22 1 mass % aqueous solution of sodium carbonate at ℃) the oxygen barrier layer is more preferable. Hereinafter, each component which can be contained in a water-soluble resin layer (intermediate layer) is demonstrated.

The water-soluble resin layer (intermediate layer) contains resin. It is preferable that the above-mentioned 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-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl Resins such as ether-based resins, polyamide resins, and copolymers thereof. Moreover, as a water-soluble resin, the copolymer of (meth)acrylic acid/vinyl compound etc. can also be used. As (meth)acrylic acid/vinyl compound copolymers, (meth)acrylic acid/allyl (meth)acrylate copolymers are preferred, and methacrylic acid/allyl methacrylate copolymers are more preferred. good. When the water-soluble resin is a copolymer of (meth)acrylic acid/vinyl compound, the composition ratios (mole %) are, for example, preferably 90/10 to 20/80, and 80/20 to 30/70 are better.

The lower limit of the weight average molecular weight of the water-soluble resin is preferably at least 5,000, more preferably at least 7,000, and still more preferably at least 10,000. Moreover, as the upper limit value, 200,000 or less is preferable, 100,000 or less is more preferable, 50,000 or less is still more preferable. The degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.

One kind of water-soluble resin may be used alone, or two or more kinds may be used. The content of the water-soluble resin is not particularly limited, but from the viewpoint of further improving the oxygen barrier property and interlayer mixing suppression ability, it is better to be 50% by mass or more relative to the total mass of the water-soluble resin layer (intermediate layer), and 70% by mass. Mass % or more is more preferable, 80 mass % or more is more preferable, and 90 mass % or more is especially preferable. In addition, the upper limit is not particularly limited, for example, it is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.

The intermediate layer may contain other components in addition to the above-mentioned water-soluble resin. As other components, polyols, alkylene oxide adducts of polyols, phenol derivatives, or amide compounds are preferable, and polyols, phenol derivatives, or amide compounds are more preferable. Moreover, as another component, a well-known surfactant is also mentioned, for example.

Examples of polyhydric alcohols include glycerin, diglycerin, and diethylene glycol. As the number of the hydroxyl groups which polyols have, 2-10 are preferable. Examples of the alkylene oxide adducts of polyols include compounds in which ethoxyl groups, propoxyl groups, and the like are added to the above polyols. The average addition number of alkyleneoxy groups is preferably from 1 to 100, more preferably from 2 to 50, and still more preferably from 2 to 20. As a phenol derivative, bisphenol A and bisphenol S are mentioned, for example. As an amide compound, N-methylpyrrolidone is mentioned, for example.

The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyether resins, phenol derivatives, and amide compounds.

The molecular weight of other components is preferably less than 5000, more preferably less than 4000, more preferably less than 3000, particularly preferably less than 2000, most preferably less than 1500. The lower limit is preferably 60 or more.

The other components may be used alone or in combination of two or more. The content of other components is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1% by mass, based on the total mass of the intermediate layer. The upper limit is preferably less than 30 mass %, more preferably 10 mass % or less, and still more preferably 5 mass % or less.

The intermediate layer may contain impurities. As an impurity, the impurity contained in the said photosensitive composition layer is mentioned, for example.

The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above-mentioned range, the interlayer mixing suppression ability is excellent without reducing the oxygen barrier property. In addition, it is also possible to further suppress an increase in the removal time of the water-soluble resin layer (intermediate layer) during image development.

[protective film] The transfer film may have a protective film on the photosensitive composition layer. As the protective film, a heat-resistant and solvent-resistant resin film can be used, for example, polyolefin films such as polypropylene film and polyethylene film, polyester film such as polyethylene terephthalate film, polycarbonate film, etc. and polystyrene film. In addition, as the protective film, a resin film made of the same material as the dummy support described above can be used. Among these, as a protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is still more preferable.

The thickness of the protective film is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, still more preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm. From the viewpoint of excellent mechanical strength, the thickness of the protective film is preferably 1 μm or more, and from the viewpoint of relatively low cost, it is preferably 100 μm or less.

In addition, in the protective film, it is preferable that the number of fisheyes (fisheye) with a diameter of 80 μm or more included in the protective film is 5 or less/m ² . In addition, "fish eye" means that when the material is thermally melted, kneaded, and extruded, and when the film is produced by biaxial stretching and casting methods, the foreign matter, undissolved matter, and oxidative deterioration of the material, etc. Taken into 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, still more preferably 5 particles/mm ² or less. Thereby, it is possible to suppress defects generated by transferring the unevenness caused by the particles contained in the protective film to the photosensitive composition layer or the metal layer.

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

[Manufacturing method of transfer film] It does not specifically limit as a manufacturing method of a transfer film, A well-known method is mentioned. As a method for producing the above-mentioned transfer film 10, for example, a method including the steps of applying a composition for forming an intermediate layer on the surface of the dummy support 11 to form a coating film, and further drying the coating film to form an intermediate layer The step of layer 13; and the step of coating the photosensitive composition on the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive composition layer 15.

When the transfer film 10 has the protective film 19, the protective film 19 can be crimped on the composition layer 17 of the transfer film 10 manufactured by the above-mentioned manufacturing method. As a method of manufacturing the transfer film 10, a process including a dummy support 11, an intermediate layer, and a process including the step of providing the protective film 19 in contact with the surface of the composition layer 17 opposite to the dummy support 11 is provided. 13. The photosensitive composition layer 15 and the transfer film 10 of the protective film 19 are preferred. After the transfer film 10 is produced by the above-mentioned production method, the transfer film in roll form can be produced and stored by winding up the transfer film 10 . The transfer film 10 in the form of a roll can be provided as it is in the step of bonding to a substrate by a roll-to-roll system described later.

In addition, the method of manufacturing the transfer film 10 described above may be a method of forming the composition layer 17 on the protective film 19 .

(Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)) The water-soluble resin composition preferably contains various components and a solvent that form the above-mentioned intermediate layer (water-soluble resin layer). In addition, in the water-soluble resin composition, the preferable range of the content of each component to the total solid content of the composition is the same as the preferable range of the content of each component to the total mass of the above-mentioned water-soluble resin layer. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferred. Water or a mixture of water and water-miscible organic solvents A solvent is more preferred. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. One kind of solvent may be used alone, or two or more kinds may be used. The content of the solvent is preferably from 50 to 2500 parts by mass, more preferably from 50 to 1900 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The formation method of the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer comprising the above-mentioned components, for example, known coating methods (slit coating, spin coating, curtain coating and inkjet coating) can be mentioned. wait).

(Photosensitive composition and method of forming photosensitive composition layer) From the viewpoint of excellent productivity, a photosensitive resin containing components (for example, resin A, polymerizable compound, polymerization initiator, thermal crosslinking agent, etc.) It is better to form a composition. As a method for producing a transfer film, specifically, a method of coating a photosensitive composition on an intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer is relatively good.

As a photosensitive composition, it is preferable to contain various components and a solvent which form the said photosensitive composition layer. In addition, in the photosensitive composition, the preferable range of content of each component with respect to the total solid content of a composition is the same as the preferable range of content of each component with respect to the total mass of the said photosensitive composition layer. The solvent is not particularly limited as long as it can dissolve or disperse components other than the solvent, and known solvents can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic Group hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, Lactone solvents and mixed solvents containing two or more of these.

As the solvent, it is preferable to contain at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among them, 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 A mixed solvent is more preferable, and a mixed solvent containing at least three types of an alkylene glycol ether, an alkylene glycol ether acetate solvent, and a ketone solvent is still more preferable.

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether , Diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol Monoalkyl ether acetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone. As the solvent, solvents described in paragraphs [0092] to [0094] of International Publication No. 2018/179640 and solvents described in paragraph [0014] of JP-A-2018-177889 can be used, and these contents are incorporated in in this manual. One kind of solvent may be used alone, or two or more kinds may be used. The content of the solvent is preferably from 50 to 1900 parts by mass, more preferably from 100 to 1200 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

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

As a method of drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably at least 90°C, more preferably at least 100°C, and still more preferably at least 110°C. Moreover, although it does not specifically limit as its upper limit, 130 degreeC or less is preferable, and 120 degreeC or less is more preferable. Moreover, as drying time, 20 seconds or more are preferable, 40 seconds or more are more preferable, and 60 seconds or more are still more preferable. Moreover, although it does not specifically limit as the upper limit, Preferably it is 450 seconds or less, More preferably, it is 300 seconds or less. The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. Moreover, as its upper limit, it is preferable that it is 130 degreeC or less, and it is more preferable that it is 120 degreeC or less. Drying can also be performed by changing the temperature continuously. Moreover, as drying time, 20 seconds or more are preferable, 40 seconds or more are more preferable, and 60 seconds or more are still more preferable. Also, the upper limit is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.

Furthermore, a transfer film can be manufactured by bonding a protective film to a photosensitive composition layer. The method of bonding the protective film to the photosensitive composition layer is not particularly limited, and known methods can be used. Known laminators, such as a vacuum laminator and an automatic cutting laminator, are mentioned as an apparatus which bonds a protective film to a photosensitive composition layer. The laminator is preferably equipped with any heatable roll such as a rubber roll, and is capable of pressurization and heating. [Example]

Hereinafter, the characteristics of the present invention will be described more specifically with reference to Examples and Comparative Examples. Materials, usage amounts, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed unless departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the specific examples shown below. In addition, in the following examples, the weight average molecular weight of resin is the weight average molecular weight calculated|required by the polystyrene conversion by gel permeation chromatography (GPC). In addition, the theoretical acid value was used for the acid value.

＜Materials used in the production of transfer film＞ The materials (photosensitive composition and composition for intermediate layer formation) used for preparation of the transfer film used in the Example are demonstrated.

(Each component of the photosensitive composition) The photosensitive composition layer which the transfer film has was formed using the photosensitive composition. The components used in the preparation of the photosensitive composition are as follows, and the components shown below were mixed in the formulations shown in Tables 2 to 3 shown in the latter paragraph to obtain the respective photosensitive compositions used in Examples or Comparative Examples . The numerical value of each component in Tables 2-3 is a mass part. In addition, when preparing the photosensitive composition, a mixture containing methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd., 60 parts by mass) and propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K., 40 parts by mass) was prepared. A solvent was mixed, and each component was added to this mixed solvent in the formula shown in the table|surface shown in the following paragraph. In addition, the solid content concentration of each photosensitive composition was 13% by mass.

[resin] ・Compounds 1 to 4: resins (compounds) each having the following characteristics In addition, Compounds 1 to 4 correspond to alkali-soluble resins.

[Table 1] composition mw Acid value (mgKOH/kg) Compound 1 Styrene/methacrylic acid/methyl methacrylate=32/28/40 (mass%) 40000 150 Compound 2 Styrene/methacrylic acid/methyl methacrylate=52/29/23 (mass%) 60000 189 Compound 3 Benzyl methacrylate/methacrylic acid=81/19 (mass %) 40000 170 Compound 4 Styrene/methacrylic acid/glycidyl methacrylate/methyl methacrylate=50/18/30/2 (mass %) 20000 124

In the above-mentioned table, in the "composition" column, the types of structural units contained in the resins (compounds) are shown for each resin (compound), and the mass ratio of the content of each structural unit is shown in parentheses. As the type of each structural unit, the name of the monomer used as the source of each structural unit is shown. For example, Compound 1 is a resin having a structural unit based on styrene, a structural unit based on methacrylic acid, and a structural unit based on methyl methacrylate in a mass ratio of 32:28:40.

[polymeric compound] ・BPE-500: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・BPE-200: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・BPE-100: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・Polymerizable compound 1: Dimethacrylate of polyethylene glycol added with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide at both ends of bisphenol A ・M-270: ARONIX M-270, polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO.,LTD. A-TMPT: trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR454: Ethoxylated (3) trimethylolpropane trimethacrylate, manufactured by Arkema S.A. SR502: Ethoxylated (9) trimethylolpropane trimethacrylate, manufactured by Arkema S.A. ・A-9300-CL1: Caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[Thermal crosslinking agent] ・SBB-70P: Duranate, manufactured by ASAHI KASEI CORPORATION ・TPA-B80E: Duranate, manufactured by ASAHI KASEI CORPORATION

[polymerization initiator] ·B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-bis Phenyl imidazole dimer) manufactured by KUROGANE KASEI Co., Ltd.

[additive] ・SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd. · Colorless crystal violet: manufactured by Tokyo Chemical Industry Co., Ltd. ・N-phenylglycine: manufactured by Tokyo Chemical Industry Co., Ltd. Bright green: manufactured by Tokyo Chemical Industry Co., Ltd. ・CBT-1: carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO.,LTD. ·Mixture 1: 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole 1:1 (mass ratio) mixture of azoles · Wako Well: Manufactured by FUJIFILM Wako Pure Chemical Corporation ·Irganox245: manufactured by BASF ・N-Nitrosophenylhydroxylamine aluminum salt: manufactured by FUJIFILM Wako Pure Chemical Corporation ・Phenidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・F-552: Fluorinated surfactant, manufactured by DIC Corporation

(Components of the intermediate layer forming composition) The composition for forming an intermediate layer was prepared by mixing the following components. In addition, the unit of the quantity of each component is a mass part. Ion-exchanged water: 38.12 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass KURARAY POVAL 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by mass Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO.,LTD.): 1.49 parts by mass MEGAFACE F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 parts by mass

＜Preparation of transfer film＞ About Examples 1, 5-7, and the comparative example 1, the transfer film was produced by the following procedure. First, the dummy support (polyethylene terephthalate film with a thickness of 16 μm (LUMIRROR 16KS40, manufactured by TORAY INDUSTRIES, INC.), haze: 0.6%) was coated on a dummy support using a bar coater. Table 2- The photosensitive composition of each Example and the comparative example was coated with the thickness shown in 3, and it was made to dry at 80 degreeC using an oven, and the photosensitive composition layer (negative photosensitive composition layer) was formed. On the obtained photosensitive composition layer, polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was pressure-bonded as a protective film to produce a transfer film.

Moreover, about Examples 2-4 and 8-10, the transfer film was produced by the following procedure. First, the dummy support (polyethylene terephthalate film with a thickness of 16 μm (LUMIRROR 16KS40, manufactured by TORAY INDUSTRIES, INC.), haze: 0.6%) was coated on a dummy support using a bar coater. Table 2- The composition for forming an intermediate layer was applied to a thickness shown in 3, and dried at 90° C. using an oven to form an intermediate layer. Furthermore, the photosensitive composition was coated on the intermediate layer using a bar coater so that the thickness after drying became the thickness shown in Tables 2 to 3, and dried at 80° C. using an oven to form a photosensitive composition layer. (Negative photosensitive composition layer). On the obtained photosensitive composition layer, polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was pressure-bonded as a protective film to produce a transfer film.

<Manufacture of a laminate> A copper layer-attached PET substrate in which a 500-nm-thick copper layer was formed on a 200-μm-thick PET film (polyethylene terephthalate film) by a sputtering method was used. Cut the produced transfer film into 10cm squares, and peel off the protective film, in such a way that the photosensitive composition layer is in contact with the copper layer on the surface of the PET substrate. /min. Laminated on the PET substrate with copper layer under lamination conditions to obtain a laminated body. At this point, when the transfer film does not include an intermediate layer, the laminate has a composition of "PET film-copper layer-photosensitive composition-dummy support", and when the transfer film includes an intermediate layer, it has a composition of "PET film- Copper layer-photosensitive composition-intermediate layer-pseudo support". Next, the dummy support was peeled off from the obtained laminate, and a photomask having a pattern with a line (μm)/space (μm) ratio of 5/5 was brought into close contact with the exposed surface of the laminate. Light was irradiated at an exposure amount of 50 mJ/cm ² using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Japan Science Engineering Co., Ltd., dominant wavelength: 365 nm). The exposure amount is set as the exposure amount of the photoresist pattern obtained after developing to reproduce the line and space shape of the mask. Thereafter, development was performed using a 30° C. 1.0% sodium carbonate aqueous solution as a developing solution. Specifically, in the development, spray processing was performed for 40 seconds, and after the developer was shaken off by air knife (Air Knife) treatment, spray processing was performed with pure water for 30 seconds, and further air knife treatment was performed. . Thereby, a laminate having a photoresist pattern in the shape of lines and spaces was obtained.

Next, the laminated body which has a photoresist pattern was heated under the heating conditions ("heating temperature and heating time") described in Tables 2-3 mentioned later. Then, the obtained laminated body was immersed in 10 mass % sulfuric acid aqueous solution (liquid temperature: 40 degreeC) for 3 minutes.

Next, the obtained laminate was placed in a copper sulfate plating solution (copper sulfate 75g/L, sulfuric acid 190g/L, chloride ion 50 mass ppm, manufactured by Meltex Inc., "Copper Glyme PCM", 5mL/L), and the Under the condition of 1A/dm ² , the copper electroplating treatment was carried out. After washing with water and drying the said laminated body after the copper plating process, it immersed in the 1 mass % potassium hydroxide aqueous solution (pH=13.5) of 50 degreeC, and the photoresist pattern was peeled off. The copper layer (seed layer) of the laminate after the resist pattern peeling step was removed with an aqueous solution containing 0.1% by mass of sulfuric acid and 0.1% by mass of hydrogen peroxide to obtain a copper wiring pattern. The copper wiring pattern was observed with an optical microscope, and the shape evaluation of the conductor pattern was performed based on the following criteria. 1: No conductor pattern was formed, or the shape of the formed conductor pattern was greatly deformed. 2: The shape of the formed conductor pattern was almost the desired shape, but deformation was observed in some parts. 3: The shape of the formed conductor pattern is a desired shape, and there is no deformation.

In Tables 2 to 3, the "heating temperature and heating time" column describes the temperature and time when the laminated body having a photoresist pattern is heated. Heat at 120°C for 20 minutes. In Tables 2 to 3, the column "Elastic modulus X (GPa)" shows the above-mentioned elastic modulus X (GPa), and the column "Elastic modulus X/Elastic modulus Y" shows the above-mentioned X/Y.

[Table 2] Comparative example 1 Example 1 Example 2 Example 3 Example 4 resin Compound 1 - - - - - Compound 2 53.27 53.07 53.07 - - Compound 3 - - - - - Compound 4 - - - 53.07 53.07 polymeric compound BPE-500 8.63 8.53 8.53 - - BPE-200 - - - - - BPE-100 25.89 25.79 25.79 35.22 35.22 polymer compound 1 - - - - - M-270 3.84 3.74 3.74 2.84 2.84 A-TMPT - - - - - SR-454 - - - - - SR-502 - - - - - A-9300-CL1 - - - - - thermal crosslinking agent SBB-70P - 0.50 0.50 0.50 - TPA-B80E - - - - 0.50 polymerization initiator B-CIM 6.83 6.83 6.83 6.83 6.83 additive SB-PI 701 0.30 0.30 0.30 0.30 0.30 colorless crystal violet 0.40 0.40 0.40 0.40 0.40 N-phenylglycine 0.14 0.14 0.14 0.14 0.14 bright green - - - - - CBT-1 0.10 0.10 0.10 0.10 0.10 Mixture 1 - - - - - Well 0.27 0.27 0.27 0.27 0.27 Irganox245 - - - - - N-Nitrosophenylhydroxylamine Aluminum Salt - - - - - Phenidone 0.01 0.01 0.01 0.01 0.01 F-552 0.32 0.32 0.32 0.32 0.32 condition Heating temperature and heating time none 120°C for 20 minutes 120°C for 20 minutes 120°C for 20 minutes 145°C for 20 minutes Thickness of photosensitive composition layer (μm) 3 3 3 3 3 The thickness of the middle layer (μm) none none 1 1 1 evaluate shape evaluation 1 2 2 2 3 Elastic modulus X (Gpa) 4.5 5.2 5.2 5.6 5.9 Elastic modulus X/Elastic modulus Y 1.35 1.08 1.08 1.05 1.05

[table 3] Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 resin Compound 1 61.70 - - - - - Compound 2 - - 50.50 - - 49.50 Compound 3 - 58.70 - 51.50 51.50 - Compound 4 - - - - - - polymeric compound BPE-500 - 27.00 15.00 7.40 7.40 36.20 BPE-200 20.00 - - 10.00 10.00 - BPE-100 - - - - - - polymer compound 1 - - 10.00 - - - M-270 - - - - - 5.00 A-TMPT 6.00 - 5.00 10.00 10.00 - SR-454 9.00 - 5.00 15.00 15.00 - SR-502 - 4.00 - - - - A-9300-CL1 - 7.80 9.77 - - - thermal crosslinking agent SBB-70P - - - 0.50 TPA-B80E 0.50 0.50 0.50 0.50 0.50 polymerization initiator B-CIM 1.90 1.10 3.00 3.80 3.80 7.00 additive SB-PI 701 0.30 0.10 0.30 0.30 0.30 0.50 colorless crystal violet 0.40 0.66 0.60 - - 0.40 N-phenylglycine - - - 1.00 1.00 0.20 bright green 0.05 - 0.02 0.05 0.05 - CBT-1 0.03 0.03 - 0.05 0.05 0.10 Mixture 1 - - 0.10 0.05 0.05 - Well - - - - - 0.30 Irganox245 0.10 0.10 0.20 0.20 0.20 - N-Nitrosophenylhydroxylamine Aluminum Salt 0.02 0.01 0.01 0.01 0.01 - Phenidone - - - 0.01 0.01 0.01 F-552 - - - 0.13 0.13 0.29 condition Heating temperature and heating time 145°C for 20 minutes 145°C for 20 minutes 145°C for 20 minutes 120°C for 20 minutes 120°C for 20 minutes 145°C for 20 minutes Thickness of photosensitive composition layer (μm) 10 10 10 3 3 3 The thickness of the middle layer (μm) none none none 1 1 1 evaluate shape evaluation 2 2 2 2 2 2 Elastic modulus X (Gpa) 5.6 5.6 5.3 5.3 5.4 5.3 Elastic modulus X/Elastic modulus Y 1.10 1.06 1.09 1.08 1.07 1.08

As shown in the table, according to the method of the present invention, it was confirmed that the desired effect can be obtained.

10: transfer film 11: Pseudo-support 13: middle layer 15: Photosensitive composition layer 17: Composition layer 19: Protective film

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

10: transfer film

11: Pseudo-support

13: middle layer

15: Photosensitive composition layer

17: Composition layer

19: Protective film

Claims (19)

A method of manufacturing a laminate with a conductor pattern, which sequentially comprises: In the bonding step, the surface of the transfer film having the dummy support and the negative-type photosensitive composition layer on the side opposite to the dummy support is in contact with the aforementioned metal layer of the substrate having a metal layer on the surface. Laminating the aforementioned transfer film to the aforementioned substrate; Exposure step, performing pattern exposure on the aforementioned photosensitive composition layer; A development step, performing a development treatment on the exposed photosensitive composition layer to form a photoresist pattern; heating step, heating the aforementioned photoresist pattern; a cleaning step, cleaning the heated photoresist pattern with an acidic solution; An electroplating step, performing electroplating treatment on the aforementioned metal layer located in the area where the aforementioned photoresist pattern is not arranged; a stripping step, stripping the aforementioned photoresist pattern; and a removing step of removing the aforementioned metal layer exposed by the aforementioned stripping step and forming a conductor pattern on the aforementioned substrate, Between the aforementioned bonding step and the aforementioned exposing step or between the aforementioned exposing step and the aforementioned developing step, there is further a dummy support stripping step for peeling off the aforementioned dummy support, The aforementioned photosensitive composition layer contains a thermal crosslinking agent. The method of manufacturing a laminate having a conductor pattern according to Claim 1, wherein The modulus of elasticity of the surface of the photoresist pattern heated in the heating step opposite to the substrate side is 5.0 GPa or more. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein Let the elastic modulus of the surface of the photoresist pattern heated by the aforementioned heating step on the side opposite to the substrate side be the elastic modulus X, When the elastic modulus near the substrate side of the photoresist pattern heated by the aforementioned heating step is defined as the elastic modulus Y, Satisfy X/Y≤1.2. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein The photosensitive composition layer includes a polymerizable compound and a polymerization initiator. The method of manufacturing a laminate having a conductor pattern according to Claim 4, wherein The aforementioned polymerizable compound has an alkylene oxide-modified bisphenol structure. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein The aforementioned thermal crosslinking agent contains a blocked isocyanate compound. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein The haze of the pseudo-support is 1.0% or less. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein The thickness of the aforementioned dummy support is 50 μm or less. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein The transfer film has an intermediate layer between the dummy support and the photosensitive composition layer. The method of manufacturing a laminate having a conductor pattern according to Claim 9, wherein The aforementioned intermediate layer is a water-soluble resin layer. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein The foregoing exposure step is a step of performing pattern exposure through a photomask. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein The exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using active light rays onto which the image of the mask is projected. The method of manufacturing a laminate having a conductor pattern according to claim 1 or claim 2, wherein There is the aforementioned dummy support stripping step between the aforementioned laminating step and the aforementioned exposing step, The exposure step is a step of pattern-exposing the photosensitive composition layer by bringing the surface exposed by peeling off the dummy support into contact with a photomask. A transfer film, which has a pseudo-support and a negative photosensitive composition layer, wherein The aforementioned photosensitive composition layer contains a thermal crosslinking agent, The haze of the pseudo-support is 1.0% or less. The transfer film as described in Claim 14, wherein The thickness of the aforementioned dummy support is 50 μm or less. The transfer film as described in Claim 14 or Claim 15, wherein The photosensitive composition layer includes a polymerizable compound and a polymerization initiator. The transfer film as described in claim 16, wherein The aforementioned polymerizable compound has an alkylene oxide-modified bisphenol structure. The transfer film according to claim 14 or claim 15, which has an intermediate layer between the dummy support and the photosensitive composition layer. The transfer film as described in Claim 18, wherein The aforementioned intermediate layer is a water-soluble resin layer.

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