JP2023020049A - Transfer film, method for producing laminate having conductor pattern, and photosensitive composition - Google Patents

Abstract

To provide a transfer film capable of forming a resist pattern, the formed resist pattern having excellent peelability, a method for producing a laminate having a conductor pattern and a photosensitive composition.SOLUTION: A transfer film has a temporary support and a photosensitive composition layer, the photosensitive composition layer containing a resin A, a polymerizable compound, and a polymerization initiator. The resin A has a constitutional unit a having a group that produces an alkali-soluble group by the action of alkali, and a constitutional unit b having an acid radical.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a transfer film, a method for producing a laminate having a conductor pattern, and a photosensitive composition.

Since the number of steps for obtaining a predetermined pattern is small, after disposing a photosensitive composition layer on an arbitrary substrate using a transfer film and exposing this photosensitive composition layer through a mask, The method of developing is widely used.

For example, in Patent Document 1, a photosensitive resin composition for projection exposure containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator is used. A method of forming a resist pattern is described.

JP 2019-109543 A

The present inventors attempted to form a conductor pattern using a transfer film having a photosensitive composition layer as described in Patent Document 1, and found that although a resist pattern could be formed, it was not possible to form a resist pattern after the etching process or the plating process. It was found that the subsequent resist pattern was difficult to peel off. In particular, in the process of forming a conductor pattern by the semi-additive method, it was found that the resist pattern after the plating process is difficult to peel off.
Hereinafter, the fact that the resist pattern is easily peeled off after the etching process or the plating process is also referred to as "excellent peelability".

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a transfer film capable of forming a resist pattern and having excellent releasability of the formed resist pattern.
Another object of the present invention is to provide a method for producing a laminate having a conductor pattern and a photosensitive composition.

As a result of intensive studies on the above problem, the inventors have found that the above problem can be solved by the following configuration.

[1]
A transfer film having a temporary support and a photosensitive composition layer,
The photosensitive composition layer contains a resin A, a polymerizable compound, and a polymerization initiator,
A transfer film, wherein the resin A contains a structural unit a having a group that generates an alkali-soluble group by the action of an alkali, and a structural unit b having an acid group.
[2]
The transfer film of [1], wherein the structural unit a contains a structural unit having an alkali-decomposable group.
[3]
The transfer film according to [1] or [2], wherein the structural unit a contains a structural unit having a group that generates an acid group by the action of an alkali.
[4]
[1 ] to [3].
[5]
The content of the structural unit a is 5 to 50% by mass with respect to the total structural units of the resin A,
The transfer film according to any one of [1] to [4], wherein the content of the structural unit b is 10 to 30% by mass based on the total structural units of the resin A.
[6]
A transfer film having a temporary support and a photosensitive composition layer,
The photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
The resin B contains a structural unit b having an acid group,
The compound D has a group that generates an alkali-soluble group by the action of alkali,
A transfer film in which the content of the compound D is 5 to 50% by mass with respect to the total mass of the photosensitive composition layer.
[7]
The transfer film of [6], wherein the compound D contains a structural unit having an alkali-decomposable group.
[8]
The transfer film of [6] or [7], wherein the compound D contains a structural unit having a group that generates an acid group by the action of an alkali.
[9]
The compound D contains at least one selected from the group consisting of a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group [6] The transfer film according to any one of [8].
[10]
The transfer film according to any one of [1] to [9], further comprising an intermediate layer between the temporary support and the photosensitive composition layer.
[11]
The transfer film of [10], wherein the intermediate layer contains a water-soluble resin.
[12]
The water-soluble resin is selected from the group consisting of polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins and polyamide resins. [11] The transfer film as described in [11].
[13]
The transfer film and the substrate are separated so that the photosensitive composition layer side of the transfer film according to any one of [1] to [12] is in contact with the conductive layer of the substrate having a conductive layer on its surface. a laminating step of laminating;
An exposure step of exposing the photosensitive composition layer;
a resist pattern forming step of developing the exposed photosensitive composition layer to form a resist pattern;
either an etching step of performing an etching process or a plating process of performing a plating process on the conductive layer in a region where the resist pattern is not arranged;
a resist pattern stripping step of stripping the resist pattern;
Manufacture of a laminate having a conductor pattern, further comprising a removal step of removing the conductive layer exposed by the resist pattern stripping step and forming a conductor pattern on the substrate when the plating step is included. a method,
Between the bonding step and the exposure step, or between the exposure step and the development step, a laminate having a conductor pattern, further comprising a temporary support peeling step for peeling the temporary support. Production method.
[14]
The resist pattern stripping step is a step of stripping the resist pattern using a stripping solution,
The method for producing a laminate having a conductor pattern according to [13], wherein the stripping solution has a pH of 13 or higher.
[15]
The resist pattern forming step is a step of performing development using a developer to form a resist pattern,
The method for producing a laminate having a conductor pattern according to [13] or [14], wherein the developer has a pH of less than 13.
[16]
The method for producing a laminate having a conductor pattern according to any one of [13] to [15], wherein the exposure method in the exposure step is any one of mask exposure, direct imaging exposure and projection exposure.
[17]
The method for producing a laminate having a conductor pattern according to any one of [13] to [16], wherein the temporary support has a thickness of less than 16 μm.
[18]
Between the bonding step and the exposure step, the temporary support peeling step is provided,
The laminate having a conductor pattern according to any one of [13] to [17], wherein the exposed surface exposed in the temporary support peeling step is brought into contact with a mask to expose the photosensitive composition layer. manufacturing method.
[19]
including a resin C, a polymerizable compound, and a polymerization initiator,
The photosensitive composition, wherein the resin C contains a structural unit having a lactone group and a structural unit b having an acid group.
[20]
The content of the structural unit having the lactone group is 5 to 50% by mass based on the total structural units of the resin C, and the content of the structural unit b is 10 to 30% based on the total structural units of the resin C. % by mass, the photosensitive composition according to [19].
[21]
including a resin B, a polymerizable compound, a polymerization initiator, and a compound DA different from the resin B;
The resin B contains a structural unit b having an acid group,
The compound DA has a group having a lactone group,
A photosensitive composition, wherein the content of the compound DA is 5 to 50% by mass based on the total solid content of the photosensitive composition.

ADVANTAGE OF THE INVENTION According to this invention, the transfer film which can form a resist pattern and is excellent in the peelability of the formed resist pattern can be provided.
Moreover, according to the present invention, a method for producing a laminate having a conductor pattern and a photosensitive composition can also be provided.

It is the schematic which shows an example of a structure of a transfer film.

The present invention will be described in detail below.
The meaning of each notation below in this specification is shown.
A numerical range represented using "to" means a range including the numerical values described before and after "to" as lower and upper limits.
In the numerical ranges described stepwise, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. Moreover, in the numerical ranges described in this specification, the upper or lower limits described in a certain numerical range may be replaced with the values shown in the examples.
A "process" is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, it is included in the process as long as the intended purpose of the process is achieved.
“Transparent” means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more, unless otherwise specified.
The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 (manufactured by Hitachi Ltd.).
A refractive index is a value measured using an ellipsometer at a wavelength of 550 nm unless otherwise specified.
The hue is a value measured using a color difference meter (CR-221, manufactured by Minolta) unless otherwise specified.

Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) as a column, and THF (tetrahydrofuran) as an eluent. ), using a differential refractometer as a detector and polystyrene as a standard substance, it is a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer.
The molecular weights of compounds having a molecular weight distribution are weight average molecular weights (Mw) unless otherwise specified.
The content of metal elements is a value measured using an inductively coupled plasma (ICP) spectrometer unless otherwise specified.
"(Meth)acryl" is a concept that includes both acryl and methacryl, and "(meth)acryloxy group" is a concept that includes both acryloxy and methacryloxy.
The “alkali-soluble resin” means a resin having a solubility of 0.1 g or more in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C.
The term “water-soluble” means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more. In other words, the "water-soluble resin" means a resin that satisfies the above solubility.

The "solid content" of a composition (e.g., photosensitive composition, etc.) means a component that forms a composition layer (e.g., photosensitive composition layer, etc.) formed using the composition. When contains a solvent (eg, organic solvent, water, etc.), it means all components except the solvent. In addition, as long as it is a component that forms a composition layer (for example, a photosensitive composition layer, etc.), a liquid component is also regarded as a solid content.

[Transfer film]
<<First Embodiment>>
A first embodiment of the transfer film comprises:
A transfer film having a temporary support and a photosensitive composition layer,
The photosensitive composition layer contains a resin A, a polymerizable compound, and a polymerization initiator,
Resin A includes a structural unit a having a group that forms an alkali-soluble group by the action of an alkali (hereinafter also referred to as a "specific group") and a structural unit b having an acid group.

Although the details of the action mechanism by which the transfer film of the present invention exerts the desired effects are not clear, the present inventors presume as follows.
By including the structural unit b in the resin A contained in the photosensitive composition layer, a resist pattern can be formed by generating a dissolution contrast in the exposed area and the unexposed area. On the other hand, for example, when an alkaline stripping solution is used to strip the resist pattern after the etching step or after the plating process, the alkaline stripping solution causes the specific group of the structural unit a to generate an alkali-soluble group. do. As a result, it is presumed that the solubility of the resist pattern in the alkaline stripping solution is improved, and the stripping property is excellent. When an alkaline developer and an alkaline stripping solution are used in the development process and the resist pattern stripping step, the specific group does not generate an alkali-soluble group with the alkaline developer, and the specific group becomes alkali-soluble with the alkaline stripping solution. It is preferred to generate groups.
Hereinafter, more excellent peelability is also referred to as "more excellent effect of the present invention".

The transfer film may have other layers in addition to the temporary support and the photosensitive composition layer.
Other layers include, for example, an intermediate layer to be described later. Moreover, the transfer film may have other members (for example, a protective film, etc.) which will be described later.

Embodiments of the transfer film include, for example, the following configuration (1) or (2), with configuration (2) being preferred.
(1) "Temporary support/photosensitive composition layer/protective film"
(2) "Temporary support/intermediate layer/photosensitive composition layer/protective film"
Preferably, the transfer film has an intermediate layer.
As the photosensitive composition layer in each of the above configurations, a negative photosensitive composition layer described later or a colored resin layer described later is preferable.

From the viewpoint of suppressing the generation of air bubbles in the later-described bonding step, the maximum width of the undulation of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. The lower limit is preferably 0 µm or more, more preferably 0.1 µm or more, and even more preferably 1 µm or more.
The maximum width of waviness of the transfer film is a value measured by the following procedure.
A test sample is prepared by cutting the transfer film in a direction perpendicular to the main surface so as to have a size of 20 cm long by 20 cm wide. In addition, when a transfer film has a protective film, a protective film is peeled from a transfer film. Next, the test sample is placed on a flat and horizontal stage so that the surface of the temporary support faces the stage. After standing still, the surface of the sample sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Corporation) for the center 10 cm square range of the test sample to acquire a three-dimensional surface image, and the obtained three-dimensional surface image. Subtract the minimum concave height from the maximum convex height observed in . The above operation is performed for 10 test samples, and the arithmetic average value is taken as the maximum waviness width of the transfer film.

In the photosensitive composition layer of the transfer film, on the surface opposite to the temporary support of the photosensitive composition layer, there is another composition layer (for example, a photosensitive composition layer and an intermediate layer). The total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the total thickness of the photosensitive composition layers.

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

Example embodiments of transfer films are described.
The transfer film 10 shown in FIG. 1 has a temporary 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, the intermediate layer 13 and the protective film 19 may be omitted.
In FIG. 1, each layer (for example, a photosensitive composition layer, an intermediate layer, etc.) other than the protective film 19 that can be placed on the temporary support 11 is also referred to as a "composition layer".

Each member and each component of the transfer film will be described in detail below.
In addition, although description of the constituent elements described below may be made based on a representative embodiment of the present invention, the present invention is not limited to such an embodiment.
The first embodiment of the transfer film will be described in detail below.

[Temporary support]
The transfer film has a temporary support.
A temporary support is a member that supports the photosensitive composition layer, and is finally removed by a peeling treatment.

The temporary support may have either a single layer structure or a multilayer structure.
The temporary support is preferably a film, more preferably a resin film. In addition, as the temporary support, a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat is also preferable, and a film that is free from deformation such as wrinkles and scratches is also preferable. preferable.
Examples of the film include polyethylene terephthalate film (eg, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film, with polyethylene terephthalate film being preferred.

The temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support. Specifically, the transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. The upper limit is preferably less than 100%.
From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the haze of the temporary support is preferably as small as possible. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more.

From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matter and defects in the temporary support is preferably as small as possible. Specifically, the number of fine particles (for example, fine particles with a diameter of 1 μm), foreign matter and defects in the temporary support is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, and 3/10 mm. ² or less is more preferable, and less than 1/10 mm ² is particularly preferable. The lower limit is preferably 0 pieces/10 mm ² or more.

The thickness of the temporary support is preferably 5 μm or more, more preferably 6 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably less than 16 μm from the viewpoint of ease of handling and versatility.
The thickness of the temporary support is calculated as an average value of arbitrary five points measured by cross-sectional observation with a SEM (Scanning Electron Microscope).

The temporary support may have a layer containing fine particles (lubricant layer) on one side or both sides of the temporary support from the viewpoint of handling.
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 adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support in contact with the photosensitive composition layer may be subjected to a surface modification treatment.
Examples of surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like.
The exposure amount in UV irradiation is preferably 10-2000 mJ/cm ² , more preferably 50-1000 mJ/cm ² .
As long as the exposure amount is within the above range, the lamp output and illuminance are not particularly limited.
Light sources for UV irradiation include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength band of 150 to 450 nm. (LED).

Examples of the temporary support include a 16 μm thick biaxially stretched polyethylene terephthalate film, a 12 μm thick biaxially stretched polyethylene terephthalate film, and a 9 μm thick biaxially stretched polyethylene terephthalate film.
Further, as the temporary support, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-027363, International Publication No. 2012/081680 and paragraphs [0029] to [0040] of WO2018/179370, the contents of which are incorporated herein.
Examples of commercially available temporary supports include Lumirror 16KS40 (registered trademark) and Lumirror 16FB40 (registered trademark) (manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4300 and Cosmoshine A8300 (manufactured by Toyobo Co., Ltd.).

[Photosensitive composition layer]
The transfer film has a photosensitive composition layer.
As the photosensitive composition layer, a negative photosensitive composition layer is preferred. When the photosensitive composition layer is a negative photosensitive composition layer, the formed resist pattern corresponds to a cured film.
The photosensitive composition layer contains 10.0 to 90.0% by weight of the resin A, 5.0 to 70.0% by weight of the polymerizable compound, and a polymerization initiator with respect to the total weight of the photosensitive composition layer. It preferably contains 0.01 to 20.0% by mass.

The thickness (film thickness) of the photosensitive composition layer is often 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, further preferably 0.5 to 30 μm. ~20 μm is particularly preferred. Thereby, the developability of the photosensitive composition layer can be improved, and the resolution can be improved.

The photosensitive composition layer contains resin A, a polymerizable compound, and a polymerization initiator.
Each component that the photosensitive composition layer may contain will be described below.

<Resin A>
Resin A contains a structural unit a having a specific group and a structural unit b having an acid group.
As the resin A, an alkali-soluble resin containing the structural unit a and the structural unit b is preferable.

(Constituent unit a)
Structural unit a is a structural unit having a specific group (a group that forms an alkali-soluble group by the action of alkali).
The term "group which forms an alkali-soluble group by the action of alkali" means a group which is decomposed by the action of alkali to form an alkali-soluble group.
However, groups derived from alkyl (meth)acrylates (eg, --COO-alkyl groups, etc.) are not included in the specific groups. Therefore, structural units derived from alkyl (meth)acrylates are not included in structural unit a. The above alkyl group may be linear, branched or cyclic.
Examples of monomers constituting structural units derived from alkyl (meth)acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (Meth)acrylates such as butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate mentioned.
In addition, it is permissible for the resin A to contain a group derived from an alkyl (meth)acrylate and/or a structural unit derived from an alkyl (meth)acrylate.

Examples of the alkali-soluble group in which a specific group is generated by the action of alkali include acid groups such as phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups and sulfonic acid groups, as well as sulfonamide groups and sulfonylimide groups. Acid groups are preferred, and carboxy groups are more preferred.

Structural unit a preferably contains a structural unit having an alkali-decomposable group, and more preferably contains a structural unit having a group capable of being decomposed by alkali to generate an acid group, in terms of reactivity and storage stability. From, a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group. and a structural unit having an acid anhydride group, and most preferably a structural unit having a lactone group.

The “alkali-decomposable group” means a group that is decomposed by the action of alkali to produce an alkali-soluble group. For example, it can be determined whether or not it corresponds to an alkali-decomposable group by the following method.
A verification compound having a group to be measured is provided. Examples of verification compounds include γ-butyrolactone methacrylate as a verification compound having a lactone group, and phenylsuccinic anhydride as a verification compound having an acid anhydride group.
Next, the verification compound is dissolved in a solvent (eg, acetonitrile, etc.), and a certain amount of an alkaline aqueous solution is added at room temperature to carry out a hydrolysis reaction. Acid is then added to the resulting solution to acidify the solution. This solution can be judged by measuring the remaining amount of the verification compound using HPLC (High Performance Liquid Chromatography).
Specifically, if the residual amount of the verification compound measured by the above method is 80% by mass or less with respect to the total mass of the verification compound before hydrolysis, the verification compound has an alkali-decomposable group. Suppose that it corresponds to a compound. The residual amount of the verification compound is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is often 0% by mass or more.
Further, whether or not an alkaline-possible group is generated can be confirmed by isolating the compound produced by alkaline decomposition and using NMR (Nuclear Magnetic Resonance) or the like.

-Structural Unit Having a Lactone Group-
The lactone group may be a group having a lactone structure, and may be either a lactone group itself or a group having a lactone group.
The lactone group is preferably a group having a 5- to 7-membered lactone structure, more preferably a group in which the 5- to 7-membered lactone structure is condensed with another ring structure such as a bicyclo structure or a spiro structure.
In addition, in the structural unit having a lactone group, the lactone group may be directly bonded to the main chain of the resin A, or may form a part of the main chain of the resin A.

The lactone group is preferably a group formed by removing one or more hydrogen atoms from a lactone compound.
As the lactone compound, compounds represented by any one of formulas (LC1-1) to (LC1-17) are preferable, and formulas (LC1-1), formula (LC1-4), formula (LC1-5), formula (LC1-6), formula (LC1-13), formula (LC1-14) and compounds represented by any of formula (LC1-17) are more preferable, formula (LC1-1), formula (LC1-4 ) and compounds represented by formulas (LC1-17) are more preferred.
In the case of the above compound, the pattern shape is improved and the resist pattern peelability is improved.

In addition, lactone compounds usually have optical isomers.
Any optical isomer may be used as the lactone compound. You may use the optical isomer of a lactone compound individually by 1 type or in 2 or more types. In other words, mixtures of optical isomers may be used. When using one kind of optical isomer, the optical purity (ee) of the lactone compound is preferably 90 or more, more preferably 95 or more.

In formulas (LC1-1) to (LC1-17), _Rb2 represents a substituent. _n2 represents an integer of 0 or more.
Examples of the substituent represented by Rb ₂ include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 1 to 8 carbon atoms. , a carboxyl group, a halogen atom, a hydroxyl group and a cyano group.
When _n2 is 2 or more, multiple _Rb2 may be the same or different, and multiple _Rb2 may combine to form a ring.

As a structural unit having a lactone group, a structural unit represented by formula (AI) is preferable.

In formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. Ab represents an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a divalent group combining these, or a single bond. V represents a group formed by removing one hydrogen atom from the compound represented by any one of formulas (LC1-1) to (LC1-17).

Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms.
Examples of substituents that the optionally substituted alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
Rb ₀ is preferably a hydrogen atom or a methyl group.

Ab represents an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a divalent group combining these, or a single bond.
Ab is preferably a single bond or -Ab ₁ -CO ₂ -. Ab ₁ represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group. Ab ₁ is preferably a methylene group, ethylene group, cyclohexyl group, adamantyl group or norbornyl group.

V represents a group formed by removing one hydrogen atom from the compound represented by any one of formulas (LC1-1) to (LC1-17).
The compounds represented by any one of formulas (LC1-1) to (LC1-17) are as described above.

Specific examples of structural units having a lactone group are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, a methyl group, --CH ₂ OH or --CF ₃ .

A structural unit having a lactone group may be used alone or in combination of two or more.
The content of structural units having a lactone group is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 7 to 30% by mass, based on all structural units of Resin A.

- Structural Unit Having an Acid Anhydride Group -
The acid anhydride group may be a group having an acid anhydride structure, and may be either an acid anhydride group itself or a group having an acid anhydride group.
The acid anhydride group is preferably a carboxylic anhydride group (-C(=O)-OC(=O)-), and a cyclic carboxylic anhydride group (-C(=O)-OC A ring group containing (=O)- is more preferred.
The carboxylic anhydride group may be linear, branched or cyclic, preferably cyclic.
The number of ring members of the ring constituting the cyclic carboxylic anhydride group is preferably 5 to 7, more preferably 5 or 6, and still more preferably 5.

As the acid anhydride group, a group having a structure derived from an acid anhydride is preferable.
Acid anhydrides include, for example, maleic anhydride, itaconic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, phthalic anhydride and benzoic anhydride, and maleic anhydride or itaconic anhydride preferable.
As the acid anhydride, a compound represented by formula (P-1) is preferable.

In formula (P-1), R ^A1a represents a substituent. Z ^1a represents a (n ^1a +2) valent group forming a ring containing -C(=O)-OC(=O)-. ^n1a represents an integer of 0 or more.

Examples of the substituent represented by ^RA1a include an alkyl group.
When Z ^1a represents a divalent group, Z ^1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms.

^n1a represents an integer of 0 or more.
n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.
When ^n1a represents an integer of 2 or more, multiple R ^A1a may be the same or different. In addition, multiple ^RA1a groups may combine with each other to form a ring, but preferably do not combine with each other to form a ring.

As a structural unit having an acid anhydride group, a structural unit represented by formula (AII) or a structural unit represented by formula (AIII) is also preferable.

In Formula (AII) and Formula (AIII), each RIII independently represents a hydrogen atom or a substituent. RIII is preferably a hydrogen atom.
ahd ₁ represents a group formed by removing one hydrogen atom from each adjacent ring member atom from the compound represented by formula (P-1).
ahd ₂ represents a group formed by removing two hydrogen atoms from one of the ring member atoms of the compound represented by formula (P-1).

The structural unit having an acid anhydride group is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from a compound represented by formula (P-1), and represented by formula (AII). The structural unit represented by or the structural unit represented by (AIII) is more preferable.

Specific examples of structural units having an acid anhydride group are given below, but the structural units having an acid anhydride group are not limited to these specific examples. Rx represents a hydrogen atom, a methyl group, —CH ₂ OH or —CF ₃ .

Structural unit a may be used alone or in combination of two or more.
The content of the structural unit a is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 5 to 40% by mass, and 5 to 30% by mass with respect to all the structural units of the resin A. More preferably, 5 to 20% by mass is even more preferable.

(Constituent unit b)
Structural unit b is a structural unit having an acid group.
Examples of the acid group possessed by the structural unit b include a carboxy group, a sulfo group, a phosphoric acid group and a phosphonic acid group, with the carboxy group being preferred.

As the structural unit b, a structural unit derived from the first monomer is preferable, and a structural unit derived from (meth)acrylic acid is more preferable.
A 1st monomer is a monomer which has a carboxy group. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid and 4-vinylbenzoic acid, with (meth)acrylic acid being preferred.

As the structural unit b, a structural unit represented by formula (B) is preferable.

In formula (B), Rb represents a hydrogen atom, a methyl group, --CH ₂ OH or --CF ₃ .

Structural unit b may be used alone or in combination of two or more.
The content of the structural unit b is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 30% by mass, and 14 to 25% by mass with respect to all the structural units of the resin A. Especially preferred.

In resin A, the content of structural unit a is 5 to 50% by mass based on all structural units of resin A, and the content of structural unit b is 10 to 30% by mass based on all structural units of resin A. Preferably, the content of the structural unit a is 7 to 30% by mass based on the total structural units of the resin A, and the content of the structural unit b is 14 to 25% by mass based on the total structural units of the resin A. % is more preferred.

(Other structural units)
The resin A may contain other structural units in addition to the structural unit a and the structural unit b.

Resin A preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group in order to suppress line width thickening and deterioration of resolution when the focus position shifts during exposure.
Examples of the aromatic hydrocarbon group include an optionally substituted phenyl group and an optionally substituted aralkyl group.
The content of structural units derived from a monomer having an aromatic hydrocarbon group is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more, based on all the structural units of Resin A. More preferred. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to all structural units of Resin A. When the photosensitive composition layer contains two or more resins A, the weight average content of structural units derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.), preferably an aralkyl group-containing monomer or styrene, more preferably styrene.
When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units derived from styrene is preferably 10 to 80% by mass, preferably 20 to 60% by mass, based on the total structural units of Resin A. is more preferred, and 25 to 55% by mass is even more preferred. When the photosensitive composition layer contains two or more resins A, the mass average content of structural units having an aromatic hydrocarbon group is preferably within the above range.

The aralkyl group includes, for example, a phenylalkyl group which may have a substituent, and a benzyl group which may have a substituent is preferred.

Examples of the monomer having an optionally substituted phenylalkyl group include phenylethyl (meth)acrylate.

Examples of monomers having a benzyl group which may have a substituent include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinylbenzyl chloride and vinylbenzyl Examples thereof include vinyl monomers having a benzyl group such as alcohol, preferably (meth)acrylates having a benzyl group, more preferably benzyl (meth)acrylates.
When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of structural units derived from benzyl (meth)acrylate is 10 to 80% by mass with respect to the total structural units of Resin A. is preferred, 20 to 60 mass % is more preferred, and 25 to 55 mass % is even more preferred.

Other structural units include structural units derived from the second monomer.
The second monomer is a monomer that is non-acidic (has no acid group) and has a polymerizable group in its molecule.
The polymerizable group has the same meaning as the polymerizable group possessed by the polymerizable compound described below, and the preferred embodiments are also the same.
Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; vinyl acetate esters of vinyl alcohol such as; (meth)acrylonitrile;
Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate and ethyl (meth)acrylate are more preferred.
The content of structural units derived from the second monomer is preferably 1 to 80% by mass, more preferably 1 to 60% by mass, more preferably 1 to 50% by mass, based on the total structural units of Resin A. preferable.

The resin may have any one of a linear structure, a branched structure and an alicyclic structure in the side chain.
By using a monomer having a group having a branched structure in its side chain or a monomer having a group having an alicyclic structure in its side chain, a branched structure or alicyclic structure can be introduced into the side chain of the resin. can. A group having an alicyclic structure may be either monocyclic or polycyclic.
"Side chain" means an atomic group branched off from the main chain. The “main chain” means the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin.
Examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, Isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert- (meth)acrylate octyl.
Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl methacrylate are preferred, and isopropyl methacrylate and tert-butyl methacrylate are more preferred.
Examples of the monomer having a group having an alicyclic structure in its side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also included.
Specifically, (meth) acrylic acid (bicyclo[2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic acid- 3-methyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-1-adamantyl, (meth)acrylate-3-ethyladamantyl, (meth)acrylate-3-methyl-5-ethyl-1 -adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylate 2-methyl- 2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-menthanoinden-5-yl (meth) acrylate, ( Octahydro-4,7-menthanoinden-1-ylmethyl meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6 (meth)acrylate ,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acrylic acid (nor ) bornyl, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate.
Among them, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (meth)acrylate Fentyl acrylate, 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate is preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth) ) 2-adamantyl acrylate or tricyclodecane (meth)acrylate is more preferred.

Other structural units include structural units having a polymerizable group.
Examples of the polymerizable group include a polymerizable group possessed by a polymerizable compound to be described later, preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
Further, the polymerizable group is preferably a polymerizable group capable of undergoing a polymerization reaction with the polymerizable group of the polymerizable compound.

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

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

Examples of the third monomer include glycidyl (meth)acrylate.

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

In 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.
R 2 ^P is preferably a hydrogen atom.

^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 divalent group. ^RN represents a substituent.
Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group and an arylene group.
The alkylene group may be linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms. The alkylene group may have a heteroatom, and the methylene group in the alkylene group may be replaced with a heteroatom. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
The cycloalkylene group may be either monocyclic or polycyclic. The cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to 8 carbon atoms.
The arylene group may be monocyclic or polycyclic. The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. A phenylene group is preferable as the arylene group.
The cycloalkylene group and the arylene group may have a heteroatom as a ring member atom. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom.
The hydrocarbon group may further have a substituent.
Examples of the substituent include halogen atoms (eg, fluorine atoms), hydroxy groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups and alkenyl groups, with hydroxy groups being preferred.
As L ^P , an alkylene group optionally having a heteroatom is preferable.

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

Examples of structural units having a polymerizable group include the following structural units.
In the formula, Rx and Ry each independently represent a hydrogen atom or a methyl group.

The content of the structural unit having a polymerizable group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, and 20 to 40% by weight is particularly preferred.

As a method for introducing a polymerizable group into the resin A, for example, epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds and carboxylic acid anhydrides.
As a preferred embodiment of the method for introducing a polymerizable group into the resin A, after synthesizing a polymer having a carboxy group by a polymer reaction, a part of the carboxy group of the obtained polymer is added with an epoxy group such as glycidyl (meth)acrylate. (Meth)acryloxy groups are introduced into the polymer by reacting (meth)acrylates having As another method, after synthesizing a polymer having a hydroxyl group by a polymer reaction, some of the hydroxyl groups of the obtained polymer are reacted with a (meth)acrylate having an isocyanate group to form a (meth)acryloxy group on the polymer. There is a method of introduction.
Resin A having a (meth)acryloxy group in the side chain can be obtained by these means.

The reaction temperature for the polymer reaction is preferably 80 to 110.degree. The polymer reaction preferably uses a catalyst, more preferably an ammonium salt (tetraethylammonium bromide).
The reaction temperature of the polymerization reaction is preferably 70 to 100°C, more preferably 80 to 90°C. The polymerization reaction preferably uses a polymerization initiator, and more preferably uses an azo initiator as the polymerization initiator. Fuji Film Wako Pure Chemical Industries, Ltd.) is more preferable.

As the resin A, the following aspects are preferable.
(Aspect 1): It includes a structural unit a, a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from styrene or a structural unit derived from benzyl methacrylate.
(Aspect 2): It contains a structural unit a, a structural unit derived from methacrylic acid, a structural unit having a polymerizable group, and a structural unit derived from styrene or a structural unit derived from benzyl methacrylate.
In each of the above aspects, it is also preferable to set the content of each structural unit to the respective preferred aspects described above. In addition, preferred aspects of the structural unit a are as described above.

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

The glass transition temperature Tg of Resin A is preferably 30 to 135°C. By using the resin A having a Tg of 135° C. or less, it is possible to suppress thickening of the line width and deterioration of the resolution when the focus position is shifted during exposure. From this point of view, the Tg of Resin A is more preferably 130° C. or lower, still more preferably 120° C. or lower, and particularly preferably 110° C. or lower. Further, it is preferable to use the resin A having a Tg of 30° C. or more from the viewpoint of improving the edge fuse resistance. From this point, the Tg of Resin A is more preferably 40° C. or higher, more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher.

The acid value of Resin A is preferably 250 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 190 mgKOH/g or less, and particularly preferably 180 mgKOH/g or less. The lower limit is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 60 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, most preferably 90 mgKOH/g or more.
"Acid number (mg KOH/g)" means the mass (mg) of potassium hydroxide required to neutralize 1 g of sample. The acid value can be determined according to JIS K0070:1992, for example.
The acid value of Resin A can be adjusted by the type of structural unit contained in the resin and/or the content of the structural unit containing an acid group.

Further, the acid value derived from the carboxy group of Resin A is preferably 60 to 250 mgKOH/g, more preferably 80 to 200 mgKOH/g, even more preferably 90 to 180 mgKOH/g. In addition, the acid value derived from the carboxyl group does not include the carboxyl group generated by the action of alkali.
The acid value of the resin A derived from the alkali-soluble group of the specific group generated by the action of alkali is preferably 5 to 200 mgKOH/g, more preferably 20 to 100 mgKOH/g, and even more preferably 20 to 80 mgKOH/g.
A theoretical acid value calculated from the structure of the resin can be used as the acid value derived from the alkali-soluble group that the specific group is generated by the action of the alkali of the resin A. Specifically, when the resin A has lactone groups, the theoretical acid value can be calculated based on the structure of the resin in which all the lactone groups are ring-opened to generate alkali-soluble groups.

The weight average molecular weight of Resin A is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, even more preferably 10,000 to 60,000, and particularly preferably 10,000 to 50,000. .
When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. again. When the weight-average molecular weight is 5,000 or more, properties of development aggregates and properties of unexposed films such as edge-fuse properties and cut-chip properties of transfer films can be controlled. The “edge-fusibility” means the extent to which the photosensitive composition layer easily protrudes from the end face of the roll when the transfer film is wound into a roll. The term "cut chip resistance" means the degree of easiness of chip flying when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the transfer film or the like, it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products.
The dispersity of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

Resin A may be used alone or in combination of two or more.
The content of resin A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and 40 to 60% by mass, based on the total mass of the photosensitive composition layer. is particularly preferred. When the content of the resin A is 90% by mass or less with respect to the total mass of the photosensitive composition layer, the development time can be controlled. Moreover, when the content of the resin A is 10% by mass or more with respect to the total mass of the photosensitive composition layer, the edge fuse resistance can be improved.

As a method for synthesizing the resin A, for example, one or more of the monomers described above are combined with a peroxide polymerization initiator (e.g., benzoyl peroxide) and an azo polymerization initiator (e.g., azobisisobutyro Nitrile, etc.) is used for polymerization using a radical polymerization initiator. As a polymerization method, a monomer solution and a radical polymerization initiator solution are added dropwise to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or isopropanol) under a nitrogen stream. , is preferably carried out by heating and stirring. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a method for synthesizing resin A, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

<Polymerizable compound>
The photosensitive composition layer contains a polymerizable compound.
"Polymerizable compound" means a compound that has a polymerizable group and polymerizes under the action of a polymerization initiator described later, and is different from the resin A described above.

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

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

The polymerizable compound may have an alkyleneoxy group.
The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 30, more preferably 2 to 20, per molecule.

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

The content of the bifunctional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably 40.0% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. 0% by mass or more is more preferable. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive composition layer may be bifunctional ethylenically unsaturated compounds.
The content of the trifunctional ethylenically unsaturated compound is preferably 10.0% by mass or more, more preferably 15.0% by mass or more, relative to the total mass of the polymerizable compound. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 50.0% by mass or less. That is, all polymerizable compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds.
Moreover, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferable.

(Polymerizable compound B1)
The polymerizable compound also preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups.
Examples of the polymerizable compound B1 include bifunctional ethylenically unsaturated compounds having one or more aromatic rings among the above polymerizable compounds.

Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring Heterocycles; condensed rings obtained by combining them are mentioned, and aromatic hydrocarbon rings are preferred, and benzene rings are more preferred. The aromatic ring may further have a substituent.

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

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

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

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

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

The content of the polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, with respect to the total mass of the photosensitive composition layer from the viewpoint of better resolution. 0% by mass or more is more preferable. The upper limit is preferably 70.0% by mass or less with respect to the total mass of the photosensitive composition layer, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive composition oozes out from the edge of the transfer member), and 60 0% by mass or less is more preferable.

The content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, more preferably 55.0% by mass, based on the total mass of the polymerizable compound, from the viewpoint of better resolution. % by mass or more is more preferable, and 60.0% by mass or more is particularly preferable. The upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, still more preferably 95.0% by mass or less, and 90.0% by mass or less, based on the total mass of the polymerizable compound, from the viewpoint of releasability. 0% by mass or less is particularly preferable, and 85.0% by mass or less is most preferable.

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

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

Bifunctional ethylenically unsaturated compounds having no aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate.
Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate and neopentyl glycol di(meth)acrylate.
Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di(meth)acrylate.
Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products of urethane di(meth)acrylate include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). be done.

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

Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include, for example, caprolactone-modified (meth)acrylate compounds (e.g., Nippon Kayaku Co., Ltd. KAYARAD (registered trademark) DPCA-20 and Shin-Nakamura Chemical Co., Ltd. A -9300-1CL etc.), alkylene oxide-modified (meth) acrylate compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL manufactured by Daicel Allnex Co., Ltd. (registered trademark) 135, etc.), ethoxylated glycerin triacrylate (e.g., Shin-Nakamura Chemical Co., Ltd. A-GLY-9E, etc.), Aronix (registered trademark) series (e.g., Toagosei Co., Ltd. TO-2349, M-520 and M-510, etc.).

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

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

You may use a polymerizable compound individually by 1 type or in 2 or more types.
The content of the polymerizable compound is preferably 10.0 to 70.0% by mass, more preferably 15.0 to 70.0% by mass, and 20.0 to 70% by mass, based on the total mass of the photosensitive composition layer. 0 mass % is more preferred.

<Polymerization initiator>
The photosensitive composition layer contains a polymerization initiator.
As the polymerization initiator, for example, a known polymerization initiator can be used depending on the type of polymerization reaction. Specific examples include thermal polymerization initiators and photopolymerization initiators.
The polymerization initiator may be either a radical polymerization initiator or a cationic polymerization initiator.

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

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

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

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

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

A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving an actinic ray. The photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more (preferably a wavelength of 300 to 450 nm) to generate an acid. In addition, for photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or more, if they are compounds that react to actinic rays with a wavelength of 300 nm or more and generate an acid by using them in combination with a sensitizer, the sensitizer can be used. It can be preferably used in combination with
The photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less. Photocationic polymerization initiators that generate are more preferred. The lower limit is preferably -10.0 or more.

Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
Examples of the ionic photocationic polymerization initiator include ionic photocationic polymerization initiators described in paragraphs [0114] to [0133] of JP-A-2014-085643.

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

A polymerization initiator may be used individually by 1 type, and may be used in 2 or more types.
The content of the polymerization initiator 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. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the photosensitive composition layer.

<Pigment>
The photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development from the viewpoint of visibility of exposed and unexposed areas, and pattern visibility and resolution after development. In addition, it may contain a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter also referred to as “dye N”).
It is preferable that the maximum absorption wavelength of the dye be changed by an acid or a radical. Also, the dye is a compound different from the compound D described above.
When the dye N is contained, although the detailed mechanism is unknown, the adhesion to the adjacent layer (for example, the intermediate layer) is improved and the resolution is improved.

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

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

As the coloring mechanism of the dye N, for example, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive composition layer, and the photoradical polymerization initiator is added after exposure. , Radical-reactive dyes, acid-reactive dyes or base-reactive dyes (e.g., leuco dyes, etc.) develop colors by radicals, acids, or bases generated from a photocationic polymerization initiator or a photobase generator.

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

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

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

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

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

Dyes N include, for example, dyes and leuco compounds.
Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, and paramethyl red. , Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd. ), oil blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industry Co., Ltd.), oil scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxanilino-4-p-diethyaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p -N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino- 5-pyrazolones.

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

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

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

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

<Thermal crosslinkable compound>
The photosensitive composition layer may contain a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
A thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds, and blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when the resin and/or the polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film is lowered and the photosensitive composition The function tends to be enhanced when a film obtained by curing a material layer is used as a cured film.
A "blocked isocyanate compound" means a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent.

The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160°C, more preferably 130 to 150°C.
As a method for measuring the dissociation temperature of the blocked isocyanate compound, for example, DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter (e.g., DSC6200, Seiko Instruments Inc., etc.) is performed to determine the deprotection reaction of the blocked isocyanate compound. A method of measuring the temperature of the accompanying endothermic peak as the degree of dissociation can be mentioned.

Examples of blocking agents having a dissociation temperature of 100 to 160° C. include active methylene compounds such as malonic acid diesters and oxime compounds.
Malonic acid diesters include, for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate and di-2-ethylhexyl malonate.
Examples of oxime compounds include compounds having a structure represented by -C(=N-OH)- in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime and cyclohexanone oxime.
Among them, oxime compounds are preferable as blocking agents having a dissociation temperature of 100 to 160° C. from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesion to the transferred material.
A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
Among them, as a blocked isocyanate compound having an isocyanurate structure, an oxime compound is used as a blocking agent because it is easier to adjust the dissociation temperature to a preferable range than a compound having no oxime structure and can reduce development residue. Compounds having an oxime structure are preferred.

The blocked isocyanate compound may have a polymerizable group.
The polymerizable group has, for example, the same definition as the polymerizable group possessed by the polymerizable compound, and the preferred embodiments are also the same.

Examples of blocked isocyanate compounds include Karenz series (registered trademark) such as AOI-BM, MOI-BM and MOI-BP (manufactured by Showa Denko KK); ) (manufactured by Asahi Kasei Chemicals).
As the blocked isocyanate compound, the following compounds are preferred.

You may use a thermal crosslinkable compound individually by 1 type or in 2 or more types.
The content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

<Pigment>
The photosensitive composition layer may contain a pigment.
When the photosensitive composition layer contains a pigment, the photosensitive composition layer corresponds to the colored resin layer.
In order to protect the liquid crystal display window of electronic equipment in recent years, there are cases where a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is attached to the liquid crystal display window. be. A colored resin layer may be used to form such a light shielding layer.
The pigment may be appropriately selected according to the desired hue. Examples thereof include black pigments, white pigments, and chromatic pigments other than black and white. As such, a black pigment is preferable.

(black pigment)
Examples of black pigments include known black pigments (eg, organic pigments, inorganic pigments, etc.).
Among them, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide or graphite are preferable as the black pigment, and carbon black is more preferable, from the viewpoint of optical density. From the viewpoint of surface resistance, the carbon black is preferably surface-modified carbon black having at least a portion of the surface coated with a resin.

The particle size (number average particle size) of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability.
The term "particle size" means the diameter of a circle obtained by determining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. Further, the "number average particle size" means an average value obtained by determining the particle size of 100 arbitrary particles and averaging the obtained 100 particle sizes.

Examples of white pigments include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of JP-A-2005-007765.
The inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate, more preferably titanium oxide or zinc oxide, still more preferably titanium oxide, 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 subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, organic substance treatment, or two or more of these treatments. Thereby, the catalytic activity of titanium oxide is suppressed, and the heat resistance and fade resistance can be improved.
From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and both alumina treatment and zirconia treatment are performed. is more preferable.

When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
The particle size (number average particle size) of the chromatic 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 10 nm or more.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter also referred to as “CI”) 42595), Auramine (CI 41000), Fat Black HB (CI .26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Splash (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64 and C.I. I. Pigment Violet 23, C.I. I. Pigment Red 177 is preferred.

The pigments may be used singly or in combination of two or more.
The content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, and more than 5% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer. More preferably, 10 to 35% by mass is particularly preferable.

When the photosensitive composition layer contains pigments other than black pigments (e.g., white pigments, chromatic pigments, etc.), the content of pigments other than black pigments is 30% by mass or less with respect to the total mass of black pigments. is preferred, 1 to 20 mass % is more preferred, and 3 to 15 mass % is even more preferred.

When the photosensitive composition layer contains a black pigment, the black pigment (preferably carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.
The dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. A pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used.
By "vehicle" is meant that portion of the medium in which the pigment is dispersed when made into a pigment dispersion. The vehicle is liquid and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

Examples of dispersers include known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers and sand mills.
Moreover, it may be finely pulverized using frictional force by mechanical grinding. Dispersers and fine pulverization are described, for example, in "Encyclopedia of Pigments" (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

<Other additives>
The photosensitive composition layer may contain other additives, if necessary, in addition to the above components.
Other additives include, for example, resins other than resin A, compound D described later, radical polymerization inhibitors, antioxidants (e.g., phenidone, etc.), rust inhibitors (e.g., benzotriazoles, carboxybenzotriazoles, etc.). , sensitizers, surfactants, plasticizers, heterocyclic compounds (eg triazole etc.), pyridines (eg isonicotinamide etc.) and purine bases (eg adenine etc.).
Other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, organic Or inorganic suspending agents and paragraphs [0165] to [0184] of JP-A-2014-085643, the contents of which are incorporated herein.
Other additives may be used singly or in combination of two or more.

(Radical polymerization inhibitor)
Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784, and phenothiazine, phenoxazine and 4-methoxyphenol are preferred.
The radical polymerization inhibitor includes, for example, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt and diphenylnitrosamine. Nitrosophenylhydroxyamine aluminum salt is preferred from the viewpoint of not impairing the sensitivity of the photosensitive composition layer. .
The content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, based on the total mass of the photosensitive composition layer, and 0.02 to 2.0% by mass is more preferred.
The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound. 0% by mass is more preferred.

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

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

The total content of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. preferable. When the total 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 total content is 3% by mass or less, the maintenance of sensitivity and suppression of decolorization of the dye are more excellent.

(sensitizer)
Sensitizers include, for example, known sensitizers, dyes and pigments.
Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole, etc.), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds.

The content of the sensitizer is 0.01 to 5% by mass with respect to the total mass of the photosensitive composition layer, from the viewpoint of improving the sensitivity to light sources and improving the curing speed due to the balance between polymerization speed and chain transfer. Preferably, 0.05 to 1% by mass is more preferable.

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

As the surfactant, a nonionic surfactant, a fluorosurfactant or a silicone surfactant is preferred.
Examples of fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F- 437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94 and DS-21 (above, DIC); Florard FC430, FC431 and FC171 (manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393 and KH-40 (manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA); 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683 (manufactured by NEOS).

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

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

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl Ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; Pluronic L10, L31, L61, L62, 10R5, 17R2 and 25R2 (manufactured by BASF); Tetronic 304, 701, 704, 901, 904 and 150R1 (manufactured by BASF); Solsperse 20000 (manufactured by Nippon Lubrizol); NCW-101, NCW-1001 and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Pionin D-6112, D-6112-W and D-6315 (manufactured by Takemoto Oil Co., Ltd.); Olphine E1010, Surfynol 104, 400 and 440 ( (manufactured by Nissin Chemical Industry Co., Ltd.).

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

Specific examples of silicone-based surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above , manufactured by Dow Corning Toray Co.); -643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445 , TSF-4460 and TSF-4452 (manufactured by Momentive Performance Materials); BYK307, BYK323 and BYK330 (manufactured by BYK-Chemie).

The content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.0% by mass, based on the total mass of the photosensitive composition layer. 0.8% by weight is more preferred.

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

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

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

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

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

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

(remaining monomer)
The photosensitive composition layer may contain residual monomers derived from each structural unit of the resin A.
The content of the remaining monomers is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less relative to the total mass of Resin A from the viewpoint of patterning properties and reliability. . The lower limit is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, relative to the total mass of Resin A.
From the viewpoint of patterning property and reliability, the residual monomer derived from each structural unit of resin A is preferably 3000 ppm by mass or less, and 600 ppm by mass or less with respect to the total mass of the photosensitive composition layer. More preferably, 100 ppm by mass or less is even more preferable. The lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive composition layer.

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

The photosensitive composition layer may contain water.
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, from the viewpoint of improving reliability and laminating properties.

[Intermediate layer]
The transfer film may have an intermediate layer between the temporary 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 the intermediate layer, an oxygen-blocking layer is preferable from the viewpoint that the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved. More preferred is an oxygen barrier layer dispersed or dissolved in a 1% by weight aqueous solution of sodium carbonate.
Each component that the intermediate layer may contain will be described below.

<Water-soluble resin>
The intermediate layer may contain a water-soluble resin.
Examples of water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, polyether-based resins, gelatin, and polyamide resins.
The water-soluble resin may include at least one selected from the group consisting of polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, and polyamide resins. preferable.

Cellulose-based resins include, for example, water-soluble cellulose derivatives.
Water-soluble cellulose derivatives include, for example, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose.

Examples of polyether-based resins include polyethylene glycol, polypropylene glycol, alkylene oxide side adducts thereof, and vinyl ether-based resins.
Polyamide resins include, for example, acrylamide-based resins, vinylamide-based resins, and allylamide-based resins.

Examples of water-soluble resins include copolymers of (meth)acrylic acid/vinyl compounds, preferably copolymers of (meth)acrylic acid and allyl (meth)acrylate, and methacrylic acid and allyl methacrylate. and copolymers are more preferred.
When the water-soluble resin is a copolymer of (meth)acrylic acid and a vinyl compound, each composition ratio (mol% of (meth)acrylic acid/mol% of vinyl compound) is 90/10 to 20/80. is preferred, and 80/20 to 30/70 is more preferred.

The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less.
The dispersity of the water-soluble resin is preferably 1-10, more preferably 1-5, even more preferably 1-3.

The water-soluble resin may be used singly or in combination of two or more.
The content of the water-soluble resin is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass, based on the total mass of the intermediate layer, in order to further improve the oxygen barrier property and the interlayer mixing suppression property. The above is more preferable, and 90% by mass or more is particularly preferable. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less, relative to the total mass of the intermediate layer.

<Other ingredients>
The intermediate layer may contain other components in addition to the above water-soluble resin.

As other components, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferred, and polyhydric alcohols, phenol derivatives or amide compounds are more preferred.
In addition, other components include, for example, known surfactants.

Polyhydric alcohols include, for example, glycerin, diglycerin and diethylene glycol.
The number of hydroxy groups possessed by the polyhydric alcohol is preferably 2-10.
Examples of alkylene oxide adducts of polyhydric alcohols include compounds obtained by adding ethyleneoxy groups, propyleneoxy groups, and the like to the above polyhydric alcohols.
The average number of alkyleneoxy groups to be added is preferably 1-100, preferably 2-50, more preferably 2-20.
Phenol derivatives include, for example, bisphenol A and bisphenol S.
Amide compounds include, for example, N-methylpyrrolidone.

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

The molecular weight of other components is preferably less than 5,000, more preferably 4,000 or less, still more preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.

Other components may be used singly or in combination of two or more.
The content of other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

<Impurities>
The intermediate layer may contain impurities.
Impurities include, for example, impurities contained in the photosensitive composition layer.

The thickness of the intermediate layer is preferably 0.1-5 μm, more preferably 0.5-3 μm. When the thickness of the intermediate layer is within the above range, the inter-layer mixing suppression ability is excellent without lowering the oxygen barrier properties. Furthermore, the intermediate layer removal time during development can be shortened.

[Other parts]
The transfer film may have other members in addition to the above members.
Other members include, for example, a protective film.

Protective films include, for example, resin films having heat resistance and solvent resistance. Specific examples include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. As the protective film, a resin film made of the same material as the temporary support may be used.
Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film.

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

The number of fisheyes with a diameter of 80 μm or more contained in the protective film is preferably 5/m ² or less. The lower limit is preferably 0/m ² or more.
"Fish eye" means that when a film is produced by methods such as heat melting, kneading, extrusion, biaxial stretching, casting, etc., foreign substances, undissolved substances, and oxidation-degraded substances of the material are found in the film. It means what is taken.

The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, and even more preferably 5 particles/mm ² or less. The lower limit is preferably 0/mm ² or more. When it is within the above range, it is possible to suppress defects caused by the unevenness caused by the particles contained in the protective film being transferred to the photosensitive composition layer or the conductive layer.

From the viewpoint of imparting winding properties, the surface of the protective film opposite to the surface in contact with the photosensitive composition layer or the surface in contact with the surface has an arithmetic mean roughness Ra of preferably 0.01 μm or more, more preferably 0.02 μm or more. It is preferably 0.03 μm or more, and more preferably 0.03 μm or more. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, even more preferably 0.30 μm or less.

<<Second Embodiment>>
A second embodiment of the transfer film comprises:
A transfer film having a temporary support and a photosensitive composition layer,
The photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
Resin B contains a structural unit b having an acid group,
Compound D has a group that generates an alkali-soluble group by the action of alkali,
The content of compound D is 5 to 50% by mass with respect to the total mass of the photosensitive composition layer.
The temporary support, the polymerizable compound, and the polymerization initiator have the same meanings as those described in the first embodiment of the transfer film, and the preferred embodiments are also the same. In addition to the above, the second embodiment of the transfer film further includes components that the photosensitive composition layer of the first embodiment of the transfer film may contain, an intermediate layer that the first embodiment of the transfer film may have, and other You may have a member.
A first embodiment of the transfer film is a mode in which the same resin contains the structural unit a having a specific group and the structural unit b having an acid group. On the other hand, the second embodiment of the transfer film is an embodiment in which the resin containing the structural unit b having an acid group and the different compound D have specific groups.

<Resin B>
The photosensitive composition layer contains resin B.
Resin B contains structural unit b having an acid group.
The structural unit b has the same definition as the structural unit b in the resin A, and the preferred embodiments are also the same.
The resin B may further contain other structural units in the resin A.
In addition, it is preferable that the resin B does not contain the above specific group and the above structural unit a.

<Compound D>
The photosensitive composition layer contains Compound D.
Compound D is a compound different from Resin B.
Compound D is a compound having a group (specific group) that generates an alkali-soluble group by the action of alkali. The group that generates an alkali-soluble group by the action of alkali has the same definition as the specific group described above, and the preferred embodiments are also the same.
Compound D may further have other groups in addition to the above specific groups. In addition, it is preferable that the compound D does not contain the structural unit b having an acid group.
Compound D may be either a low-molecular-weight compound or a resin.

Compound D is preferably a compound having a lactone group or an acid anhydride group, more preferably a low-molecular-weight compound having a lactone group or an acid anhydride group, or a resin having a lactone group or an acid anhydride group. Compound D is preferably a compound having two or more lactone groups or acid anhydride groups in the molecule, more preferably a resin having two or more lactone groups or acid anhydride groups in the molecule.
The lactone group and the acid anhydride group are, for example, the same as the lactone group and the acid anhydride group in the structural unit a contained in the resin A, and preferred embodiments are also the same.
When compound D is a resin, compound D may contain other structural units that resin A may contain. Other structural units are preferably structural units derived from at least one selected from the group consisting of styrene, styrene derivatives, alkyl (meth)acrylates and alicyclic alkyl methacrylates.
Compound D includes, for example, a styrene/maleic anhydride copolymer (SMA EF-40, manufactured by Cray Valley), a resin such as a copolymer of methyl methacrylate/γ-butyrolactone methacrylate, and two molecules in the molecule. Examples of low-molecular-weight compounds having a lactone group include reaction products of polycarboxylic acid and bromobutyrolactone (for example, reaction products of adipic acid and bromobutyrolactone). Further, a resin obtained by removing the structural unit b from the resin A is preferable.

When compound D is a low-molecular-weight compound, the molecular weight of compound D is preferably 80 to 2,000, more preferably 100 to 1,500, even more preferably 150 to 1,000.
When compound D is a resin, the molecular weight of compound D is preferably 5,000 to 100,000, more preferably 8000 to 80,000, even more preferably 10,000 to 50,000.

You may use the compound D individually by 1 type or in 2 or more types.
The content of compound D is 5 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and 5 to 20% by mass with respect to the total mass of the photosensitive composition layer. More preferred.

[Photosensitive composition]
The photosensitive composition preferably contains the components contained in the photosensitive composition layer and a solvent. The content of each component contained in the photosensitive composition layer is as described above.
Specific embodiments of the photosensitive composition are described in detail below.

<<First Embodiment>>
A first embodiment of the photosensitive composition comprises:
including a resin A, a polymerizable compound, and a polymerization initiator,
Resin A contains a structural unit a having a group capable of forming an alkali-soluble group by the action of an alkali and a structural unit b having an acid group.
The above resin A, the above polymerizable compound, the above polymerization initiator, the above structural unit a, and the above structural unit b are synonymous with the components that can be contained in the above photosensitive composition layer, and the preferred embodiments are also the same.

<<Second Embodiment>>
A second embodiment of the photosensitive composition comprises:
The photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
Resin B contains a structural unit b having an acid group,
Compound D has a group that generates an alkali-soluble group by the action of alkali,
The content of compound D is 5 to 50% by mass with respect to the total mass of the photosensitive composition layer.
The resin B, the polymerizable compound, the polymerization initiator, the compound D, the structural unit b, and the group that generates an alkali-soluble group by the action of an alkali are components that can be contained in the photosensitive composition layer, respectively. They are synonymous and preferred embodiments are also the same.

<<Third Embodiment>>
A third embodiment of the photosensitive composition comprises
including a resin C, a polymerizable compound, and a polymerization initiator,
Resin C contains a structural unit having a lactone group and a structural unit b having an acid group.
The above-mentioned polymerizable compound and the above-mentioned polymerization initiator are synonymous with the components that can be contained in the above-mentioned photosensitive composition layer, and the preferred embodiments are also the same.

<Resin C>
Resin C contains a structural unit having a lactone group and a structural unit b having an acid group.
The structural unit having a lactone group and the structural unit b having an acid group are the same as the structural units that can be contained in the resin A, and the preferred embodiments are also the same.
Examples of the resin C include, among the above resins A, a resin containing a structural unit having a lactone group and a structural unit b having an acid group.
Resin C may contain other structural units in addition to the above structural units. Other structural units include, for example, other structural units that the resin A may contain.

Resin C may be used alone or in combination of two or more.
The content of the structural unit having a lactone group is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 5 to 40% by mass, and 7 to 30% by mass, based on the total structural units of Resin C. % by weight is particularly preferred.
The content of the structural unit b having an acid group is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 30% by mass, and 14 to 25% by weight is particularly preferred.
In Resin C, the content of structural units having a lactone group is 5 to 50% by mass based on all structural units of Resin C, and the content of structural unit b is 10 to 30% based on all structural units of Resin C. % by mass, the content of structural units having a lactone group is 7 to 30% by mass based on all structural units of Resin C, and the content of structural unit b is based on all structural units of Resin C. more preferably 14 to 25% by mass.

<<Fourth Embodiment>>
A fourth embodiment of the photosensitive composition comprises
including a resin B, a polymerizable compound, a polymerization initiator, and a compound DA different from the resin B;
Resin B contains a structural unit b having an acid group,
compound DA has a group having a lactone group,
The content of compound DA is 5 to 50% by mass based on the total solid content of the photosensitive composition.
The resin B, the polymerizable compound, the polymerization initiator, and the structural unit b have the same meanings as the components that can be contained in the photosensitive composition layer, and the preferred embodiments are also the same.

<Compound DA>
Compound DA is a different compound from Resin B.
Compound DA has a group with a lactone group.
Examples of the group having a lactone group include groups having a lactone group that compound D may have.
Examples of the compound DA include compounds having a group having a lactone group among the compounds D described above.
Compound DA may further have other groups in addition to the group having the lactone group. Note that the compound DA preferably does not contain the structural unit b having an acid group.

Compound DA may be used singly or in combination of two or more.
The content of compound DA is 5 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and 5 to 20% by mass, based on the total solid content of the photosensitive composition. More preferred.

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

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

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

[Manufacturing method of transfer film]
The method for producing the transfer film is not particularly limited, and includes known methods.
As a method for producing the transfer film 10, for example, a process of applying an intermediate layer forming composition to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the intermediate layer 13. and a step of applying a photosensitive composition to 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 a protective film 19, the protective film 19 may be pressure-bonded onto the composition layer 17 of the transfer film 10 manufactured by the manufacturing method described above.
The method for producing the transfer film 10 includes a step of providing a protective film 19 so as to be in contact with the surface of the composition layer 17 opposite to the temporary support 11 side, whereby the temporary support 11, the intermediate layer 13, the photosensitive Preferably, the transfer film 10 is manufactured with a protective composition layer 15 and a protective film 19 .
After manufacturing the transfer film 10 by the manufacturing method described above, the transfer film 10 may be wound up to produce and store a roll-shaped transfer film. The roll-shaped transfer film 10 can be provided as it is to the laminating step with a substrate in a roll-to-roll system, which will be described later.

Moreover, the method of manufacturing the transfer film 10 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 intermediate layer (water-soluble resin layer) described above. In the water-soluble resin composition, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the water-soluble resin layer described above.
The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, water or water- and water-miscible organic solvents. A mixed solvent with is more preferable.
Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
A solvent may be used individually by 1 type, and may be used 2 or more types.
The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, even more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. mentioned.

<Photosensitive composition and method for forming photosensitive composition layer>
In terms of excellent productivity, components constituting the photosensitive composition layer (e.g., resin A, a polymerizable compound, a polymerization initiator, etc.) and a photosensitive composition containing a solvent are used to form by a coating method. It is desirable that
Specifically, the transfer film is produced by coating a photosensitive composition on the intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer. A method of forming is preferred.

The photosensitive composition is as described above.

Examples of the method of applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

Heat drying and reduced pressure drying are preferable as a method for drying the coating film of the photosensitive composition.
The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. The upper limit is preferably 130°C or lower, more preferably 120°C or lower.
Moreover, the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The upper limit is preferably 600 seconds or less, more preferably 300 seconds or less.

Furthermore, a transfer film can be produced by laminating a protective film to the photosensitive composition layer.
Examples of the method for bonding the protective film to the photosensitive composition layer include known methods.
Examples of the apparatus for laminating the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an autocut laminator.
Preferably, the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.

[Method for producing laminate having conductor pattern]
A laminate having a conductor pattern can also be produced by using the transfer film.
A method for producing a laminate having a conductor pattern is not particularly limited as long as it is a method for producing a laminate having a conductor pattern using the transfer film.
Among others, the method for producing a laminate having a conductor pattern of the present invention includes:
A bonding step of bonding the transfer film and the substrate such that the photosensitive composition layer side of the transfer film is in contact with the conductive layer of the substrate having the conductive layer on the surface;
An exposure step of exposing the photosensitive composition layer;
a resist pattern forming step of forming a resist pattern by developing the exposed photosensitive composition layer;
either an etching step of performing an etching process or a plating process of performing a plating process on the conductive layer in a region where the resist pattern is not arranged;
a resist pattern stripping step of stripping the resist pattern;
Furthermore, in the case of having a plating process, a method for manufacturing a laminate having a conductor pattern, comprising a removal step of removing the conductive layer exposed by the resist pattern stripping step and forming a conductor pattern on the substrate, ,
A method for producing a laminate having a conductor pattern, which further includes a temporary support peeling step for peeling the temporary support between the bonding step and the exposure step or between the exposure step and the developing step, is preferred.
Further, the method for producing a laminate having a conductor pattern includes the bonding step, the exposure step, the resist pattern forming step, the etching step or the plating step, the resist pattern stripping step, and the plating step. preferably have the above-described removal step in this order.
Each step of the method for manufacturing a laminate having a conductor pattern will be described below.

<Lamination process>
In the lamination step, a transfer film having a temporary support and a photosensitive composition layer is attached to the transfer film so that the photosensitive composition layer is in contact with the conductive layer of a substrate having a conductive layer on the surface. This is the step of bonding with the substrate.
When the transfer film has a protective film which will be described later, it is preferable to carry out the bonding step after peeling off the protective film.
The transfer film preferably further has an intermediate layer between the temporary support and the photosensitive composition layer.
The transfer film is as described above.

In lamination, the photosensitive composition layer side of the transfer film (the surface opposite to the temporary support side) is preferably brought into contact with the conductive layer on the substrate and pressure-bonded.
Examples of the pressure bonding method include known transfer methods and lamination methods, in which the surface of the photosensitive composition layer of the transfer film opposite to the temporary support side is superimposed on the substrate, and a method of pressing and heating with a roll or the like. is preferred.
Examples of the lamination method include a method using a known laminator such as a vacuum laminator and an autocut laminator.
The lamination temperature is preferably 70 to 130°C.

A substrate having a conductive layer on its surface (a substrate with a conductive layer) has a substrate and a conductive layer disposed on the surface of the substrate.
The substrate with a conductive layer may have any layer other than the conductive layer formed on the substrate, if necessary. That is, the substrate with a conductive layer preferably has at least a substrate and a conductive layer arranged on the surface of the substrate.
Examples of substrates include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, and substrates described in paragraph [0140] of WO2018/155193 are preferable.
As a material for the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable.
The thickness of the resin substrate is preferably 5-200 μm, more preferably 10-100 μm.

The conductive layer is at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and fine line formation. Preferably.
Also, one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When two or more conductive layers are arranged, the conductive layers are preferably made of different materials.
Preferred embodiments of the conductive layer are described, for example, in paragraph [0141] of WO2018/155193, the content of which is incorporated herein.

Preferably, the conductive layer is a metal layer.
The metal layer is a layer containing metal, and the metal is not particularly limited, and known metals can be used. Preferably, the metal layer is a conductive layer.
Main components of the metal layer (so-called main metals) include, for example, copper, chromium, lead, nickel, gold, silver, tin and zinc. In addition, "main metal" means the metal with the largest content among the metals contained in the metal layer.

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

The method for 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 sintering the coating film, a sputtering method, a vapor deposition method, and the like.

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

One or more conductive layers may be disposed on the substrate.
When two or more conductive layers are arranged, the two or more conductive layers may be the same or different, and are preferably made of different materials.

The substrate having a conductive layer may be a substrate having at least one of a transparent electrode and lead wiring. The substrate as described above can be suitably used as a touch panel substrate.
A transparent electrode can function suitably as an electrode for touch panels.
The transparent electrode is preferably composed of metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), metal meshes, and thin metal wires such as metal nanowires.
Examples of thin metal wires include thin wires of silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

A metal is preferable as the material of the routing wiring.
Examples of the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys thereof in combination, preferably copper, molybdenum, aluminum or titanium, more preferably copper. .

<Exposure process>
The exposure step is a step of exposing the photosensitive composition layer, and is preferably a step of pattern exposure.
"Pattern exposure" is a form of exposure in a pattern, and means an exposure form in which an exposed portion and an unexposed portion are present.
The positional relationship between the exposed portion (exposed area) and the unexposed portion (unexposed area) in the pattern exposure can be appropriately adjusted.
As for the exposure direction, the exposure may be performed from the side of the photosensitive composition layer or the side (substrate side) opposite to the side of the photosensitive composition layer.

Exposure methods in the exposure step include, for example, mask exposure, direct imaging exposure and projection exposure, and mask exposure is preferred.

When the temporary support peeling step described later is performed between the bonding step and the exposure step, the exposure step includes the substrate side of the laminate from which the temporary support obtained in the temporary support peeling step has been peeled off. Preferably, the exposure step is carried out by bringing the surface on the opposite side into contact with the mask and performing pattern exposure. In other words, the exposed surface (such as the surface of the photosensitive composition layer or the surface of the intermediate layer) exposed by peeling the temporary support of the laminate from which the temporary support is peeled off is brought into contact with the mask, and the photosensitized An exposure step in which pattern exposure is performed on the optical composition layer is preferred. In addition, when the transfer film has a two-layer structure of a temporary support and a photosensitive composition layer, the exposed exposed surface corresponds to the surface of the photosensitive composition layer, and the transfer film is the temporary support and the intermediate layer. In the case of a three-layer structure consisting of a layer and a photosensitive composition layer, the surface of the intermediate layer corresponds.
By adopting such an exposure process, a finer resist pattern can be obtained, and finally a finer conductor pattern can be obtained.
Such an exposure step is preferably employed particularly when a temporary support peeling step, which will be described later, is performed between the bonding step and the exposure step.

In the case of the pattern exposure step, a curing reaction of the components contained in the photosensitive composition layer may occur in the exposed regions of the photosensitive composition layer (regions corresponding to the openings of the mask). By performing a development step after exposure, the unexposed regions of the photosensitive composition layer are removed to form a pattern.

It is also preferable to have a mask peeling step for peeling off the mask used in the exposure step between the exposure step and the development treatment.
Examples of the mask stripping process include a known stripping process.

The light source for pattern exposure may be any light source capable of irradiating at least light in a wavelength range capable of curing the photosensitive composition layer (for example, a wavelength of 365 nm and a wavelength of 405 nm), preferably a wavelength of 365 nm. By "dominant wavelength" is meant the wavelength with the highest intensity.

Examples of light sources include various lasers, light-emitting diodes (LEDs), ultrahigh-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps.
The exposure dose is preferably 5-200 mJ/cm ² , more preferably 10-200 mJ/cm ² .
Light sources, exposure doses and exposure methods include, for example, paragraphs [0146] to [0147] of WO2018/155193, the contents of which are incorporated herein.

<Temporary support peeling step>
A temporary support peeling step is performed between the bonding step and the exposure step, or between the exposure step and the developing step.
Especially, it is preferable to have a peeling process between the said bonding process and the said exposure process.
The peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the conductive layer.
Examples of the peeling method of the temporary support include known peeling methods. Specifically, there is a cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589.

<Resist pattern formation process>
The resist pattern forming step is a step of developing the exposed photosensitive composition layer to form a resist pattern.
It is preferable that the development processing is carried out using a developer.
By developing with the above developer, the unexposed regions of the photosensitive composition layer are removed, and a resist pattern having projections corresponding to the openings of the mask is formed.

As the developer, an alkaline aqueous solution containing an alkali metal salt is preferred.
The alkali metal salt contained in the developer is preferably a compound that dissolves in water and exhibits alkalinity.
Alkali metal salts include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.
The developer may contain a compound that dissolves in water and exhibits alkalinity, other than the alkali metal salt. Examples of such compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).

The liquid temperature of the developer during development is preferably 10 to 50.degree. C., more preferably 15 to 40.degree. C., even more preferably 20 to 35.degree.
The pH of the developer during development is preferably 9 or higher, more preferably 10 or higher, and even more preferably 11 or higher. The upper limit is preferably 14 or less, more preferably less than 13. pH can be measured by a method based on JIS Z8802-1984 using a known pH meter. The pH measurement temperature is 25°C.

The content of water in the developer is preferably 50% by mass or more and less than 100% by mass, more preferably 90% by mass or more and less than 100% by mass, relative to the total mass of the developer.
The content of the alkali metal salt in the developer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developer.

Examples of the developing method include known developing methods.
Specific examples include puddle development, shower development, spin development and dip development.
As the developing method, the developing method described in paragraph [0195] of WO 2015/093271 is preferable.

After development, it is also preferable to perform a rinse treatment for removing the developer remaining on the substrate with the conductive layer before proceeding to the next step. Water or the like can be used for the rinse treatment.
After the development and/or rinsing treatment, a drying treatment for removing excess liquid from the substrate with the conductive layer may be performed.

The position and size of the resist pattern formed on the substrate with the conductive layer are not particularly limited, but fine lines are preferred.
Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is often 1.0 μm or more.

<Post-exposure process, post-baking process>
Between the development step and the etching step described later, the resist pattern obtained on the substrate with the conductive layer is further subjected to a step of exposing (hereinafter also referred to as a “post-exposure step”) and / or a heating step (hereinafter , also referred to as a “post-baking step”).
When having both a post-exposure process and a post-bake process, it is preferable to implement the post-bake process after implementing the post-exposure process.
The exposure amount in the post-exposure step is preferably 100-5000 mJ/cm ² , more preferably 200-3000 mJ/cm ² .
The post-baking temperature in the post-baking step is preferably 80 to 250°C, more preferably 90 to 160°C.
The post-baking time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

<Etching process>
The etching step is a step of etching the conductive layer in the region where the resist pattern is not arranged.
Specifically, in the etching step, the resist pattern obtained by the above steps is used as an etching resist to etch the conductive layer.
When the etching process is performed, the conductive layer is removed at the openings of the resist pattern, and the conductive layer has the same pattern shape as the resist pattern.

Examples of the etching method include known etching methods.
Specifically, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, the method described in paragraphs [0048] to [0054] of JP-A-2010-152155, and the etching solution Dry etching such as immersion wet etching and plasma etching are included.

As the etchant used for wet etching, an acidic or alkaline etchant can be appropriately selected according to the object to be etched.
Examples of the acidic etchant include an acidic aqueous solution containing at least one acidic compound, and an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. A mixed aqueous solution of
The acidic compound contained in the acidic aqueous solution (the compound exhibiting acidity when dissolved in water) is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid.
Examples of the alkaline etchant include an alkaline aqueous solution containing at least one alkaline compound, and an alkaline mixed aqueous solution of an alkaline compound and a salt (eg, potassium permanganate, etc.).
Alkaline compounds contained in the alkaline aqueous solution (compounds exhibiting alkalinity when dissolved in water) include, for example, sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide, etc.). At least one selected from the group consisting of is preferred.
The etchant preferably does not dissolve the resist pattern.
The developer used in the development step may also serve as the etchant used in the etching process. In this case, the development process and the etching process may be performed simultaneously.

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

<Plating process>
The plating process is a process of forming a plated layer by plating on the conductive layer (the conductive layer exposed on the surface by the development process) in the area where the resist pattern is not arranged.
Examples of plating methods include electroplating and electroless plating, with electroplating being preferred from the standpoint of productivity.
When the plating step is carried out, a plated layer having a pattern shape similar to that of the area where the resist pattern is not arranged (the opening of the resist pattern) is obtained on the substrate with the conductive layer.

Examples of the metal contained in the plating layer include known metals.
Specific examples include metals such as copper, chromium, lead, nickel, gold, silver, tin and zinc, and alloys of these metals.
Among them, the plating layer preferably contains copper or an alloy thereof from the viewpoint of better conductivity of the conductive pattern. In addition, the plating layer preferably contains copper as a main component in order to improve the conductivity of the conductive pattern.

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

<Protective layer forming process>
It is also preferable to have a protective layer forming step between the plating step and the resist pattern stripping step described later.
The protective layer laminating step is a step of forming a protective layer on the plating layer.
As a material for the protective layer, a material having resistance to stripping solution and/or etching solution in the resist stripping process and/or removal process is preferable. Examples thereof include metals such as nickel, chromium, tin, zinc, magnesium, gold and silver, alloys thereof and resins, with nickel or chromium being preferred.

Examples of the method for forming the protective layer include electroless plating and electroplating, with electroplating being preferred.

The thickness of the protective layer is preferably 0.3 μm or more, more preferably 0.5 μm or more. The upper limit is preferably 3.0 μm or less, more preferably 2.0 μm or less.

<Resist pattern peeling process>
The resist pattern stripping step is a step of removing the remaining resist pattern after the etching step.
As a method for removing the remaining resist pattern, for example, a method of removing by chemical treatment can be mentioned, and a method of removing using a remover is preferable.
Examples of the method for removing the remaining resist pattern include a method of removing by known methods such as a spray method, a shower method and a puddle method using a remover.

Examples of stripping solutions include stripping solutions in which an alkaline compound is dissolved in at least one selected from the group consisting of water, dimethylsulfoxide and N-methylpyrrolidone.
Examples of alkaline compounds (compounds that exhibit alkalinity when dissolved in water) include alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, primary amine compounds, secondary amine compounds, and tertiary amine compounds. and alkaline organic compounds such as quaternary ammonium salt compounds. Preferred alkaline organic compounds are tetramethylammonium hydroxide and alkanolamine compounds.

As a method for removing the resist pattern, a substrate having a remaining resist pattern is immersed for 1 to 30 minutes in a stripping solution being stirred at a liquid temperature of 30 to 80° C. (preferably 50 to 80° C.). be done.
It is also preferable that the stripping solution does not dissolve the conductive layer.

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

<Removal process>
When the method of manufacturing a laminate having a conductor pattern includes a plating process, the method of manufacturing a laminate having a conductor pattern has a removal step.
The removing step is a step of removing the conductive layer exposed by the resist pattern stripping step to obtain a conductive pattern on the substrate.
In the removing step, the plating layer formed by the plating step is used as an etching resist, and the conductive layer located in the non-pattern forming region (in other words, the region not protected by the plating layer) is etched.

Although the method for removing a portion of the conductive layer is not particularly limited, it is preferable to use a known etchant.
Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixed solution, and phosphoric acid-hydrogen peroxide mixed solution. .

When the removing step is carried out, the conductive layer exposed to the surface from the substrate is removed, and the plated layer (conductor pattern) having a pattern shape remains to obtain a laminate having the conductor pattern.

The line width of the formed conductor pattern is preferably 8 μm or less, more preferably 6 μm or less. The lower limit is often 1 μm or more.

<Other processes>
The method for manufacturing a laminate having a conductor pattern may have other steps in addition to the steps described above.
Other steps include, for example, the step of reducing the visible light reflectance described in paragraph [0172] of WO 2019/022089 and the surface of the insulating film described in paragraph [0172] of WO 2019/022089 , a step of forming a new conductive layer.

(Step of reducing visible light reflectance)
A method for manufacturing a laminate having a conductor pattern may include a step of performing a process for reducing the visible light reflectance of part or all of the conductor pattern of the laminate.
The treatment for reducing the visible light reflectance includes, for example, oxidation treatment. When the laminate has a conductor pattern containing copper, the visible light reflectance of the laminate can be reduced by oxidizing the copper to form copper oxide and blackening the conductor pattern.
Examples of the treatment for reducing the visible light reflectance include paragraphs [0017] to [0025] of JP-A-2014-150118, and paragraphs [0041], [0042], and [0042] of JP-A-2013-206315 [0048] and [0058], the contents of which are incorporated herein.

(Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film)
A method for manufacturing a laminate having a conductor pattern includes a step of forming an insulating film on the surface of the laminate having the conductor pattern, and a step of forming a new conductive layer (such as a conductor pattern) on the surface of the insulating film. may be
Through the above steps, the first electrode pattern and the insulated second electrode pattern can be formed.
The process of forming the insulating film includes, for example, a method of forming a known permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive composition.
As the step of forming a new conductive layer on the surface of the insulating film, for example, a conductive photosensitive composition may be used to form a new conductive layer in a desired pattern by photolithography.

A method for producing a laminate having a conductor pattern uses a substrate having a plurality of conductive layers (metal layers, etc.) on both surfaces of the laminate, and uses conductive layers formed on both surfaces of a base material. It is also preferred to form the conductor patterns sequentially or simultaneously.
With the above configuration, it is possible to form a touch panel circuit wiring in which the first conductive pattern is formed on one substrate surface and the second conductive pattern is formed on the other substrate surface. It is also preferable to form the touch panel circuit wiring having the above configuration from both sides of the substrate by roll-to-roll.

[Use of laminate having conductor pattern]
A laminate having a conductor pattern manufactured by the manufacturing method described above is preferably used, for example, as a manufacturing process film for a semiconductor package, a printed circuit board, and an interposer rewiring layer.
Examples of a device including a laminate having a conductor pattern manufactured by the above manufacturing method include an input device, preferably a touch panel, and more preferably a capacitive touch panel. Further, the input device can be applied to display devices such as an organic EL display device and a liquid crystal display device.

The present invention will be described in more detail based on examples below.
The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below. "Parts" and "%" are based on mass unless otherwise specified.
In the following, the weight average molecular weight of the resin is the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersity (Mw/Mn) obtained in terms of polystyrene by gel permeation chromatography (GPC). Moreover, the theoretical acid value was used for the acid value.

[Various components]
〔resin〕
<Synthesis of Resin A1-1>
Propylene glycol monomethyl ether (9.7 g) and propylene glycol monomethyl ether acetate (9.7 g) were placed in a flask and heated to 90°C under a nitrogen stream. Styrene (26.9 g), methyl methacrylate (6.7 g), methacrylic acid (11.9 g), γ-butyrolactone methacrylate (GBLMA manufactured by Osaka Organic Co., Ltd.) (6.2 g) and polymerization initiator V-601 ( FUJIFILM Wako Pure Chemical Industries, Ltd.) (1.7 g) was dissolved in propylene glycol monomethyl ether (5 g) and propylene glycol monomethyl ether acetate (5 g), and a polymerization initiator V-601 (FUJIFILM Wako Pure Chemical Industries, Ltd. Co.) (1.7 g) dissolved in propylene glycol monomethyl ether (9.7 g) and propylene glycol monomethyl ether acetate (9.7 g) was added dropwise over 2 hours. After completion of dropping, V-601 (0.6 g) was added three times at intervals of 1 hour. After that, the reaction was further continued for 3 hours. Then, it was diluted with propylene glycol monomethyl ether acetate to obtain a solution of resin A1-1 with a solid concentration of 30%. The weight average molecular weight in terms of standard polystyrene by GPC was 23000, the polydispersity was 2.2, and the acid value of the polymer was 150 mgKOH/g. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the polymer solid content for any monomer.
A similar procedure was used to synthesize resins A1-2 to A1-5, A1-7 to A1-9, A2-1 and A2-2. Also, each of the above resins was obtained as a solution having a solid concentration of 30%. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the polymer solid content for any monomer.

<Synthesis of Resin A1-6>
Propylene glycol monomethyl ether (17.2 g) was charged into a flask and heated to 90° C. under a stream of nitrogen. Styrene (15.3 g), γ-butyrolactone methacrylate (GBLMA manufactured by Osaka Organic Co., Ltd.) (10.6 g), methacrylic acid (16.4 g), polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ( 3.7 g) dissolved in propylene glycol monomethyl ether (13.3 g) was added dropwise over 3 hours. After completion of dropping, V-601 (0.5 g) was added three times at intervals of 1 hour. After that, the reaction was further continued for 3 hours. After that, it was diluted with propylene glycol monomethyl ether acetate (23.8 g) and propylene glycol monomethyl ether (33.9 g). The temperature of the reaction solution was raised to 100° C. under an air stream, and tetraethylammonium bromide (0.24 g) and p-methoxyphenol (0.11 g) were added. Glycidyl methacrylate (Blenmer G manufactured by NOF Corporation) (10.5 g) was added dropwise over 20 minutes. This was reacted at 100° C. for 7 hours and then diluted with propylene glycol monomethyl ether acetate to obtain a solution of Resin A1-6 with a solid concentration of 30%. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the polymer solid content for any monomer.
Resins A2-3 and A2-4 were synthesized using similar procedures. Also, each of the above resins was obtained as a solution having a solid concentration of 30%. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the polymer solid content for any monomer.

Resins A1-1 to A1-9 and resins A2-1 to A2-4 are shown below.
In the formula, the composition ratio is a mass ratio.

In the table below, the column of "acid value before hydrolysis" shows the acid value (theoretical acid value) (mgKOH/g) before hydrolysis of the specific group of each resin.
The column of "acid value increased by hydrolysis" shows the theoretical acid value (mgKOH / g) before hydrolyzing the specific group of each resin, and the theoretical acid value of the increase when the specific group of each resin is hydrolyzed. value (mgKOH/g). Specifically, it shows the theoretical acid value (mgKOH/g) derived from the acid group (e.g., carboxyl group, etc.) generated when the specific group of each resin is hydrolyzed, and the "acid value increased by hydrolysis = Amount of carboxyl groups generated by hydrolysis (mmol/g) x molecular weight of KOH".

[Photosensitive composition]
Each photosensitive composition was prepared with the components and formulations shown in the table below.
In the table, the numerical value described in each component column represents the content (parts by mass) of each component.

<Compound (D)>
・SMA EF-40: styrene/maleic anhydride copolymer (molar ratio 80/20) (manufactured by Cray Valley)
・MMA/GBLMA: copolymer of methyl methacrylate/γ-butyrolactone methacrylate (mass ratio 60/40, weight average molecular weight 12000, degree of dispersion 2.2, synthesized with reference to the synthesis method of resin A1-1)
ADBL: a compound having the following structure (synthesized by reacting adipic acid and bromobutyrolactone under basic conditions)

<Polymerizable compound>
・SR454: Ethoxylated (3) trimethylolpropane triacrylate, manufactured by Tomoe Kogyo Co., Ltd. ・BPE-500: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・BPE-100: Ethoxylated bisphenol A dimethacrylate, Shin-Nakamura Chemical Industry Co., Ltd. M270: Aronix M-270, polypropylene glycol diacrylate (n ≈ 12), Toagosei Co., Ltd. 4G: NK Ester 4G, polyethylene glycol # 200 dimethacrylate, Shin-Nakamura Chemical Co., Ltd.

<Polymerization initiator>
2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

<Sensitizer>
・4,4′-bis(diethylamino)benzophenone

<Polymerization inhibitor>
・Phenothiazine

<Antioxidant>
・Phenidone

<Pigment>
・Leuco Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd.

<Antirust agent>
・CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd.

<Surfactant>
・F552: Megafac F-552, manufactured by DIC

<Solvent>
・MMPGAc: 1-methoxy-2-propyl acetate ・MEK: methyl ethyl ketone

[Ingredients of Intermediate Layer Forming Composition]
The intermediate layer of the transfer film was formed using an intermediate layer-forming composition prepared with the components and formulation shown in the table.

<Resin>
・PVA: Polyvinyl alcohol, product name “Kuraray Poval PVA-205”, manufactured by Kuraray Co., Ltd. ・PVP: Polypyrrolidone, product name “Polyvinylpyrrolidone K-30”, manufactured by Nippon Shokubai Co., Ltd. ・HPMC: Hydroxypropyl methylcellulose, product name “Metolose” 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.

<Surfactant>
・F444: Megafac F444, fluorosurfactant, manufactured by DIC

<Solvent>
・Methanol ・Water

[evaluation]
[Evaluation of hydrolyzability]
Using γ-butyrolactone methacrylate as a verification compound for a compound having a lactone group and phenylsuccinic anhydride as a verification compound for an acid anhydride, hydrolysis was evaluated by the following procedure.
Each verification compound was dissolved in acetonitrile, and a 10% by mass KOH aqueous solution (pH 14) was mixed so that KOH would be 2 mol equivalents with respect to each verification compound. After stirring for 1 minute, acetic acid was added to adjust the pH to 6. The resulting solution was measured for the residual amount of each verification compound using HPLC. (relative to the charged amount mass %), all of them were 1 mass % or less, and it was confirmed that the compound having a lactone group and the acid anhydride exhibit hydrolyzability. In addition, it was confirmed that a carboxy group was generated in each verification compound after adding KOH.

[Preparation of transfer film]
Each transfer film composed of a temporary support, an intermediate layer, and a photosensitive composition layer was produced. Specific procedures are shown below.
First, on a temporary support (16 μm thick polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.)), an intermediate layer forming composition was applied using a bar coater so that the thickness after drying was 1.0 μm. and dried in an oven at 90° C. to form an intermediate layer.
Furthermore, on the intermediate layer, a photosensitive composition is applied using a bar coater so that the thickness after drying becomes 3.0 μm, dried at 80° C. using an oven, and the photosensitive composition layer ( A negative photosensitive layer) was formed.
A 16 μm-thick polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded as a protective film onto the obtained photosensitive composition layer to prepare a transfer film used in each example or each comparative example.

[Preparation of laminate having conductor pattern]
A PET substrate with a copper layer was used, which was obtained by forming a copper layer with a thickness of 500 nm on a PET film (polyethylene terephthalate film) with a thickness of 188 μm by a sputtering method.
The prepared transfer film was cut into 50 cm squares, the protective film was peeled off, and the photosensitive composition layer was placed in contact with the copper layer on the surface of the PET substrate at a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m. /min. was laminated on a PET substrate with a copper layer under the lamination conditions of , to obtain a laminate. At this point, the laminate has a configuration of "PET film--copper layer--photosensitive composition layer--intermediate layer--temporary support".
Next, the temporary support was peeled off from the obtained laminate to expose the intermediate layer on the surface of the laminate. A mask having a line (μm)/space (μm) ratio of 1/1 and a line width of 1 to 10 μm in steps of 1 μm was brought into close contact with the intermediate layer exposed on the surface of the laminate.
Light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dai Nippon Kaken Co., Ltd., dominant wavelength: 365 nm). The exposure amount was such that the resist pattern obtained after development reproduced a line-and-space shape of 5 μm.
After that, development was carried out using a 1.0% sodium carbonate aqueous solution (pH 11.4) at 28° C. as a developer. Specifically, the development was performed by performing shower processing for 30 seconds, performing AirKnife processing, draining the developer, performing shower processing with pure water for 30 seconds, and then performing AirKnife processing. The steps up to this point are referred to as a first pattern formation step.
As a result, a laminate having a line-and-space resist pattern of line width:space width=1:1 was obtained. The laminate at this point has a configuration of "PET film-copper layer-resist pattern".

<Minimum Resolution Line Width>
In the first pattern formation step, the minimum line width that can be formed without causing development residue, pattern collapse, etc., was defined as the minimum resolution line width [mu]m.

<Resist pattern shape>
In addition, the cross-sectional shape of the resist pattern obtained in the first pattern formation step was observed with a scanning electron microscope (SEM), and the resist pattern shape (footing at the minimum resolution line width) was evaluated according to the following evaluation criteria. evaluated.
A: Pattern shape without hemming B: Slightly hemming shape C: Hemming shape

<Evaluation of resist pattern peelability>
The laminate obtained in the first pattern formation step was treated with a copper sulfate plating solution (copper sulfate 75 g/L, sulfuric acid 190 g/L, chloride ion 50 mass ppm, Meltex Co., Ltd., "Coppergleam PCM", 5 mL/L). ) and subjected to copper plating under the condition of 1 A/dm ² .
After the copper-plated laminate was washed with water and dried, it was immersed in a 1% by mass potassium hydroxide aqueous solution (pH 13.5) at 50° C. to remove the resist pattern. Stripping was performed by changing the stripping time, and the time required for the resist pattern to be stripped in the line-and-space pattern of 5 μm was evaluated as follows. Incidentally, the shorter the time, the better the releasability.
A: Less than 30 seconds B: 30 seconds or more and less than 60 seconds C: 60 seconds or more and less than 120 seconds D: 120 seconds or more

<Evaluation of copper pattern shape>
[Evaluation of Resist Pattern Peelability] The copper layer (seed layer) of the subsequent laminate was removed with an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide to obtain a copper wiring pattern. rice field. The cross-sectional shape of the copper wiring pattern was observed with a scanning electron microscope (SEM), and the presence or absence of undercut at the bottom of the copper pattern was evaluated in the pattern of 5 μm.
A: Shape without undercut B: Slightly undercut shape C: Undercut shape

<Conductor pattern formation by etching and evaluation of conductor pattern linearity (LWR)>
A substrate having a resist pattern formed thereon (a laminate having a resist pattern) was obtained by carrying out the steps up to the first pattern forming step in the same manner.
A substrate on which a resist pattern is formed (laminate having a resist pattern) is etched with a copper etchant (Cu-02: manufactured by Kanto Kagaku Co., Ltd.) at 23 ° C. for 30 seconds, and an aqueous alkanolamine stripping solution (pH 13.1 ) was used to strip the resist pattern at 40° C. to obtain a substrate (laminate having a conductor pattern) on which copper wiring was patterned.
The line width of 100 points randomly selected from a 5 μm line-and-space copper wiring pattern was measured. The standard deviation (unit: nm) of the obtained line width was determined, and the value of the standard deviation was defined as LWR (Line Width Roughness).
The obtained LWR values were classified based on the following categories, and conductor pattern linearity (LWR) was evaluated. Note that the smaller the LWR, the smaller the line width variation, which is preferable.
A: LWR is less than 150 nm B: LWR is 150 nm or more and less than 200 nm C: LWR is 200 nm or more and less than 300 nm D: LWR is 300 nm or more

From the results in the table, it was confirmed that the transfer film of the present invention was capable of forming a resist pattern, and that the formed resist pattern was excellent in releasability.
The amount of acid value increased by hydrolysis (acid value derived from an alkali-soluble group generated by a specific group of resin A or compound D by the action of alkali) is 20 to 100 mgKOH/g (preferably 20 to 80 mgKOH/g ), it was confirmed that the effect of the present invention is more excellent (comparison of Examples 1, 5 and 7, etc.).

Except for using the polyester film (thickness 6.9 μm) described in Example 1 of JP-A-2000-309650 as a temporary support, the procedure of Examples 1 to 17 was the same as in [Preparation of transfer film]. A transfer film was produced using the photosensitive composition. As a result of evaluating the minimum resolution line width, resist pattern shape, resist pattern peelability, copper pattern shape and LWR in the same manner as above for each of the obtained transfer films, all the evaluation results are the same as those of Examples 1 to 17. It was a good result equivalent to the result.

10 Transfer film 11 Temporary support 13 Intermediate layer 15 Photosensitive composition layer 17 Composition layer 19 Protective film

Claims (21)

A transfer film having a temporary support and a photosensitive composition layer,
The photosensitive composition layer contains a resin A, a polymerizable compound, and a polymerization initiator,
The transfer film, wherein the resin A contains a structural unit a having a group that forms an alkali-soluble group by the action of an alkali, and a structural unit b having an acid group. The transfer film according to claim 1, wherein the structural unit a contains a structural unit having an alkali-decomposable group. 3. The transfer film according to claim 1, wherein the structural unit a contains a structural unit having a group that generates an acid group by the action of an alkali. The structural unit a comprises at least one selected from the group consisting of a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group. 4. The transfer film according to any one of 1 to 3. The content of the structural unit a is 5 to 50% by mass with respect to the total structural units of the resin A,
5. The transfer film according to any one of claims 1 to 4, wherein the content of the structural unit b is 10 to 30% by mass based on the total structural units of the resin A. A transfer film having a temporary support and a photosensitive composition layer,
The photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
The resin B contains a structural unit b having an acid group,
The compound D has a group that generates an alkali-soluble group by the action of alkali,
A transfer film, wherein the content of the compound D is 5 to 50% by mass with respect to the total mass of the photosensitive composition layer. 7. The transfer film according to claim 6, wherein said compound D contains a structural unit having an alkali-decomposable group. 8. The transfer film according to claim 6, wherein said compound D contains a structural unit having a group that generates an acid group by the action of alkali. 6. The compound D contains at least one selected from the group consisting of a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group. 9. The transfer film according to any one of items 1 to 8. The transfer film according to any one of claims 1 to 9, further comprising an intermediate layer between the temporary support and the photosensitive composition layer. 11. The transfer film of Claim 10, wherein the intermediate layer comprises a water-soluble resin. The water-soluble resin is selected from the group consisting of polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins and polyamide resins. The transfer film according to claim 11. The transfer film and the substrate are laminated so that the photosensitive composition layer side of the transfer film according to any one of claims 1 to 12 is in contact with the conductive layer of the substrate having a conductive layer on the surface. a lamination process to
An exposure step of exposing the photosensitive composition layer;
a resist pattern forming step of forming a resist pattern by developing the exposed photosensitive composition layer;
either an etching step of performing an etching process or a plating process of performing a plating process on the conductive layer in a region where the resist pattern is not arranged;
a resist pattern stripping step of stripping the resist pattern;
Manufacture of a laminate having a conductor pattern, further comprising a removal step of removing the conductive layer exposed by the resist pattern stripping step and forming a conductor pattern on the substrate when the plating step is included. a method,
A laminate having a conductor pattern, further comprising a temporary support peeling step for peeling the temporary support between the bonding step and the exposure step, or between the exposure step and the developing step. Production method. The resist pattern stripping step is a step of stripping the resist pattern using a stripping solution,
14. The method for producing a laminate having a conductor pattern according to claim 13, wherein the stripping solution has a pH of 13 or higher. The resist pattern forming step is a step of performing a development treatment using a developer to form a resist pattern,
15. The method for producing a laminate having a conductor pattern according to claim 13 or 14, wherein the developer has a pH of less than 13. 16. The method for producing a laminate having a conductor pattern according to any one of claims 13 to 15, wherein the exposure method in said exposure step is any one of mask exposure, direct imaging exposure and projection exposure. The method for producing a laminate having a conductor pattern according to any one of claims 13 to 16, wherein the temporary support has a thickness of less than 16 µm. Between the bonding step and the exposure step, the temporary support peeling step is provided,
Manufacture of a laminate having a conductor pattern according to any one of claims 13 to 17, wherein the exposed surface exposed in the temporary support peeling step is brought into contact with a mask to expose the photosensitive composition layer. Method. including a resin C, a polymerizable compound, and a polymerization initiator,
The photosensitive composition, wherein the resin C contains a structural unit having a lactone group and a structural unit b having an acid group. The content of the structural unit having the lactone group is 5 to 50% by mass based on the total structural units of the resin C, and the content of the structural unit b is 10 to 30% based on the total structural units of the resin C. % by weight. including a resin B, a polymerizable compound, a polymerization initiator, and a compound DA different from the resin B;
The resin B contains a structural unit b having an acid group,
The compound DA has a group having a lactone group,
A photosensitive composition, wherein the content of the compound DA is 5 to 50% by mass relative to the total solid content of the photosensitive composition.

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