TW202309205A - Transfer film, method for manufacturing laminate having conductor pattern, photosensitive composition - Google Patents

Abstract

The present invention provides a transfer film capable of forming a photoresist pattern that is excellent in peelability, a method for manufacturing a laminate having a conductor pattern, and a photosensitive composition. A transfer film having a pseudo-support and a photosensitive composition layer, in which the photosensitive composition layer contains a resin A, a polymerizable compound, and a polymerization initiator, and the resin A contains a structural unit a having a group that generates an alkali-soluble group by the action of alkali, and a structural unit b having an acid group.

Description

Transfer film, method for producing laminate with conductor pattern, photosensitive composition

The present invention relates to a transfer film, a method for producing a laminate with conductive patterns, and a photosensitive composition.

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

For example, Patent Document 1 describes a method for forming a resist pattern using a photosensitive resin composition for projection exposure containing (A) a binder polymer, (B) A photopolymerizable compound with a sexually unsaturated bond and (C) a photopolymerization initiator.

[Patent Document 1] Japanese Patent Laid-Open No. 2019-109543

The inventors of the present invention tried to form a conductive pattern using a transfer film having a photosensitive composition layer as described in Patent Document 1. As a result, they found that although a photoresist pattern could be formed, it was difficult to peel off after the etching step or the plating treatment step. photoresist pattern. It was found that especially in the step of forming a conductor pattern based on the semi-additive method, it is difficult to lift off the photoresist pattern after the plating treatment step. Hereinafter, a photoresist pattern that is difficult to peel off after the etching step or the plating treatment step is also referred to as being excellent in "peelability".

Therefore, the subject of this invention is providing the transfer film which can form a resist pattern and is excellent in the releasability of the formed resist pattern. Another object is to provide a method for producing a layered body having a conductive pattern and a photosensitive composition.

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

〔1〕 A transfer film, which has a pseudo-support and a photosensitive composition layer, wherein The photosensitive composition layer includes resin A, a polymerizable compound, and a polymerization initiator, The said resin A contains the structural unit a which has the base which generate|occur|produces an alkali-soluble group by the action of alkali, and the structural unit b which has an acidic group. 〔2〕 The transfer film as described in [1], wherein The above-mentioned structural unit a includes a structural unit having an alkali-decomposable group. (3) The transfer film according to [1] or [2], wherein The above-mentioned structural unit a includes a structural unit having a group that generates an acidic group by the action of a base. (4) The transfer film according to any one of [1] to [3], wherein The above-mentioned structural unit a includes 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. (5) The transfer film according to any one of [1] to [4], wherein The content of the above-mentioned structural unit a is 5 to 50% by mass relative to all the structural units of the above-mentioned resin A, Content of the said structural unit b is 10-30 mass % with respect to all the structural units of the said resin A. (6) A transfer film, which has a pseudo-support and a photosensitive composition layer, wherein The photosensitive composition layer includes a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B, The above-mentioned resin B includes a structural unit b having an acid group, The above-mentioned compound D has a base that generates an alkali-soluble group by the action of a base, Content of the said compound D is 5-50 mass % with respect to the gross mass of a photosensitive composition layer. (7) The transfer film as described in [6], wherein The above-mentioned compound D includes a constitutional unit having an alkali-decomposable group. 〔8〕 The transfer film according to [6] or [7], wherein The above-mentioned compound D includes a structural unit having a group that generates an acid group by the action of a base. 〔9〕 The transfer film according to any one of [6] to [8], wherein The above-mentioned 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. (10) The transfer film according to any one of [1] to [9], further comprising an intermediate layer between the dummy support and the photosensitive composition layer. (11) The transfer film as described in [10], wherein The above-mentioned intermediate layer contains a water-soluble resin. (12) The transfer film as described in [11], wherein The above-mentioned water-soluble resins include 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. at least one of the group of amine resins. (13) A method of manufacturing a laminate with a conductor pattern, comprising: In the pasting step, the above-mentioned transfer film is bonded in such a manner that the photosensitive composition layer side of the transfer film described in any one of [1] to [12] is in contact with the above-mentioned conductive layer of the substrate having a conductive layer on the surface. Bonding with the above substrate; Exposure step, exposing the photosensitive composition layer; A photoresist pattern forming step, performing a development treatment on the exposed photosensitive composition layer to form a photoresist pattern; Any one of the etching step of performing etching treatment and the electroplating treatment step of performing electroplating treatment on the above-mentioned conductive layer located in the area where the above-mentioned photoresist pattern is not arranged; and a photoresist pattern stripping step, stripping the above photoresist pattern, When having the above-mentioned electroplating treatment step, there is further a removal step of removing the above-mentioned conductive layer exposed by the above-mentioned photoresist pattern stripping step and forming a conductive pattern on the above-mentioned substrate, wherein Between the bonding step and the exposing step or between the exposing step and the developing step, there is further a dummy support peeling step for peeling off the dummy support. (14) The method of manufacturing a laminate having a conductor pattern according to [13], wherein The step of stripping the above photoresist pattern is a step of stripping the above photoresist pattern using a stripping liquid, The pH of the stripping liquid is 13 or more. (15) The method of manufacturing a laminate having a conductor pattern according to [13] or [14], wherein The step of forming a photoresist pattern is a step of performing a development process using a developer to form a photoresist pattern, The pH of the developer was 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 above 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 thickness of the above pseudo-support is less than 16 μm. (18) The method for producing a laminate having a conductor pattern according to any one of [13] to [17], wherein There is the step of peeling off the dummy support between the step of laminating and the step of exposing, The photosensitive composition layer is exposed by bringing the exposed surface exposed in the dummy support peeling step into contact with a mask. (19) A photosensitive composition comprising a resin C, a polymerizable compound and a polymerization initiator, The said resin C contains the structural unit which has a lactone group, and the structural unit b which has an acidic group. (20) The photosensitive composition as described in [19], wherein The content of the structural unit having a lactone group is 5 to 50% by mass relative to all the structural units of the resin C, and the content of the structural unit b is 10 to 30% by mass relative to all the structural units of the resin C. 〔twenty one〕 A photosensitive composition comprising resin B, a polymerizable compound, a polymerization initiator and a compound DA different from resin B, The above-mentioned resin B includes a structural unit b having an acid group, The above-mentioned compound DA contains a base with a lactone group, Content of the said compound DA is 5-50 mass % with respect to the total solid content of a photosensitive composition. [Invention effect]

According to the present invention, a transfer film capable of forming a resist pattern and having excellent peelability of the formed resist pattern can be provided. Furthermore, according to the present invention, it is also possible to provide a method for producing a laminate having a conductive pattern and a photosensitive composition.

Hereinafter, the present invention will be described in detail. The meanings of the following symbols in this specification are shown. The numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In numerical ranges stated step by step, the upper limit or lower limit stated in a certain numerical range may be replaced with the upper limit or lower limit of other numerical ranges stated stepwise. In addition, in the numerical range described in this specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in an Example. A "step" not only includes an independent step, but also includes a step as long as the intended purpose of the step can be achieved even if it cannot be clearly distinguished from other steps. Unless otherwise specified, "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. The average transmittance of visible light is a value measured using a spectrophotometer, for example, can be measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.). Unless otherwise specified, the 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, TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by TOSOH CORPORATION) are used as columns and eluents for weight average molecular weight (Mw) and number average molecular weight (Mn). THF (tetrahydrofuran), using a differential refractometer as a detector, and using polystyrene as a standard substance, is a value in terms of polystyrene using a standard substance measured with a gel permeation chromatography (GPC) analyzer. Unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw). Unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP: Inductively Coupled Plasma) spectroscopic analyzer. "(Meth)acryl" is a concept that includes both acryl and methacryl, and "(meth)acryloxy" is a concept that includes both acryloxy and methacryloxy. concept. "Alkali-soluble resin" refers to the resin whose solubility with respect to 100 g of 1 mass % aqueous solutions of sodium carbonate at 22 degreeC is 0.1 g or more. "Water solubility" means that the solubility to 100 g of water of pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more. That is, "water-soluble resin" refers to a resin satisfying the above-mentioned solubility.

The "solid content" of a composition (such as a photosensitive composition, etc.) means a component that forms a composition layer (such as a photosensitive composition layer, etc.) formed using the composition. When the composition contains a solvent (such as an organic solvent and water, etc.), it refers to all components except solvents. Moreover, as long as it is a component which forms a composition layer (for example, a photosensitive composition layer etc.), a liquid component is also considered as a solid component.

[Transfer film] ＜＜The first embodiment＞＞ The first embodiment of the transfer film is a transfer film having a pseudo-support and a photosensitive composition layer, wherein The photosensitive composition layer includes resin A, a polymerizable compound and a polymerization initiator, Resin A contains the structural unit a which has the group (it is also called "specific group" hereafter.) which generate|occur|produces an alkali-soluble group by the action of alkali, and the structural unit b which has an acidic group.

The details of the mechanism by which the transfer film of the present invention exhibits the desired effect are not clear, but the inventors of the present invention presume as follows. When the resin A contained in the photosensitive composition layer contains the above-mentioned structural unit b, a dissolution contrast can be generated between the exposed part and the unexposed part to form a photoresist pattern. On the other hand, for example, when an alkaline stripping solution is used to strip the photoresist pattern after the etching step or after the plating treatment step, the specific group contained in the above-mentioned constituent unit a generates an alkali-soluble group by the alkaline stripping solution. As a result, it is presumed that the solubility of the photoresist pattern to the above-mentioned alkaline stripping liquid is improved, and the stripping property is excellent. In addition, when an alkaline developer and an alkaline stripping solution are used in the developing process and the photoresist pattern stripping step, the specific group will not generate an alkali-soluble group by the alkaline developer, and the specific group will not be generated by the alkaline stripping solution. It is preferred to generate alkali-soluble groups. Hereinafter, even more excellent releasability is also referred to as "the effect of the present invention is more excellent".

The transfer film may have other layers besides the dummy support and the photosensitive composition layer. As another layer, the intermediate|middle layer mentioned later is mentioned, for example. Moreover, the transfer film may have other members (for example, a protective film etc.) mentioned later.

As an embodiment of the transfer film, for example, the following constitution (1) or (2) can be mentioned, and constitution (2) is preferable. (1) "pseudo-support/photosensitive composition layer/protective film" (2) "pseudo-support/intermediate layer/photosensitive composition layer/protective film" It is preferable that the transfer film has an intermediate layer. 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 generation of air bubbles in a bonding step described later, the maximum width of the ripples of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. The lower limit is preferably at least 0 μm, more preferably at least 0.1 μm, and still more preferably at least 1 μm. The maximum width of the ripples of the transfer film is a value measured by the following procedure. The transfer film was cut into a size of 20 cm in length x 20 cm in width in a direction perpendicular to the main surface to prepare a test sample. In addition, when the transfer film has a protective film, the protective film is peeled from the transfer film. Next, the above-mentioned test sample was left still on a table with a smooth and horizontal surface so that the surface of the dummy support faced the table. After standing still, scan the surface of the test sample with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) to obtain a three-dimensional surface image of the center of the test sample within a 10 cm square area. From the obtained three-dimensional surface image The height of the largest convexity minus the height of the lowest concave. The above-mentioned operation was performed on 10 test samples, and the arithmetic mean thereof was used as the maximum corrugation width of the transfer film.

In the photosensitive composition layer of the transfer film, when there are further composition layers (for example, a photosensitive composition layer and an intermediate layer, etc.) on the surface of the photosensitive composition layer opposite to the dummy support , 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 transmittance of light having a wavelength of 365 nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.

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

Hereinafter, with regard to the transfer film, each member and each component will be described in detail. In addition, the description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. Hereinafter, the first embodiment of the transfer film will be described in detail.

〔Pseudo-support body〕 The transfer film has a pseudo-support. The member of the pseudo support system supporting the photosensitive composition layer is finally removed by peeling treatment.

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

From the viewpoint of enabling pattern exposure through the dummy support, it is preferable that the dummy support has high transparency. Specifically, the transmittance of the pseudo-support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. It is better if the upper limit is less than 100%. It is preferable that the haze of the dummy support is small from the viewpoint of the pattern formability at the time of pattern exposure through the dummy support and the transparency of the dummy support. Specifically, the haze of the pseudo-support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. The lower limit is preferably 0% or more.

It is preferable that the number of fine particles, foreign matter, and defects in the dummy support is small from the viewpoint of pattern formation properties during pattern exposure through the dummy support and transparency of the dummy support. Specifically, the number of particles (for example, particles with a diameter of 1 μm), foreign matter and defects in the pseudo-support is preferably 50 pieces/10mm ² or less, more preferably 10 pieces/10mm ² or less, and 3 pieces/10mm ² The following are more preferable, and less than 1 piece/10mm ² is particularly preferable. The lower limit is preferably 0 piece/10mm ² or more.

The thickness of the pseudo-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, 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 pseudo-support was calculated as an average value of arbitrary five points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).

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

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

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

〔Photosensitive composition layer〕 The transfer film has a photosensitive composition layer. As the photosensitive composition layer, a negative photosensitive composition layer is preferable. When the photosensitive composition layer is a negative photosensitive composition layer, the formed photoresist pattern corresponds to a cured film. The photosensitive composition layer preferably contains 10.0 to 90.0% by mass of the resin A, 5.0 to 70.0% by mass of the polymerizable compound, and 0.01 to 20.0% by mass of the polymerization initiator relative to the total mass of the photosensitive composition layer.

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, still more preferably 0.5 to 30 μm, and particularly preferably 1 to 20 μm. Thereby, the developability of a photosensitive composition layer improves and resolution can be improved.

The photosensitive composition layer contains resin A, a polymerizable compound, and a polymerization initiator. Hereinafter, each component which a photosensitive composition layer may contain is demonstrated.

＜Resin A＞ Resin A contains the structural unit a which has a specific group, and the structural unit b which has an acidic group. As the resin A, an alkali-soluble resin containing the above-mentioned structural unit a and the above-mentioned structural unit b is preferable.

(constituent unit a) The constitutional unit a is a constitutional unit having a specific group (a group that generates an alkali-soluble group by the action of a base). "A base that forms an alkali-soluble group by the action of a base" means a base that forms an alkali-soluble group by decomposition or the like under the action of a base. However, groups derived from alkyl (meth)acrylates (for example, -COO-alkyl, etc.) are not included in the specific groups. Therefore, a structural unit derived from an alkyl (meth)acrylate is not included in the structural unit a. The above-mentioned alkyl group may be any of linear, branched and cyclic. As a monomer constituting a structural unit derived from an alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylate, base) isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) (Meth)acrylates such as cyclohexyl acrylate and 2-ethylhexyl (meth)acrylate. In addition, resin A is allowed to contain a group derived from an alkyl (meth)acrylate and/or a structural unit derived from an alkyl (meth)acrylate.

Examples of alkali-soluble groups that generate specific groups by the action of bases include acid groups such as phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, and sulfonic acid groups, sulfonamide groups, sulfonimide groups, and acid groups. is preferred, carboxyl is more preferred.

The constitutional unit a preferably includes a constitutional unit having an alkali-decomposable group, more preferably a constitutional unit having a group that generates an acidic group when decomposed by alkali, and from the viewpoint of reactivity and storage stability, includes selected At least one selected from the group consisting of a constituent unit having a lactone group, a constituent unit having an acid anhydride group, and a constituent unit having a lactone group and an acid anhydride group is further preferably selected from the group consisting of constituent units having a lactone group It is particularly preferably at least one of the group consisting of structural units having an acid anhydride group, and most preferably includes a structural unit having a lactone group.

The "alkali-decomposable group" means a group that is decomposed by the action of a base to produce an alkali-soluble group. For example, whether it corresponds to an alkali decomposable group can be judged by the following method. Prepare the verification compound having the base of the measurement object. Examples of the verification compound 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 (for example, acetonitrile, etc.), and a certain amount of alkaline aqueous solution is added at room temperature to perform a hydrolysis reaction. Thereafter, an acid is added to the obtained solution to make the solution acidic. The solution was judged by measuring the residual 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 relative to the total mass of the verification compound before hydrolysis, the verification compound is regarded as corresponding to a compound having an alkali-decomposable group. In addition, the residual amount of the above-mentioned verification compound is preferably 50% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is often 0 mass % or more. In addition, whether or not a basic possibility group is generated can be confirmed by isolating a compound generated by alkali decomposition and using NMR (Nuclear Magnetic Resonance: nuclear magnetic resonance) or the like.

-Constituent unit having a lactone group- As long as the lactone group is a group having a lactone structure, any of a lactone group itself and a group having a lactone group may be used. As the lactone group, a group having a lactone structure with a 5- to 7-membered ring is preferable, and a group having another ring structure such as a bicyclic structure or a spiro ring structure condensed on the lactone structure with a 5- to 7-membered ring is more preferable. Moreover, in the structural unit which has a lactone group, a lactone group may be directly bonded to the main chain of resin A, and may form a part of the main chain of resin A.

As the lactone group, a group obtained by removing one or more hydrogen atoms from a lactone compound is preferable. As the lactone compound, the compound represented by any one of the formulas (LC1-1) to (LC1-17) is preferred, the formula (LC1-1), the formula (LC1-4), the formula (LC1-5), The compound represented by any one of formula (LC1-6), formula (LC1-13), formula (LC1-14) and formula (LC1-17) is more preferable, formula (LC1-1), formula (LC1- 4) and the compound represented by any one of the formulas (LC1-17) are further preferred. In the case of the above compound, the pattern shape becomes favorable, and the resist pattern release property improves.

In addition, lactone compounds usually have optical isomers. As the lactone compound, any optical isomer can be used. The optical isomers of the lactone compound can be used alone or in combination of two or more. In other words, mixtures of optical isomers can be used. When one optical isomer is used, the optical purity (ee) of the lactone compound is preferably 90 or higher, more preferably 95 or higher.

[chemical formula 1]

In the formulas (LC1-1) to (LC1-17), Rb ₂ represents a substituent. n ₂ represents an integer of 0 or more. Examples of the substituent represented by Rb ₂ include alkyl having 1 to 8 carbons, cycloalkyl having 4 to 7 carbons, alkoxy having 1 to 8 carbons, and alkoxy having 1 to 8 carbons. Carbonyl group, carboxyl group, halogen atom, hydroxyl group and cyano group. When n ₂ is 2 or more, the plurality of Rb ₂ may be the same or different, and the plurality of Rb ₂ may be bonded to each other to form a ring.

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

[chemical formula 2]

In formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. 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, or a divalent group or a single bond obtained by combining these. V represents a group formed by removing one hydrogen atom from the compound represented by any one of the formulas (LC1-1) to (LC1-17).

Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. As the substituent which the optionally substituted alkyl group represented by Rb ₀ may have, for example, a hydroxyl group and a halogen atom are mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. As Rb ₀ , a hydrogen atom or a methyl group is preferable.

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, or a divalent group or a single bond obtained by combining these. As Ab, a single bond or -Ab ₁ -CO ₂ - is preferable. Ab ₁ represents a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group. As Ab ₁ , a methylene group, an ethylidene group, a cyclohexyl group, an adamantyl group or a norbornyl group is preferable.

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

Although the specific example of the structural unit which has a lactone group is mentioned below, this invention is not limited to these. In the formula, Rx represents a hydrogen atom, a methyl group, -CH ₂ OH or -CF ₃ .

[chemical formula 3]

[chemical formula 4]

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

-Constituent unit having acid anhydride group- The acid anhydride group may be any of an acid anhydride group itself and a group having an acid anhydride group as long as it has an acid anhydride structure. As an acid anhydride group, a carboxylic acid anhydride group (-C(=O)-O-C(=O)-) is preferred, and a cyclic carboxylic acid anhydride group (a ring group containing -C(=O)-O-C(=O)- ) is better. The carboxylic acid anhydride group may be any of linear, branched and cyclic, and cyclic is preferred. The number of ring members of the ring constituting the cyclic carboxylic anhydride group is preferably from 5 to 7, more preferably from 5 or 6, and still more preferably from 5.

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

[chemical formula 5]

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

As a substituent represented by R ^A1a , an alkyl group is mentioned, for example. When Z ^1a represents a divalent group, as Z ^1a , an alkylene group having 2 to 4 carbons is preferable, an alkylene group having 2 or 3 carbons is more preferable, and an alkylene group having 2 carbons is still more preferable. good.

n ^1a represents an integer of 0 or more. n ^1a is preferably an integer of 0-4, more preferably an integer of 0-2, and further preferably 0. When n ^1a represents an integer of 2 or more, the plural R ^A1a may be the same or different. In addition, a plurality of R ^A1a may be bonded to each other to form a ring, but it is preferable not to bond to each other to form a ring.

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

[chemical formula 6]

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

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

Although the specific example of the structural unit which has an acid anhydride group is mentioned below, the structural unit which has an acid anhydride group is not limited to these specific examples. Rx represents a hydrogen atom, a methyl group, -CH ₂ OH or -CF ₃ .

[chemical formula 7]

The constituent unit a can 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 more preferably 5 to 30% by mass, relative to all the structural units of the resin A. , 5 to 20% by mass is still more preferable.

(constituent unit b) The structural unit b is a structural unit having an acid group. As the acidic group which the structural unit b has, a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group are mentioned, for example, A carboxyl group is preferable.

As the structural unit b, a structural unit derived from the first monomer is preferred, and a structural unit derived from (meth)acrylic acid is more preferred. The first monomer is a monomer having a carboxyl group. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and 4-vinylbenzoic acid, and (meth)acrylic acid is preferred.

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

[chemical formula 8]

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

The constituent unit b can 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 most preferably 14 to 25% by mass relative to all the structural units of the resin A .

In the resin A, the content of the structural unit a is preferably 5 to 50% by mass relative to all the structural units of the resin A and the content of the structural unit b is 10 to 30% by mass relative to all the structural units of the resin A. The structural unit The content of a is more preferably 7 to 30 mass % with respect to all the structural units of the resin A, and the content of the structural unit b is more preferably 14 to 25 mass % with respect to all the structural units of the resin A.

(other constituent units) Resin A may contain other structural units other than the above-mentioned structural unit a and the above-mentioned structural unit b.

It is preferable that the resin A contains a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing deterioration of line width and resolution when the focal position shifts during exposure. As said aromatic hydrocarbon group, the phenyl group which may have a substituent, and the aralkyl group which may have a substituent are mentioned, for example. The content of the structural units derived from monomers having an aromatic hydrocarbon group is preferably at least 10% by mass, more preferably at least 20% by mass, and still more preferably at least 25% by mass, based on all the structural units of the resin A. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less with respect to all the constituent units of the resin A. When the photosensitive composition layer contains two or more resins A, it is preferable that the mass average value of the content of the structural unit derived from the monomer which has an aromatic hydrocarbon group exists in the said range.

As monomers having an aromatic hydrocarbon group, for example, monomers having an aralkyl group, styrene and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tertiary butoxystyrene , Acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer, etc.), monomers with aralkyl groups or styrene are preferred, and styrene is more preferred. When the monomer having an aromatic hydrocarbon group is styrene, the content of the constituent units derived from styrene is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and 25% to all constituent units of resin A. -55 mass % is still more preferable. When the photosensitive composition layer contains two or more resins A, it is preferable that the mass average value of the content of the structural unit which has an aromatic hydrocarbon group exists in the said range.

As an aralkyl group, the phenylalkyl group which may have a substituent is mentioned, for example, The benzyl group which may have a substituent is preferable.

As a monomer containing a phenylalkyl group which may have a substituent, phenylethyl (meth)acrylate is mentioned, for example.

Examples of monomers containing benzyl groups which may have substituents include benzyl (meth)acrylates such as benzyl (meth)acrylate and benzyl chloride (meth)acrylate; vinylbenzyl chloride; Vinyl monomers having a benzyl group, such as vinyl benzyl alcohol, are preferably (meth)acrylates having a benzyl group, and more preferably benzyl (meth)acrylate. When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of the constituent units derived from benzyl (meth)acrylate is preferably 10 to 80% by mass relative to all the constituent units of the resin A, 20-60 mass % is more preferable, and 25-55 mass % is still more preferable.

As another structural unit, the structural unit derived from a 2nd monomer is also mentioned. The second monomer is a monomer that is non-acidic (does not have an acid group) and has a polymerizable group in the molecule. The meaning of the polymerizable group is the same as that of the polymerizable group described later in the polymerizable compound, and the preferred aspects are also the same. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, Butyl ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ring (meth)acrylate (Meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or n-butyl (meth)acrylate are preferred, methyl (meth)acrylate or Ethyl (meth)acrylate is more preferred. The content of the structural unit derived from the second monomer is preferably 1 to 80% by mass, more preferably 1 to 60% by mass, and still more preferably 1 to 50% by mass with respect to all the structural units of the resin A.

The resin may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. By using a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain, it is possible to introduce a branched structure or an alicyclic structure into the side chain of the resin. The group having an alicyclic structure may be either monocyclic or polycyclic. "Side chain" refers to a group of atoms branching from the main chain. "Main chain" refers to the relatively longest bonded chain in the molecules of the polymer compound constituting the resin. Examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, (meth)acrylate ) tertiary butyl acrylate, isopentyl (meth) acrylate, tertiary pentyl (meth) acrylate, secondary pentyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) 3-octyl acrylate and tertiary octyl (meth)acrylate. Among them, isopropyl (meth)acrylate, isobutyl (meth)acrylate or tertiary butyl methacrylate is preferred, and isopropyl methacrylate or tertiary butyl methacrylate is more preferred. As a monomer containing the group which has an alicyclic structure in a side chain, the monomer which has a monocyclic aliphatic hydrocarbon group, and the monomer which has a polycyclic aliphatic hydrocarbon group are mentioned, for example. Moreover, (meth)acrylate which has an alicyclic hydrocarbon group with 5-20 carbon atoms is mentioned. As more specific examples, (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl Alkyl ester, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-(meth)acrylate -Ethyl adamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester Alkyl esters, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (methyl ) 2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-methanoinden-5 (meth)acrylate -yl ester, octahydro-4,7-inden-1-ylmethyl (meth)acrylate, 1-menthol (meth)acrylate, tricyclodecane (meth)acrylate, ( Meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[ 4.1.0] Heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenzyl (meth)acrylate, 2,2,5-tri-(meth)acrylate Methylcyclohexyl and cyclohexyl (meth)acrylate. Among the above, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, ( 2-adamantyl methacrylate, fenzyl (meth)acrylate, 1-menthol (meth)acrylate and tricyclodecane (meth)acrylate are preferred, and (meth) Cyclohexyl acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate and tricyclodecane (meth)acrylate are better.

As another structural unit, the structural unit which has a polymeric group is also mentioned. Examples of the above-mentioned polymerizable group include polymerizable groups possessed by polymerizable compounds described later, and ethylenically unsaturated groups are preferred, and acryl groups or methacryl groups are more preferred. Moreover, it is also preferable that the above-mentioned polymerizable group is a polymerizable group capable of a polymerization reaction with a polymerizable group of a polymerizable compound.

It is preferable that the resin containing the structural unit which has a polymeric group is obtained by reacting the resin containing the structural unit derived from the 1st monomer, and a 3rd 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. As said polymeric group, the polymeric group which the polymeric compound mentioned later has is mentioned, for example. Among them, it is preferable that the third monomer has two kinds of polymerizable groups, it is more preferable to have an ethylenically unsaturated group and a cationic polymerizable group, and it is still more preferable to have an acryl group or a methacryl group and an epoxy group. .

Glycidyl (meth)acrylate is mentioned as a 3rd monomer, for example.

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

[chemical formula 9]

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

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

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

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

As a structural unit which has a polymeric group, the following structural units are mentioned, for example. In the formula, Rx and Ry each independently represent a hydrogen atom or a methyl group.

[chemical formula 10]

The content of the structural unit having a polymerizable group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and 20 to 40% by mass based on all the structural units of the resin A. % is the best.

As a method for introducing a polymerizable group into the resin A, for example, an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfide compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride and the resin A have The method of reacting hydroxyl group, carboxyl group, primary amino group, secondary amino group, acetyl acetyl group and sulfo group. As a preferred aspect of the method of introducing a polymerizable group into resin A, there is a method of synthesizing a polymer having a carboxyl group by a polymer reaction, and then making glycidyl (meth)acrylate or the like have a ring The (meth)acrylate of the oxy group reacts with a part of the carboxyl groups of the obtained polymer to introduce the (meth)acryloxy group into the polymer. As another method, there is a method of synthesizing a polymer having a hydroxyl group by a polymer reaction, and reacting a (meth)acrylate having an isocyanate group with a part of the hydroxyl group of the obtained polymer to convert ( A meth)acryloxy group is introduced into the polymer. By these methods, the resin A which has a (meth)acryloxy group in a side chain can be obtained.

The reaction temperature of the above polymer reaction is preferably 80-110°C. It is better to use a catalyst in the above polymer reaction, and it is more preferable to use an ammonium salt (tetraethylammonium bromide). The reaction temperature of the above polymerization reaction is preferably 70-100°C, more preferably 80-90°C. It is better to use a polymerization initiator in the above-mentioned polymerization reaction. As a polymerization initiator, it is more preferable to use an azo initiator. As a polymerization initiator, V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) or V- 65 (manufactured by FUJIFILM Wako Pure Chemical Corporation) is further preferred.

As resin A, the following aspects are preferable. (Aspect 1): Contains structural unit a, a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from styrene, or a structural unit derived from benzyl methacrylate. (Aspect 2): Contains 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-mentioned aspects, it is also preferable to set the content of each structural unit to each of the above-mentioned preferable aspects. Moreover, it is as above-mentioned about the preferable aspect of the structural unit a.

The photosensitive composition layer may contain other resins other than the resin A described above. Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxy Styrene resin, polyimide resin, polyamide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycol.

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

The acid value of the resin A is preferably 250 mgKOH/g or less, more preferably 200 mgKOH/g or less, still 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 value (mgKOH/g)" refers to the mass (mg) of potassium hydroxide required to neutralize 1g of the sample. The acid value can be calculated|required based on JISK0070:1992, for example. The acid value of resin A can be adjusted according to the kind of structural unit which resin has, and/or content of the structural unit containing an acid group.

Moreover, the acid value derived from the carboxyl group of resin A is preferably 60-250 mgKOH/g, more preferably 80-200 mgKOH/g, and still more preferably 90-180 mgKOH/g. In addition, the above-mentioned acid value derived from a carboxyl group does not include a carboxyl group that generates a specific group by the action of a base. The acid value of the resin A derived from the alkali-soluble group formed by the action of the alkali is preferably 5-200 mgKOH/g, more preferably 20-100 mgKOH/g, and still more preferably 20-80 mgKOH/g. The acid value derived from the alkali-soluble group which generate|occur|produces the specific group by the action of alkali can use the theoretical acid value computed from the structure of resin A mentioned above. Specifically, when the resin A has a lactone group, the theoretical acid value can be calculated from 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 the resin A is preferably from 5,000 to 500,000, more preferably from 10,000 to 100,000, still more preferably from 10,000 to 60,000, and most preferably from 10,000 to 50,000. When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. Moreover, when a weight average molecular weight is 5,000 or more, the property of the image development aggregate and the property of an unexposed film, such as the edge melting property of a transfer film, and chipping property, can be controlled. "Edge meltability" refers to the ease with which the photosensitive composition layer protrudes from the end surface of the roll when the transfer film is wound up into a roll. "Cutting property" refers to the ease with which shavings are scattered when the unexposed film is cut with a cutter. If this swarf adheres to the upper surface of the transfer film, etc., it will be transferred to the mask in the subsequent exposure process, etc., and will become a cause of defective products. The degree of dispersion of the resin is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

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

As a synthesis method of resin A, radical polymerization using, for example, peroxide-based polymerization initiators (for example, benzoyl peroxide, etc.) and azo-based polymerization initiators (for example, azobisisobutyronitrile, etc.) The initiator polymerizes the above-mentioned single or plural monomers. As a polymerization method, by adding dropwise to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or isopropanol) under nitrogen flow It is preferable to add a monomer solution and a radical polymerization initiator solution, and to heat and stir it. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a method for synthesizing the resin A, block polymerization, suspension polymerization, or emulsion polymerization can be used other than solution polymerization.

＜Polymerizable compound＞ The photosensitive composition layer contains a polymerizable compound. The "polymerizable compound" refers to a compound different from the above-mentioned resin A which has a polymerizable group and polymerizes under the action of a polymerization initiator described later.

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

As the polymerizable compound, a compound having one or more ethylenically unsaturated groups in the molecule (hereinafter, also referred to as "ethylenically unsaturated compound") is a viewpoint that the photosensitivity of the photosensitive composition layer is more excellent. ) is preferred, and a compound having two or more ethylenically unsaturated groups in the molecule (hereinafter also referred to as "polyfunctional ethylenically unsaturated compound") is more preferred. Also, from the standpoint of better resolving properties and exfoliation properties, the number of ethylenically unsaturated groups in the molecule of the ethylenically unsaturated compound is 1 or more, preferably 1-6, and more preferably 1-3. 2 to 3 are further preferred.

The polymerizable compound may have an alkyleneoxy group. As the above-mentioned alkyleneoxy group, ethoxyl or propoxyl is preferable, and ethoxyl is more preferable. The number of additions of the alkyleneoxy groups added to the polymerizable compound is preferably 2-30 per molecule, more preferably 2-20.

From the standpoint of a better balance between photosensitivity, resolution and peelability of the photosensitive composition layer, the polymerizable compound contains a difunctional or trifunctional ethylenic unsaturated group having 2 or 3 ethylenically unsaturated groups in the molecule. Saturated compounds are preferred.

From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably 40.0% by mass or more, and still more preferably 50.0% by mass or more, relative to the total mass of the polymerizable compound. good. The upper limit is preferably at most 100.0 mass %, more preferably at most 80.0 mass %. That is, all polymeric compounds contained in the photosensitive composition layer may be bifunctional ethylenically unsaturated compounds. The content of the trifunctional ethylenically unsaturated compound is preferably at least 10.0% by mass, more preferably at least 15.0% by mass, based on the total mass of the polymerizable compound. The upper limit is preferably at most 100.0 mass %, more preferably at most 80.0 mass %, and still more preferably at most 50.0 mass %. That is, all polymeric compounds contained in the photosensitive composition layer may be trifunctional ethylenically unsaturated compounds. Also, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryl group as a polymerizable group is preferable.

(polymerizable compound B1) As the polymerizable compound, it is also preferable to include 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-mentioned polymerizable compounds.

Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic rings such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; Heterocyclic ring; the condensed ring formed by combining these rings is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The above-mentioned aromatic ring may further have a substituent.

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

Examples of the polymerizable compound B1 having a bisphenol structure include those having a bisphenol structure and two polymerizable groups (preferably (meth)acryl groups) bonded to both ends of the bisphenol structure. compound. Both ends of the bisphenol structure may be directly bonded to the polymerizable group, or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group which can be added to both ends of the bisphenol structure, an ethoxyl group or a propoxyl group is preferable, and an ethoxyl group is more preferable. The number of alkyleneoxy groups (preferably ethoxylate groups) added to the bisphenol structure is preferably 2 to 30 per molecule, more preferably 2 to 20. Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs [0072] to [0080] of JP-A-2016-224162, and these contents are incorporated in the present specification.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is better. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy) yl)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane and 2, Ethoxylated bisphenol A dimethacrylate such as 2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE series, manufactured by Shin-Nakamura Chemical Co., Ltd.) , 2,2-bis(4-(methacryloxydodecyloxytetrapropoxy)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.).

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

[chemical formula 11]

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 the integer of 1-39. n1+n3 represents the integer of 2-40. n2 and n4 each independently represent the integer of 0-29. n2+n4 represents an integer of 0-30. The arrangement of the constituent units of -(AO)- and -(BO)- may be either random or block. In the case of a block, any of -(AO)- and -(BO)- may be on the side of a bisphenyl group. As n1+n2+n3+n4, 2-20 are preferable, 2-16 are more preferable, 4-12 are still more preferable. Also, n2+n4 is preferably 0-10, more preferably 0-4, still more preferably 0-2, and particularly preferably 0.

From the viewpoint of better resolution, the content of the polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, and still more preferably 25.0% by mass or more, relative to the total mass of the photosensitive composition layer. good. From the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive composition bleeds from the end of the transfer member), the upper limit is preferably 70.0% by mass or less, 60.0% by mass relative to the total mass of the photosensitive composition layer Below % is better.

From the standpoint of better resolution, the content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, and still more preferably 55.0% by mass or more, based on the total mass of the polymerizable compound. More than 60.0% by mass is particularly preferred. From the viewpoint of detachability, 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 particularly preferably 90.0% by mass or less with respect to the total mass of the polymerizable compound. , below 85.0% by mass is the best.

(other polymeric compounds) The photosensitive composition layer may contain other polymerizable compounds in addition to the above. As another polymeric compound, a well-known polymeric compound is mentioned, for example. Specifically, compounds having one ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or more functional ethylenically unsaturated compounds include saturated compounds.

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

Examples of bifunctional ethylenically unsaturated compounds not having an aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and urethane di(meth)acrylate. base) acrylate and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol Dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 , 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl Glycol di(meth)acrylate. Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Acrylate. Examples of the urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. Moreover, examples of commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of ethylenically unsaturated compounds having a trifunctional or higher function include diperythritol (tri/tetra/penta/hexa)(meth)acrylate, neopentylthritol (tri/tetra)(meth)acrylic acid ester, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate Meth)acrylate, glycerol tri(meth)acrylate and their alkylene oxide modified substances. "(Three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates concept. Also, "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (for example, KAYARAD (registered trademark) manufactured by Nippon Kayaku Co., Ltd. DPCA-20 and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compounds (for example, KAYARAD RP- 1040, ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glycerin trimethacrylate (for example, A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX (registered trademark) series (for example, TO-2349, M-520, and M-510 manufactured by TOAGOSEI CO., LTD., etc.).

The polymeric compound may be a polymeric compound having an acid group (eg, carboxyl group, etc.). The above-mentioned acid groups may form groups derived from acid anhydrides. 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 those described in paragraphs [0025] to [0030] of JP-A-2004-239942.

The molecular weight of the polymerizable compound is preferably at most 3,000, more preferably 200 to 3,000, still more preferably 280 to 2,200, and most preferably 300 to 2,200.

A polymeric compound can be used individually by 1 type or in 2 or more types. The content of the polymerizable compound is preferably from 10.0 to 70.0 mass %, more preferably from 15.0 to 70.0 mass %, and still more preferably from 20.0 to 70.0 mass % with respect to the total mass of the photosensitive composition layer.

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

It is preferable that the photosensitive composition layer contains a photoinitiator. The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving active rays such as ultraviolet rays, visible rays, and X-rays. As a photoinitiator, a well-known photoinitiator is mentioned, for example. As a photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, A photoradical polymerization initiator is preferable.

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

From the viewpoints of photosensitivity, visibility and resolution of exposed and non-exposed parts, the photoradical polymerization initiator is selected from the group consisting of 2,4,5-triaryl imidazole dimers and derivatives thereof. At least one of the group is preferred. In addition, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triaryl imidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)- 4,5-diphenylimidazole dimer and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

Examples of photoradical polymerization initiators include those described in paragraphs [0031] to [0042] of JP-A-2011-095716 and paragraphs [0064]-[0081] of JP-A-2015-014783. Recorded photoradical polymerization initiator.

Examples of photoradical polymerization initiators include dimethylaminobenzoic acid ethyl ester (DBE), benzoin methyl ether, (p,p'-dimethoxybenzyl) anisyl ester, TAZ-110 (manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (manufactured by Midori Kagaku Co., Ltd.), 1- [4-(Phenylthio)]-1,2-octanedione-2-(O-benzoyl oxime) (IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 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 Corporation), IRGACURE OXE-04 (manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Endolinyl)phenyl]-1-butanone (Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-enderinylpropan-1- Ketone (Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane- 1-keto (Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-portolinylphenyl)butanone-1 (Omnirad 369, manufactured by IGM Resins B.V. company), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins B.V. ), 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins B.V.), oxime ester-based Photopolymerization initiator (Lunar 6, manufactured by DKSH Japan K.K.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2- Chlorophenyl)-4,5-diphenylimidazole dimer) (B-CIM, manufactured by Hampford), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) ( TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)- 9H-carbazol-3-yl]-,2-(O-acetyloxime) (TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.) and 3-cyclohexyl-1-(6- (2-(Benzyloxyimino)hexyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials CO., LTD.).

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

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned, for example. As an ionic photocationic polymerization initiator, an onium salt compound, such as a diaryl iodonium salt and a triaryl permeicium salt, and a quaternary ammonium salt are mentioned, for example. As an ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraph [0114]-[0133] of Unexamined-Japanese-Patent No. 2014-085643 is mentioned, for example.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-trisulfones, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Examples of trichloromethyl-s-trisulfones, diazomethane compounds, and imidesulfonate compounds include those described in paragraphs [0083] to [0088] of JP-A-2011-221494 compound. Examples of the oxime sulfonate compound include compounds described in paragraphs [0084] to [0088] of International Publication No. 2018/179640.

One kind of polymerization initiator may be used alone, or two or more kinds may be used. The content of the polymerization initiator is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, based on the total mass of the photosensitive composition layer. The upper limit is preferably at most 20% by mass, more preferably at most 15% by mass, and still more preferably at most 10% by mass with respect to the total mass of the photosensitive composition layer.

＜Pigment＞ From the viewpoint of the visibility of the exposed portion and the non-exposed portion, and the pattern visibility and resolution after development, the photosensitive composition layer may have a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm during color development and A dye whose maximum absorption wavelength is changed by acid, alkali, or free radicals (hereinafter also referred to as "dye N"). It is preferable that the maximum absorption wavelength of the pigment is changed by acid or free radicals. In addition, the dye is a compound different from the compound D described above. When the dye N is contained, although the detailed mechanism is not clear, the adhesiveness with the adjacent layer (for example, the intermediate layer) improves and resolution becomes more excellent.

The "maximum absorption wavelength of the pigment is changed by acid, alkali or free radical" can refer to the state that the pigment in the color development state is decolorized by acid, alkali or free radical, and the pigment in the decolorized state is decolorized by acid or alkali. Any of the state in which the color is developed by free radicals and the state in which the pigment in the color state changes to another color state. Specifically, the dye N may be any of a compound that develops color by changing from a decolorized state by exposure and a compound that decolorizes by changing from a color-developed state by exposure. In the above case, it may be a pigment that generates acid, alkali, or free radicals in the photosensitive composition layer by exposure, and these acts to change the state of color development or decolorization, or it may be a photosensitive composition. A pigment in which the state (for example, pH, etc.) in the material layer is changed to develop or decolorize due to changes in acid, alkali, or free radicals. In addition, it may be a pigment that undergoes a change in the state of color development or decolorization by directly being stimulated by an acid, an alkali, or a free radical without exposure to light.

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

As the coloring mechanism of the dye N, for example, a radical-reactive dye, an acid-reactive dye, or an alkali-reactive dye (for example, a leuco dye, etc.) can be initiated by adding photoradical polymerization to the photosensitive composition layer. agent, photocationic polymerization initiator (photoacid generator) or photobase generator and the free radicals, acid or The form of alkali and color development.

From the viewpoint of the visibility of the exposed part and the non-exposed part, as the maximum absorption wavelength in the wavelength range of 400 to 780 nm in the color development of the dye N, a wavelength of 550 nm or more is preferable, and a wavelength of 550 to 700 nm is more preferable. 550-650 nm is still more preferable. In addition, the dye N may have one or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm for color development. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm for color development, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths has a wavelength of 450 nm or more.

The maximum absorption wavelength of pigment N can be measured by measuring the transmission spectrum of a solution (liquid temperature: 25°C) containing pigment N in the wavelength range of 400 to 780 nm and detecting the intensity of light by using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric environment. Intensity is measured at an extremely small wavelength (maximum absorption wavelength).

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

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

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

Examples of the dye N include dyes and colorless compounds. Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal Rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzorubin (benzopurpurine) 4B, α-naphthyl red, nile blue (nile blue) 2B, nile blue A, methyl violet, malachite green, parafuchsin, victoria pure blue )-Naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industries Co., Ltd. .), oil red 5B (manufactured by Orient Chemical Industries Co., Ltd.), oil scarlet (oil scarlet) #308 (manufactured by Orient Chemical Industries Co., Ltd.), oil red OG (manufactured by Orient Chemical Industries Co., Ltd. .), oil red RR (manufactured by Orient Chemical Industries Co., Ltd.), oil green #502 (manufactured by Orient Chemical Industries Co., Ltd.), spilon red (manufactured by Orient Chemical Industries Co., Ltd.) BEH special (Hodogaya Chemical Co., Ltd. Manufactured), m-cresyl violet, cresyl red, rhodamine B, rhodamine 6G, sulforhodamine B, auretamine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino -4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone , 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylene Amino-5-pyrazolone.

Examples of colorless compounds include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green Lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow precursor, 2-anilino -3-Methyl-6-(N-ethyl-p-toluidyl) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N,N-diethylamino) -5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorescent Luminous yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl -7-stibamidofluorescent yellow precursor, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino )-6-methoxy-7-amino fluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino) fluorescent yellow precursor, 3-(N, N-diethylamino)-7-chlorofluorescent yellow precursor, 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow precursor, 3-(N,N-di Ethylamino)-7,8-benzofluorescent yellow precursor, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorescent yellow precursor, 3-(N, N-dibutylamino)-6-methyl-7-stibamidofluorescent yellow precursor, 3-piperidinyl-6-methyl-7-anilinyl fluorescent yellow precursor, 3-pyrrolidinyl- 6-Methyl-7-anilinofluorescent yellow precursor, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl -2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-di Ethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethyl Aminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1 (3H), 9'-[9H]koukousing-3-one.

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

Pigment N can be used alone or in combination of two or more. From the viewpoint of the visibility of the exposed portion and the non-exposed portion, and the pattern visibility and resolution after development, the content of the pigment N is preferably 0.1% by mass or more with respect to the total mass of the photosensitive composition layer, and 0.1% by mass is preferable. -10 mass % is more preferable, 0.1-5 mass % is still more preferable, and 0.1-1 mass % is especially preferable.

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

＜Heat-crosslinkable compound＞ From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the photosensitive composition layer may contain a heat-crosslinkable compound. The heat-crosslinkable compound which has an ethylenically unsaturated group mentioned later is handled not as a polymeric compound, but as a heat-crosslinkable compound. Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds, and blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. good. The blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group. Therefore, for example, when the resin and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the film formed will decrease, which will harden the photosensitive composition layer. The resulting film tends to enhance its function when used as a hardened film. "Blocked isocyanate compound" means a compound having a structure in which the isocyanate group of isocyanate is protected by a blocking agent.

The dissociation temperature of the blocked isocyanate compound is preferably from 100 to 160°C, more preferably from 130 to 150°C. As a method of measuring the dissociation temperature of the blocked isocyanate compound, for example, using a differential scanning calorimeter (for example, DSC6200, manufactured by Seiko Instruments Inc., etc.), by DSC (Differential scanning calorimetry: differential scanning calorimetry) analysis, The temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound was used as a measure of the degree of dissociation.

As a terminal blocking agent whose dissociation temperature is 100-160 degreeC, active methylene compounds, such as malonate diester, and an oxime compound are mentioned, for example. Examples of the malonate diester include 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 formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketone oxime, and cyclohexanone oxime. . Among them, an oxime compound is preferred as a terminal blocking agent having a dissociation temperature of 100 to 160° C. from the viewpoint of storage stability.

It is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesive force with the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate. Among them, as a blocked isocyanate compound having an isocyanurate structure, there are oxime compounds having Compounds with an oxime structure used as a blocking agent are preferred.

The blocked isocyanate compound may have a polymerizable group. As a polymeric group, the meaning is the same as the polymeric group which the said polymeric compound has, for example, and a preferable aspect is also the same.

Examples of blocked isocyanate compounds include Karenz series (registered trademarks) such as AOI-BM, MOI-BM, and MOI-BP (manufactured by SHOWA DENKO K.K.); blocked duranate series such as TPA-B80E and WT32-B75P ( registered trademark) (manufactured by Asahi Kasei Chemicals Corporation). As the blocked isocyanate compound, the following compounds are preferable.

[chemical formula 12]

The heat-crosslinkable compound can be used individually by 1 type, or may use 2 or more types. The content of the heat-crosslinkable compound is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, relative to 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 a colored resin layer. In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the back peripheral portion of a transparent glass substrate or the like may be attached to a liquid crystal display window of an electronic device in order to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer can be used. As a pigment, what is necessary is just to select suitably according to a desired hue, For example, black pigment, a white pigment, and color pigments other than black and white are mentioned. When forming a black pattern, a black pigment is preferable as a pigment.

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

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

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

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

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

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

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

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

＜Other additives＞ The photosensitive composition layer may contain other additives as needed in addition to the above components. Examples of other additives include resins other than resin A, compound D described later, radical polymerization inhibitors, antioxidants (such as phenidone, etc.), rust inhibitors (such as benzotriazoles and carboxyl benzotriazoles, etc.), sensitizers, surfactants, plasticizers, heterocyclic compounds (such as triazoles, etc.), pyridines (such as isonicotinamide, etc.) and purine bases (such as, adenine, etc.). In addition, examples of other additives include metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic precipitation inhibitors and paragraphs [0165] to [0184] of JP-A-2014-085643, the contents of which are incorporated in this specification. Other additives may be used alone 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, among which phenthiazine, phenanthrene, or 4-methoxyphenol are preferable. As the radical polymerization inhibitor, for example, naphthylamine, copper (I) chloride, nitrosophenylhydroxylamine aluminum salt and diphenylnitrosoamine, which never impair the sensitivity of the photosensitive composition layer From a viewpoint, aluminum salt of nitrosophenylhydroxylamine is preferable. The content of the radical polymerization inhibitor is preferably from 0.001 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, and still more preferably from 0.02 to 2.0% by mass, relative to the total mass of the photosensitive composition layer. The content of the radical polymerization inhibitor is preferably from 0.005 to 5.0% by mass, more preferably from 0.01 to 3.0% by mass, and still more preferably from 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound.

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

(Carboxybenzotriazoles) Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di -2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N,N - Di-2-ethylhexyl)aminoethylenylcarboxybenzotriazole. As a commercial item of carboxybenzotriazoles, CBT-1 (made by JOHOKU CHEMICAL CO., LTD.) is mentioned, for example.

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

(sensitizer) As a sensitizer, a well-known sensitizer, dye, and a pigment are mentioned, for example. Examples of sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone (xanthone) compounds, thioxanthone (thioxanthone) compounds, Pyridone compound, oxazole compound, benzoxazole compound, thiazole compound, benzothiazole compound, triazole compound (for example, 1,2,4-triazole, etc.), stilbene compound, trioxazole compound, thiophene compound, naphthalene Diformimide compounds, triarylamine compounds and aminoacridine compounds.

From the perspective of improving the sensitivity to the light source and improving the hardening speed by balancing the polymerization speed and chain transfer, the content of the sensitizer is preferably 0.01 to 5 mass % relative to the total mass of the photosensitive composition layer, and 0.05 ~1% by mass is more preferable.

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

As the surfactant, a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant is preferable. Examples of fluorine-based surfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F- 437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, 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 (the above are DIC Corporation); Fluorad FC430, FC431, and FC171 (the above are manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393 and KH-40 (manufactured by AGC Inc. above); PolyFox PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc. above); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by Neos Corporation).

Also, as the fluorine-based surfactant, an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, wherein the functional group containing a fluorine atom is partially broken when heat is applied, and the fluorine atom volatilizes is also preferable. Examples of such fluorine-based surfactants include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016)). Furthermore, 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 as the fluorine-based surfactant. As the fluorine-based surfactant, a blocked polymer can also be used. As a fluorine-based surfactant, a fluorine-containing polymer compound is also preferred, and the fluorine-containing polymer compound includes a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structure unit derived from a (meth)acrylate compound having two or more (preferably It is a constituent unit of (meth)acrylate compound having 5 or more) alkoxyl groups (preferably ethoxyl groups, propoxyl groups). In addition, examples of fluorine-based surfactants include fluorine-containing polymers having ethylenically unsaturated groups in side chains, such as MEGAFACE RS-101, RS-102, RS-718K, and RS-72- K (the above are manufactured by DIC Corporation).

From the viewpoint of improving environmental suitability, fluorine-based surfactants are derived from compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). The surfactant of the alternative material is preferred.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate and glycerol ethyl oxides, 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 (the above are manufactured by BASF Corporation); Solsperse 20000 (the above are manufactured by Lubrizol Japan Limited.); NCW-101, NCW-1001 and NCW-1002 (the above are manufactured by FUJIFILM Wako Pure Chemical Corporation); PIONIN D-6112, D-6112-W, and D-6315 (the above are manufactured by Takemoto Oil & Fat Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (the above are manufactured by Nissin Chemical Co., Ltd.).

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

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 are manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (the above are manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.); BYK307, BYK323, and BYK330 (the above are manufactured by BYK Chemie).

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

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

＜Impurities＞ The photosensitive composition layer may contain impurities. Examples of impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.

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

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

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

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

(residual monomer) The photosensitive composition layer may contain residual monomers derived from each constituent unit of the resin A. From the viewpoint of patternability and reliability, the residual monomer content is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and still more preferably 500 mass ppm or less, based on the total mass of resin A. The lower limit is preferably at least 1 mass ppm with respect to the total mass of the resin A, more preferably at least 10 mass ppm. From the viewpoint of patternability and reliability, the residual monomer derived from each constituent unit of resin A is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, with respect to the total mass of the photosensitive composition layer , 100 mass ppm or less is still more preferable. The lower limit is preferably 0.1 mass ppm or more with respect to the total mass of the photosensitive composition layer, more preferably 1 mass ppm or more.

When the alkali-soluble resin is synthesized by polymer reaction, the residual amount of the monomer is also preferably within the above-mentioned range. For example, when synthesizing an alkali-soluble resin by making glycidyl acrylate and a carboxylic acid side chain react, it is preferable to make content of glycidyl acrylate into the said range. As a method of adjusting the content of residual monomers, for example, a method of adjusting the content of the above-mentioned impurities is mentioned. 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 from 0.01 to 1.0% by mass, more preferably from 0.05 to 0.5% by mass, from the viewpoint of improving reliability and lamination.

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

＜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 comprises polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, and polyamide At least one of the group of resins is preferred.

Examples of cellulose-based resins include water-soluble cellulose derivatives. Examples of water-soluble cellulose derivatives include hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose.

Examples of polyether-based resins include polyethylene glycol, polypropylene glycol, and their alkylene oxide adducts, and vinyl ether-based resins. Examples of polyamide resins include acrylamide resins, vinylamide resins, and allylamide resins.

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

The weight average molecular weight of the water-soluble resin is preferably at least 5,000, more preferably at least 7,000, and still more preferably at least 10,000. The upper limit is preferably at most 200,000, more preferably at most 100,000, and further preferably at most 50,000. The degree of dispersion of the water-soluble resin is preferably 1-10, more preferably 1-5, and still more preferably 1-3.

The water-soluble resins may be used alone or in combination of two or more. From the viewpoint of further improving the oxygen barrier properties and interlayer mixing suppression ability, the content of the water-soluble resin is preferably 50% by mass or more, more preferably 70% by mass or more, and furthermore 80% by mass or more relative to the total mass of the intermediate layer. Preferably, more than 90% by mass is particularly preferred. 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, based on the total mass of the intermediate layer.

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

As other components, polyols, alkylene oxide adducts of polyols, phenol derivatives, or amide compounds are preferable, and polyols, phenol derivatives, or amide compounds are more preferable. Moreover, as another component, a well-known surfactant is also mentioned, for example.

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

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

The molecular weight of other components is preferably not more than 5,000, more preferably not more than 4,000, still more preferably not more than 3,000, particularly preferably not more than 2,000, and most preferably not more than 1,500. The lower limit is preferably 60 or more.

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

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

The thickness of the intermediate layer is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not lowered, and the interlayer mixing suppression ability is excellent. In addition, the intermediate layer removal time during development can be further shortened.

[other components] The transfer film may have other members in addition to the above-mentioned members. As another member, a protective film is mentioned, for example.

As a protective film, the resin film which has heat resistance and solvent resistance is mentioned, for example. Specifically, polyolefin films, such as a polypropylene film and a polyethylene film, polyester films, such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film are mentioned. In addition, as the protective film, a resin film made of the same material as the dummy support described above can be used. Among them, as the protective film, a polyolefin film is preferable, and a polypropylene film or a polyethylene film is more preferable.

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

The number of fisheyes with a diameter of 80 μm or more included in the protective film is preferably 5 or less/m ² . The lower limit is preferably 0 piece/m ² or more. "Fish eye" means that when the material is thermally melted, kneaded, extruded, and produced by biaxial stretching and casting methods, foreign matter, undissolved matter, and oxidative deterioration of the material are taken in. Those in the film.

The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, still more preferably 5 particles/mm ² or less. The lower limit is preferably 0 piece/mm ² or more. When it is in the said range, the defect which arises by transcribe|transferring the unevenness|corrugation by the particle|grains contained in a protective film to a photosensitive composition layer or a conductive layer can be suppressed.

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

＜＜Second Embodiment＞＞ The second embodiment of the transfer film is a transfer film having a dummy support and a photosensitive composition layer, wherein The photosensitive composition layer includes a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B, Resin B comprises a constituent unit b having an acid group, Compound D has a base that generates an alkali-soluble group through the action of a base, Content of compound D is 5-50 mass % with respect to the gross mass of a photosensitive composition layer. The meanings of the pseudo-support, the polymerizable compound, and the polymerization initiator are the same as those described in the first embodiment of the transfer film, and preferred embodiments are also the same. In addition, the second embodiment of the transfer film may further include components that may be contained in the photosensitive composition layer of the first embodiment of the transfer film, and the first embodiment of the transfer film may have the above-mentioned middle layer and other components. The first embodiment of the above-mentioned transfer film is an aspect in which the same resin includes 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 compound D which is different from the resin containing the structural unit b having an acidic group has a specific group.

＜Resin B＞ The photosensitive composition layer contains resin B. Resin B contains the structural unit b which has an acidic group. The meaning of the said structural unit b is the same as that of the structural unit b in the said resin A, and a preferable aspect is also the same. Resin B may further contain other structural units in resin A described above. Moreover, it is preferable that resin B does not contain the said specific group and the said 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 a base. The meaning of the group forming an alkali-soluble group by the action of a base is the same as the above-mentioned specific group, and the preferred aspects are also the same. Compound D may further have other groups in addition to the above-mentioned specific groups. Moreover, it is preferable that compound D does not contain the structural unit b which has an acidic group. Compound D may be any of low molecular weight compounds and resins.

Compound D is preferably a compound having a lactone group or an acid anhydride group, more preferably a low-molecular compound having a lactone group or an acid anhydride group or a resin having a lactone group or an acid anhydride group. Moreover, as compound D, the compound which has 2 or more lactone groups or an acid anhydride group in a molecule|numerator is preferable, and the resin which has 2 or more lactone groups or an acid anhydride group in a molecule|numerator is more preferable. As said lactone group and said acid anhydride group, it is the same as the lactone group and acid anhydride group in the structural unit a contained in the said resin A, for example, and a preferable aspect is also the same. When compound D is a resin, compound D may contain other constituent units that resin A may contain. As other structural units, structural units derived from at least one selected from the group consisting of styrene, styrene derivatives, alkyl (meth)acrylates, and aliphatic cycloalkyl methacrylates are preferable. As the compound D, for example, a copolymer of styrene/maleic anhydride (SMA EF-40, manufactured by Cray Valley Corporation), a copolymer of methyl methacrylate/γ-butyrolactone methacrylate, etc. Reaction products of polycarboxylic acid and bromobutyrolactone (for example, reaction products of adipic acid and bromobutyrolactone, etc.), which are low-molecular-weight compounds having two or more lactone groups in the molecule. Moreover, it is preferable to remove the resin of the structural unit b from resin A.

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

Compound D can be used alone or in combination of two or more. The content of compound D is 5-50 mass % with respect to the total mass of the photosensitive composition layer, Preferably it is 5-40 mass %, More preferably, it is 5-30 mass %, More preferably, it is 5-20 mass %.

[Photosensitive composition] It is preferable that the photosensitive composition contains the components and solvent contained in the photosensitive composition layer. The content of each component contained in the photosensitive composition layer is as above-mentioned. Hereinafter, specific implementation aspects of the photosensitive composition will be described in detail.

＜＜The first embodiment＞＞ The first embodiment of the photosensitive composition includes a resin A, a polymerizable compound, and a polymerization initiator, Resin A contains the structural unit a which has the base which forms an alkali-soluble group by the action of alkali, and the structural unit b which has an acidic group. The above-mentioned resin A, the above-mentioned polymerizable compound, the above-mentioned polymerization initiator, the above-mentioned structural unit a, and the above-mentioned structural unit b have the same meanings as the components that may be contained in the above-mentioned photosensitive composition layer, and the preferred aspects are also the same.

＜＜Second Embodiment＞＞ In the second embodiment of the photosensitive composition, The photosensitive composition layer includes a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B, Resin B comprises a constituent unit b having an acid group, Compound D has a base that generates an alkali-soluble group through the action of a base, Content of compound D is 5-50 mass % with respect to the gross mass of a photosensitive composition layer. The meanings of the above-mentioned resin B, the above-mentioned polymerizable compound, the above-mentioned polymerization initiator, the above-mentioned compound D, the above-mentioned structural unit b, and the above-mentioned group forming an alkali-soluble group by the action of a base are the same as those in the above-mentioned photosensitive composition layer. The ingredients are the same, and the preferred form is also the same.

＜＜Third Embodiment＞＞ A third embodiment of the photosensitive composition includes a resin C, a polymerizable compound, and a polymerization initiator, Resin C contains the structural unit which has a lactone group, and the structural unit b which has an acidic group. The meanings of the above-mentioned polymerizable compound and the above-mentioned polymerization initiator are respectively the same as the components that may be contained in the above-mentioned photosensitive composition layer, and the preferred aspects are also the same.

＜Resin C＞ Resin C contains the structural unit which has a lactone group, and the structural unit b which has an acidic group. The structural unit having the above-mentioned lactone group and the structural unit b having the above-mentioned acid group are respectively the same as the structural units that may be contained in the above-mentioned resin A, and the preferred aspects are also the same. As resin C, the resin which contains the structural unit which has a lactone group and the structural unit b which has an acid group among the said resin A is mentioned, for example. Resin C may contain other structural units other than the above-mentioned structural units. As another structural unit, the other structural unit which the said resin A may contain is mentioned, for example.

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, more preferably 5 to 40% by mass, and 7 to 30% by mass relative to all the structural units of the resin C. % is the best. 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, more preferably 10 to 30% by mass, and 14 to 25% by mass relative to all the structural units of the resin C. % is the best. In the resin C, the content of the structural unit having a lactone group is 5 to 50% by mass relative to all the structural units of the resin C, and the content of the structural unit b is 10 to 30% by mass relative to all the structural units of the resin C. Preferably, the content of the structural unit having a lactone group is 7 to 30% by mass relative to all the structural units of the resin C, and the content of the structural unit b is more preferably 14 to 25% by mass relative to all the structural units of the resin C.

＜＜Fourth Embodiment＞＞ Fourth embodiment of the photosensitive composition The photosensitive composition includes resin B, a polymerizable compound, a polymerization initiator, and a compound DA different from resin B, Resin B comprises a constituent unit b having an acid group, Compound DA contains a radical with a lactone group, Content of compound DA is 5-50 mass % with respect to the total solid content of a photosensitive composition. The above-mentioned resin B, the above-mentioned polymerizable compound, the above-mentioned polymerization initiator, and the above-mentioned structural unit b have the same meanings as the components that may be contained in the above-mentioned photosensitive composition layer, and the preferred aspects are also the same.

＜Compound DA＞ Compound DA is a different compound from resin B. Compound DA contains a group having a lactone group. Examples of the above-mentioned group having a lactone group include groups having a lactone group that the compound D may contain. As compound DA, the compound containing the group which has a lactone group among the said compound D is mentioned, for example. Compound DA may further have other groups in addition to the above-mentioned group having a lactone group. Moreover, it is preferable that compound DA does not contain the structural unit b which has an acidic group.

Compound DA can be used alone or in combination of two or more. Content of compound DA is 5-50 mass % with respect to the total solid content of a photosensitive composition, Preferably it is 5-40 mass %, More preferably, it is 5-30 mass %, More preferably, it is 5-20 mass %.

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

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

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether , Diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol Monoalkyl ether acetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone and cyclohexanone. As the solvent, for example, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvents described in paragraph 0014 of Japanese Patent Application Laid-Open No. 2018-177889 can be used, and these contents are incorporated in this specification. One kind of solvent may be used alone, or two or more kinds may be used. The content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1200 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

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

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

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

<Method for forming water-soluble resin composition and intermediate layer (water-soluble resin layer)> The water-soluble resin composition preferably contains various components and a solvent that form the above-mentioned intermediate layer (water-soluble resin layer). In addition, in the water-soluble resin composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the above-mentioned water-soluble resin layer. The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin. At least one selected from the group consisting of water and water-miscible organic solvents is preferred. Water or a mixture of water and water-miscible organic solvents A solvent is more preferred. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, and alcohols having 1 to 3 carbon atoms are preferred, and methanol or ethanol is more preferred. One kind of solvent may be used alone, or two or more kinds may be used. The content of the solvent is preferably from 50 to 2,500 parts by mass, more preferably from 50 to 1,900 parts by mass, and still more preferably from 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

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

<Formation method of photosensitive composition and photosensitive composition layer> From the viewpoint of excellent productivity, it is formed by a coating method using a photosensitive composition containing components (for example, resin A, polymerizable compound, and polymerization initiator, etc.) and a solvent that constitute the photosensitive composition layer. is better. As a method for producing a transfer film, specifically, a method of coating a photosensitive composition on an intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer is relatively good.

As a photosensitive composition, it is as above-mentioned.

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

As a method of drying the coating film of the photosensitive composition, heat drying and reduced-pressure drying are preferable. The drying temperature is preferably 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. Also, the drying time is preferably at least 20 seconds, more preferably at least 40 seconds, and still more preferably at least 60 seconds. The upper limit is preferably 600 seconds or less, more preferably 300 seconds or less.

Furthermore, a transfer film can be manufactured by bonding a protective film to a photosensitive composition layer. As a method of bonding a protective film to a photosensitive composition layer, a well-known method is mentioned, for example. As an apparatus which bonds a protective film to a photosensitive composition layer, well-known laminators, such as a vacuum laminator and an automatic cutting laminator, are mentioned, for example. The laminator is preferably equipped with any heatable roll such as a rubber roll, and is capable of pressurization and heating.

[Manufacturing method of laminated body having conductive pattern] By using the above transfer film, it is also possible to manufacture a laminate having a conductor pattern. The method of manufacturing the layered body having a conductive pattern is not particularly limited as long as it is a method of manufacturing a layered body having a conductive pattern using the transfer film described above. Among them, the method for manufacturing a laminate with a conductor pattern of the present invention is preferably the following method for manufacturing a laminate with a conductor pattern, which has: a bonding step, bonding the transfer film and the substrate in such a way that the photosensitive composition layer side of the transfer film is in contact with the conductive layer of the substrate having a conductive layer on the surface; exposing step, exposing the photosensitive composition layer; Photoresist pattern forming step, performing development treatment on the exposed photosensitive composition layer to form a photoresist pattern; Any one of the etching step of performing etching treatment and the electroplating treatment step of performing electroplating treatment on the conductive layer located in the area where the photoresist pattern is not arranged; and a photoresist pattern stripping step, stripping the photoresist pattern, When there is an electroplating treatment step, there is further a removal step of removing the conductive layer exposed due to the photoresist pattern stripping step and forming a conductive pattern on the substrate, wherein Between the bonding step and the exposure step or between the exposure step and the development step, there is further a dummy support peeling step for peeling off the dummy support. In addition, the method for manufacturing a laminate having a conductive pattern includes the above lamination step, the above exposure step, the above photoresist pattern formation step, the above etching step or the above plating treatment step, the above photoresist pattern stripping step, and the above removal step ( When having the above electroplating treatment step) is preferred. Hereinafter, each step of the manufacturing method of the laminated body which has a conductor pattern is demonstrated.

＜Fitting procedure＞ The bonding step is as follows: For the transfer film having a pseudo-support and a photosensitive composition layer, the transfer film and The above substrates are bonded together. When the transfer film has a protective film described later, it is preferable to carry out the bonding step after peeling the protective film. It is also preferable that the transfer film further has an intermediate layer between the dummy support and the photosensitive composition layer. About the transfer film, it is as above-mentioned.

In bonding, it is preferable to press-bond the photosensitive composition layer side (the surface opposite to the dummy support side) of the transfer film in contact with the conductive layer on the substrate. As the pressure-bonding method, for example, a known transfer method and a lamination method can be mentioned. The surface of the photosensitive composition layer of the transfer film on the side opposite to the dummy support is superimposed on the substrate and applied with a roller or the like. The methods of pressing and heating are preferred. As a bonding method, the method of using a well-known laminator, such as a vacuum laminator and an automatic cutting laminator, is mentioned, for example. The lamination temperature is preferably 70-130°C.

A substrate having a conductive layer on its surface (a substrate with a conductive layer) has a substrate and a conductive layer arranged on the surface of the substrate. Substrate with conductive layer Any layer other than the above-mentioned conductive layer may be formed on the substrate as needed. That is, it is preferable that the substrate with a conductive layer has at least a substrate and a conductive layer arranged on the surface of the substrate. Examples of the substrate include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, and the substrates described in paragraph [0140] of International Publication No. 2018/155193 are preferred. As the material of the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable. The thickness of the resin substrate is preferably 5 to 200 μm, more preferably 10 to 100 μm.

As the conductive layer, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphite layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and thin line formability is better. In addition, only one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When disposing two or more conductive layers, conductive layers having different materials are preferred. As a preferred aspect of the conductive layer, for example, it is described in paragraph [0141] of International Publication No. 2018/155193, and the content thereof is incorporated in this specification.

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

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

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

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

One or more 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 from each other, and conductive layers of different materials are preferred.

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

As a material for laying out wiring, metal is preferable. Examples of the above-mentioned metals include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys combining these. Copper, molybdenum, aluminum, or titanium are preferred, and copper is more preferred. .

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

Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, and mask exposure is preferred.

When the dummy support peeling step described later is carried out between the bonding step and the exposure step, as the exposure step, the side of the layered body from which the dummy support has been peeled off in the dummy support peeling step is made to be opposite to the substrate side The exposure step of performing pattern exposure by contacting one surface with a mask is preferable. In other words, the exposed surface (the surface of the photosensitive composition layer, the surface of the intermediate layer, etc.) The exposure step of pattern exposure is preferred. In addition, as the above-mentioned exposed surface, when the transfer film is composed of two layers of a dummy support and a photosensitive composition layer, the surface of the photosensitive composition layer corresponds to this, and when the transfer film is a dummy support, the middle In the case of a three-layer configuration of the layer and the photosensitive composition layer, the surface of the intermediate layer corresponds to this. If this exposure step is adopted, a higher-definition photoresist pattern can be obtained, and a higher-definition conductor pattern can be finally obtained. In particular, it is preferable to use such an exposure step when the dummy support peeling step described later is performed between the bonding step and the exposure step.

In the exposure step of performing pattern exposure as described above, a curing reaction of components contained in the photosensitive composition layer may occur in the exposed region (region corresponding to the opening of the mask) of the photosensitive composition layer. By performing a developing step after exposure, unexposed regions of the photosensitive composition layer are removed to form a pattern.

It is also preferable to have a mask stripping step of stripping the mask used in the exposure step between the exposure step and the development treatment. As a mask peeling process, a well-known peeling process can be mentioned, for example.

As a light source for pattern exposure, any light in a wavelength range capable of hardening the photosensitive composition layer (for example, a wavelength of 365 nm and a wavelength of 405 nm) may be irradiated, and the wavelength of 365 nm is preferable. "Dominant wavelength" means the wavelength of highest intensity.

Examples of light sources include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 to 200 mJ/cm ² , more preferably 10 to 200 mJ/cm ² . Examples of the light source, exposure amount, and exposure method include paragraphs [0146] to [0147] of International Publication No. 2018/155193, and these contents are incorporated in this specification.

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

＜Resist pattern formation process＞ The step of forming a photoresist pattern is a step of performing a development process on the exposed photosensitive composition layer to form a photoresist pattern. Development Treatment It is preferable to perform development treatment using a developer. By developing using the above-mentioned developing solution, the unexposed region of the photosensitive composition layer is removed, and a resist pattern having the openings of the mask as protrusions is formed.

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

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

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

As an image development method, a well-known image development method is mentioned, for example. Specifically, spin-on-dip image development, shower image development, spin image development, and immersion image development are mentioned. As a developing method, the developing method described in paragraph [0195] of International Publication No. 2015/093271 is preferable.

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

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

<Post-exposure step and post-baking step> Between the development step and the etching step described later, there may be a step of further exposing the photoresist pattern obtained on the substrate with a conductive layer (hereinafter also referred to as "post-exposure step"). ".) and/or a step of heating (hereinafter, also referred to as "post-baking step".). When there are both the post-exposure process and the post-baking process, after implementing a post-exposure process, it is preferable to implement a post-baking process. The exposure amount in the post-exposure step is preferably 100 to 5000 mJ/cm ² , more preferably 200 to 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 step＞ The etching step is a step of etching the above-mentioned conductive layer in the region where the photoresist pattern is not arranged. Specifically, in an etching process, it is a process of performing an etching process on a conductive layer using the photoresist pattern obtained up to the said process as an etching resist. If the etching step is performed, the conductive layer will be removed at the opening of the photoresist pattern, and the conductive layer will have the same pattern shape as the photoresist pattern.

As a method of the etching treatment, for example, a known etching method can be mentioned. Specifically, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435 and the method described in paragraphs [0048]-[0054] of JP-A-2010-152155 can be mentioned. method, wet etching immersed in etching solution, and dry etching such as plasma etching.

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 etching solution include an acidic aqueous solution containing at least one acidic compound and an acidic mixed aqueous solution of an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. At least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid is preferred as the acidic compound (a compound that dissolves in water and exhibits acidity) contained in the acidic aqueous solution. Examples of the alkaline etching solution include an alkaline aqueous solution containing at least one alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (for example, potassium permanganate, etc.). As the basic compound contained in the alkaline aqueous solution (a compound that dissolves in water and exhibits basicity), for example, it is selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (for example, hydroxide At least one of the group of tetramethylammonium, etc.) is preferred. It is preferable that the etching solution does not dissolve the photoresist pattern. The developing solution used in the developing step can also be used as an etching solution for etching. In this case, the developing step and the etching step may be performed simultaneously.

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

＜Plating treatment steps＞ The electroplating treatment step is the following step; an electroplating layer is formed by electroplating treatment on the conductive layer (conductive layer exposed on the surface due to the development step) located in the area where the photoresist pattern is not arranged. As a method of electroplating treatment, an electrolytic plating method and an electroless plating method are mentioned, for example, The electrolytic plating method is preferable from a viewpoint of productivity. If the electroplating step is performed, an electroplating layer having the same pattern shape as the region (opening of the photoresist pattern) on which the photoresist pattern is not arranged on the substrate with the conductive layer can be obtained.

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

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

＜Protective layer formation process＞ It is also preferable to have a protective layer forming step between the plating treatment step and the resist pattern stripping step described later. The protective layering step is a step of forming a protective layer on the electroplating layer. As a material of the protective layer, a material having resistance to the stripping liquid and/or etching liquid in the photoresist stripping step and/or removing step 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.

As a method of forming the protective layer, for example, an electroless plating method, an electroplating method, etc. are mentioned, and an electroplating method is preferable.

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

<Resist Pattern Stripping Step> The photoresist pattern stripping step is a step of removing the photoresist pattern remaining after the etching step. As a method of removing the remaining photoresist pattern, for example, a method of removing by chemical treatment is mentioned, and a method of removing using a stripper is preferable. As a method of removing the remaining photoresist pattern, for example, a method of removing by a known method such as a spray method, a shower method, and a spin-on-dip method using a stripping liquid is mentioned.

As a stripping liquid, for example, a stripping liquid obtained by dissolving a basic compound in at least one selected from the group consisting of water, dimethylsulfoxide, and N-methylpyrrolidone is mentioned. Examples of basic compounds (compounds that dissolve in water and exhibit basicity) include basic inorganic compounds such as sodium hydroxide and potassium hydroxide, primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary amine compounds. Basic organic compounds such as ammonium salt compounds. As the basic organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferable.

As a method for removing the photoresist pattern, there is a method of immersing the substrate with the remaining photoresist pattern in a stripping solution with a liquid temperature of 30-80°C (preferably 50-80°C) for 1-30 minutes. . It is also preferable that the stripping solution does not dissolve the conductive layer.

The pH of the stripping liquid at the time of the stripping treatment is preferably 11 or higher, more preferably 12 or higher, and still more preferably 13 or higher. The upper limit is preferably 14 or less, more preferably 13.8 or less. pH can be measured by the method based on JIS Z8802-1984 using a well-known pH meter. The measurement temperature of pH was set at 25°C. It is preferable that the liquid temperature °C of the stripping solution when performing the stripping treatment is higher than the liquid temperature °C of the developing solution when performing the developing treatment. Specifically, the value obtained by subtracting the liquid temperature °C of the above-mentioned developer from the liquid temperature °C of the above-mentioned stripping liquid (the liquid temperature °C of the above-mentioned stripping liquid-the liquid temperature °C of the above-mentioned developer) is preferably 10 °C or more, and 20 °C The above is better. The upper limit is preferably 100°C or lower, more preferably 80°C or lower. It is preferable that the pH of the stripping solution when performing the stripping treatment is higher than the pH of the developing solution when performing the developing treatment. Specifically, the value obtained by subtracting the pH of the developer from the pH of the stripping solution (pH of the stripping solution−pH of the developer) is preferably 1 or more, more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.

After stripping the photoresist pattern with the stripping solution, it is also preferable to perform a rinse process for removing the stripping solution remaining on the substrate. Water or the like can be used for the rinsing treatment. After the stripping and/or rinsing process of the photoresist pattern by the stripping liquid, a drying process for removing excess liquid from the substrate may be performed.

＜Removal procedure＞ When the method of manufacturing a laminate having a conductor pattern has a plating treatment step, 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 stripping step of the photoresist pattern to obtain a conductive pattern on the substrate. In addition, in the removal step, etching treatment of the conductive layer located in the non-pattern formation region (in other words, the region not protected by the plating layer) is performed using the plating layer formed by the plating step as an etching resist.

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

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

The 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 steps＞ The method of manufacturing a laminate having a conductor pattern may include other steps in addition to the above-mentioned steps. As other steps, for example, the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. 2019/022089 and the step of reducing the reflectance of visible light described in paragraph [0172] of International Publication No. The step of forming a new conductive layer on the surface of the film.

(Steps to reduce reflectance of visible light) The manufacturing method of the laminated body which has a conductor pattern may have the process of performing the process which reduces the visible light reflectance of a part or all of the conductor pattern which a laminated body has. As a treatment for lowering the reflectance of visible light, for example, an oxidation treatment is mentioned. When the laminate has a conductor pattern made of copper, the visible light reflectance of the laminate can be reduced by oxidizing the copper to become copper oxide and blackening the conductor pattern. As a treatment for reducing the reflectance of visible light, for example, paragraphs [0017] to [0025] of JP-A-2014-150118 and paragraphs [0041], [0042], and [0048] of JP-A-2013-206315 can be cited. ] and [0058] paragraphs, which are incorporated into this manual.

(The step of forming an insulating film, the step of forming a new conductive layer on the surface of the insulating film) The method of manufacturing a laminate having a conductive pattern may include a step of forming an insulating film on the surface of the laminate having a conductive pattern and a step of forming a new conductive layer (conductive pattern, etc.) on the surface of the insulating film. Through the above steps, the first electrode pattern and the insulated second electrode pattern can be formed. As a step of forming an insulating film, for example, a method of forming a known permanent film can be mentioned. In addition, an insulating film having a desired pattern can also be formed by photolithography using a photosensitive composition having insulating properties. As a step of forming a new conductive layer on the surface of the insulating film, for example, a photosensitive composition having conductivity can be used to form a new conductive layer of a desired pattern by photolithography.

In the method of manufacturing a laminate with a conductor pattern, a substrate having a plurality of conductive layers (metal layers, etc.) is used on both surfaces of the laminate, and a conductor pattern is formed sequentially or simultaneously using the conductive layers formed on both surfaces of the substrate Also better. With the above configuration, it is possible to form circuit wiring for a touch panel in which the first conductive pattern is formed on one substrate surface and the second conductive pattern is formed on the other substrate surface. Moreover, it is also preferable to form the circuit wiring for touch panels of the said structure from both surfaces of a board|substrate in a roll-to-roll system.

[Applications of laminates having conductor patterns] The laminated body having a conductor pattern manufactured by the above-mentioned manufacturing method is preferably used for a semiconductor package, a printed circuit board, and a process film of an interposer rewiring layer, for example. As a device provided with a layered body having a conductive pattern manufactured by the above-mentioned manufacturing method, for example, an input device is mentioned, and a touch panel is preferable, and a capacitive type touch panel is more preferable. In addition, the input device described above can be applied to display devices such as organic EL display devices and liquid crystal display devices. [Example]

Hereinafter, the present invention will be further described in detail based on examples. Materials, usage amounts, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed unless departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the Examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass. Hereinafter, the weight average molecular weight of the resin is the weight average molecular weight (Mw), the number average molecular weight (Mn) and the degree of dispersion (Mw/Mn) obtained in terms of polystyrene based on the gel permeation chromatography (GPC) above. . In addition, the theoretical acid value was used for the acid value.

[various ingredients] [resin] ＜Synthesis of Resin A1-1＞ Propylene glycol monomethyl ether (9.7 g) and propylene glycol monomethyl ether acetate (9.7 g) were charged into 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 (OSAKA ORGANIC CHEMICAL GBLMA (manufactured by INDUSTRY LTD.) (6.2 g) and polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) (1.7 g) were dissolved in propylene glycol monomethyl ether (5 g), propylene glycol monomethyl ether acetate (5 g ) and polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) (1.7g) dissolved in propylene glycol monomethyl ether (9.7g) and propylene glycol monomethyl ether acetate (9.7g) solution. After the dropwise addition was completed, V-601 (0.6 g) was added 3 times every 1 hour. Thereafter, it was further reacted for 3 hours. Thereafter, it was diluted with propylene glycol monomethyl ether acetate to obtain a solution of resin A1-1 with a solid content concentration of 30%. The weight average molecular weight in terms of standard polystyrene based on GPC was 23,000, the degree of dispersion was 2.2, and the acid value of the polymer was 150 mgKOH/g. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers. Resins A1-2 to A1-5, A1-7 to A1-9, A2-1, and A2-2 were synthesized by the same method. In addition, any of the above-mentioned resins was obtained as a solution having a solid content concentration of 30%. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers.

＜Synthesis of Resin A1-6＞ Propylene glycol monomethyl ether (17.2 g) was charged to the flask and heated to 90°C under nitrogen flow. To this liquid, styrene (15.3 g), γ-butyrolactone methacrylate (GBLMA manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) (10.6 g), methacrylic acid (16.4 g) were added dropwise over 3 hours. ), a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) (3.7 g) dissolved in propylene glycol monomethyl ether (13.3 g). After the dropwise addition was completed, V-601 (0.5 g) was added three times per hour. Thereafter, it was further reacted for 3 hours. Then, it diluted with propylene glycol monomethyl ether acetate (23.8g) and propylene glycol monomethyl ether (33.9g). Under air flow, the temperature of the reaction liquid was raised to 100° C., and tetraethylammonium bromide (0.24 g) and p-methoxyphenol (0.11 g) were added thereto. Glycidyl methacrylate (BLEMMER G manufactured by NOF CORPORATION) (10.5 g) was added dropwise thereto over 20 minutes. It was made to react at 100 degreeC for 7 hours, after that, it diluted with propylene glycol monomethyl ether acetate, and obtained the solution of resin A1-6 whose solid content concentration was 30%. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers. Resins A2-3 and A2-4 were synthesized by the same method. In addition, any of the above-mentioned resins was obtained as a solution having a solid content concentration of 30%. The amount of residual monomers measured by gas chromatography did not reach 0.1% by mass with respect to the polymer solid content in any of the monomers.

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

[chemical formula 13]

In the following table, the column of “acid value before hydrolysis” shows the acid value (theoretical acid value) (mgKOH/g) before hydrolyzing the specific group of each resin. The "acid value increased by hydrolysis" column shows the theoretical acid value (mgKOH/g) of the amount increased from the theoretical acid value (mgKOH/g) before hydrolyzing the specific group of each resin when the specific group of each resin is hydrolyzed. Specifically, the theoretical acid value (mgKOH/g) derived from the acid group (for example, carboxyl group, etc.) generated when a specific group of each resin is hydrolyzed is shown, and "acid value increased by hydrolysis=acid value increased by hydrolysis The amount of generated carboxyl groups (mmol/g) × molecular weight of KOH" was calculated.

[Table 1] Table 1 Weight average molecular weight (Mw) Dispersion Acid value before hydrolysis (mgKOH/g) Acid value increased by hydrolysis (mgKOH/g) A1-1 23000 2.3 150 40 A1-2 27000 2.8 150 76 A1-3 40000 2.5 98 79 A1-4 46000 2.6 150 50 A1-5 12000 2.1 150 172 A1-6 24000 2.8 124 66 A1-7 23000 2.3 150 99 A1-8 23000 2.3 150 twenty three A1-9 20000 2.2 124 26 A2-1 22000 2.1 150 - A2-2 22000 2.1 190 - A2-3 18000 2.6 124 - A2-4 17000 2.4 95 -

〔Photosensitive composition〕 Each photosensitive composition was prepared with the components and formulation shown in the table below. In the table, the numerical value described in the column of each component shows the content (parts by mass) of each component.

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

[chemical formula 14]

＜Polymerizable compound＞ SR454: Ethoxylated (3) trimethylolpropane trimethacrylate, manufactured by TOMOE Engineering Co., Ltd. ・BPE-500: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・BPE-100: Ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. ・M270: ARONIX M-270, polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO.,LTD. 4G: NK Ester 4G, polyethylene glycol #200 dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

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

＜Sensitizer＞ 4,4'-bis(diethylamino)benzophenone

＜Polymerization inhibitor＞ · Phenothiophene 𠯤

＜Antioxidant＞ ·Phenidone

＜Pigment＞ ・Colorless crystal violet, manufactured by Tokyo Chemical Industry Co., Ltd.

＜Rust inhibitor＞ ・CBT-1: carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO.,LTD.

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

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

[Components of the intermediate layer forming composition] The intermediate layer included in the transfer film was formed using the composition for intermediate layer formation prepared using the components and formulations shown in the table.

＜Resin＞ ・PVA: Polyvinyl alcohol, product name "KURARAY POVAL PVA-205", manufactured by Kuraray Co., Ltd. ・PVP: Polyvinylpyrrolidone, 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: MEGAFACE F444, fluorine-based surfactant, manufactured by DIC Corporation

<Solvent> · Methanol ·water

[evaluate] 〔Evaluation of hydrolyzability〕 Hydrolyzability was evaluated by the following procedure for the verification compound using γ-butyrolactone methacrylate as a compound having a lactone group and the verification compound using phenylsuccinic anhydride as an acid anhydride. The compounds for verification were respectively dissolved in acetonitrile, and a 10% by mass KOH aqueous solution (pH 14) was mixed so that KOH became 2 mol equivalents with respect to each compound for verification. After stirring for 1 minute, acetic acid was added to adjust the pH to 6. The remaining amount of each verification compound was measured for the obtained solution using HPLC. As a result, it was confirmed that the residual amount of γ-butyrolactone methacrylate and phenylsuccinic anhydride was higher than that of each verification compound before adding KOH. The total mass (mass % relative to the input amount) is all 1 mass % or less, and the compound and acid anhydride having a lactone group show hydrolyzability. In addition, it was confirmed that a carboxyl group was generated in each verification compound after addition of KOH.

〔Production of transfer film〕 Each transfer film composed of a dummy support, an intermediate layer and a photosensitive composition layer was produced. The specific procedure is shown below. First, an intermediate layer is formed by applying a bar coater on a dummy support (polyethylene terephthalate film with a thickness of 16 μm (LUMIRROR 16KS40, manufactured by TORAY INDUSTRIES, INC.)) so that the thickness after drying becomes 1.0 μm. Using the composition, an intermediate layer was formed at 90° C. using an oven. Furthermore, a photosensitive composition was applied on the intermediate layer with a bar coater so that the thickness after drying became 3.0 μm, and dried at 80° C. using an oven to form a photosensitive composition layer (negative photosensitive layer ). On the obtained photosensitive composition layer, polyethylene terephthalate (16KS40, manufactured by TORAY INDUSTRIES, INC.) with a thickness of 16 μm was crimped as a protective film, and the transfer used in each example or each comparative example was produced. membrane.

[Manufacturing of laminates with conductor patterns] A PET substrate with a copper layer in which a copper layer with a thickness of 500 nm was formed on a PET film (polyethylene terephthalate film) with a thickness of 188 μm by sputtering was used. Cut the produced transfer film into 50cm squares, peel off the protective film, and make the photosensitive composition layer contact with the copper layer on the surface of the PET substrate, at a roller temperature of 90°C, a line pressure of 0.8MPa, and a line speed of 3.0m/ The laminated body was obtained by laminating on a PET substrate with a copper layer under lamination conditions of min. At this point, the laminate has a configuration of "PET film-copper layer-photosensitive composition layer-intermediate layer-dummy support". For bonding, the dummy support is 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 is 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 Japan Science Engineering Co., Ltd., dominant wavelength: 365 nm). The exposure amount was set as the exposure amount for reproducing a 5 μm line-and-space shape in the resist pattern obtained after development. Thereafter, development was performed using a 28° C. 1.0% sodium carbonate aqueous solution (pH 11.4) as a developing solution. Specifically, after performing shower processing for 30 seconds during image development and performing air knife (Air Knife) processing to shake off the developing solution, shower processing was performed with pure water for 30 seconds and further air knife processing was performed. Let the up to now be the first pattern formation stage. Thereby, a laminate having a resist pattern in a line and space shape with line width:space width=1:1 was obtained. The laminate at this point had a configuration of "PET film-copper layer-photoresist pattern".

<Minimum analytical line width> In the above-mentioned first pattern formation stage, the minimum line width that can be formed without developing residue, pattern collapse, etc. is defined as the minimum analysis line width μm.

＜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 (curling at the minimum analytical line width) was evaluated based on the following evaluation criteria. A: Pattern shape without curling B: Slightly curled C: curled shape

<Evaluation of photoresist pattern detachability> The laminate obtained in the first pattern forming step was put into a copper sulfate plating solution (copper sulfate 75g/L, sulfuric acid 190g/L, chloride ion 50 mass ppm, manufactured by Meltex Inc., In "Copper Glyme PCM", 5mL/L), copper plating was performed under the condition of 1A/dm ² . The laminated body after the copper plating treatment was washed with water and dried, and then immersed in a 1 mass % potassium hydroxide aqueous solution (pH 13.5) at 50° C., thereby peeling off the resist pattern. The peeling was performed while changing the peeling time, and the time for the resist pattern to be peeled in the 5 μm line-and-space pattern was evaluated as follows. In addition, the shorter the time, the better the detachability. A: Less than 30 seconds B: More than 30 seconds and less than 60 seconds C: More than 60 seconds and less than 120 seconds D: More than 120 seconds

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

＜Etching-based conductor pattern formation and conductor pattern linearity (LWR) evaluation＞ It carried out similarly up to the said 1st pattern formation stage, and obtained the board|substrate (layered body which has a photoresist pattern) on which the resist pattern was formed. The substrate on which the photoresist pattern was formed (the laminate with the photoresist pattern) was etched with a copper etchant (Cu-02: manufactured by Kanto Chemical Co., Inc.) at 23°C for 30 seconds, and then an alkanolamine aqueous solution system was used to etch The stripping solution (pH 13.1) stripped the photoresist pattern at 40° C., thereby obtaining a substrate (laminated body having a conductor pattern) on which copper wiring was patterned. The measurement was performed at 100 locations about the line widths at locations randomly selected from the 5 μm line-and-space copper wiring pattern. The standard deviation (unit: nm) of the obtained line width was obtained, and the value of the standard deviation was defined as LWR (Line Width Roughness: line width roughness). The obtained LWR values were classified according to the following classification, and the conductor pattern linearity (LWR) was evaluated. In addition, the smaller the LWR is, the smaller the variation in the line width is, which is preferable. A: LWR does not reach 150nm B: LWR is more than 150nm and less than 200nm C: LWR is more than 200nm and less than 300nm D: LWR is 300nm or more

[Table 2] Example 1 2 3 4 5 6 7 8 9 10 11 photosensitive composition Resin (30% by mass solution) A1-1 25.2 A1-2 25.2 A1-3 25.2 A1-4 25.2 A1-5 25.2 A1-6 25.2 A1-7 25.2 A1-8 25.2 A1-9 25.2 A2-1 24.2 A2-2 A2-3 24.2 A2-4 Compound (D) SMA EF-40 1.5 MMA/GBLMA 1.5 ADBL polymeric compound SR454 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 BPE500 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 BPE100 M270 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 4G polymerization initiator 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer 1 1 1 1 1 1 1 1 1 1 1 Sensitizer 4,4'-Bis(diethylamino)benzophenone 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 polymerization inhibitor phenothiophene 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Antioxidants Phenidone 0 0 0 0 0 0 0 0 0 0 0 pigment colorless crystal violet 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Rust inhibitor CBT-1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Surfactant F552 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 solvent MMPGAc 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 MEK 30 30 30 30 30 30 30 30 30 30 30 Composition for intermediate layer formation resin PVA 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 pvp 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 HPMC 1 1 1 1 1 1 1 1 1 1 1 Surfactant F444 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent Methanol 630 630 630 630 630 630 630 630 630 630 630 water 270 270 270 270 270 270 270 270 270 270 270 Evaluation results Minimum analytical line width (μm) 1 1 1 1 2 1 2 1 1 1 1 Photoresist pattern shape A A A A B A A A A A A Photoresist Pattern Release A A A A A A A A A A A copper pattern shape A A A A A A A A A A A LWR A A A A A A A A A A A

[table 3] Example comparative example 12 13 14 15 16 17 1 2 photosensitive composition Resin (30% by mass solution) A1-1 25.2 25.2 25.2 25.2 25.2 A1-2 A1-3 A1-4 A1-5 A1-6 A1-7 A1-8 A1-9 A2-1 25.2 A2-2 25.2 A2-3 A2-4 24.2 Compound (D) SMA EF-40 MMA/GBLMA ADBL 1.5 polymeric compound SR454 2.8 1.4 2.8 2.8 BPE500 2.8 2.8 1.4 5.6 5.6 2.8 2.8 BPE100 2.8 2.8 M270 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 4G 5.6 polymerization initiator 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer 1 1 1 1 1 1 1 1 Sensitizer 4,4'-Bis(diethylamino)benzophenone 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 polymerization inhibitor phenothiophene 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Antioxidants Phenidone 0 0 0 0 0 0 0 0 pigment colorless crystal violet 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Rust inhibitor CBT-1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Surfactant F552 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 solvent MMPGAc 37.3 37.3 37.3 37.3 37.3 37.3 37.3 37.3 MEK 30 30 30 30 30 30 30 30 Composition for intermediate layer formation resin PVA 67.5 67.5 67.5 67.5 67.5 67.5 67.5 67.5 pvp 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 HPMC 1 1 1 1 1 1 1 1 Surfactant F444 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent Methanol 630 630 630 630 630 630 630 630 water 270 270 270 270 270 270 270 270 Evaluation results Minimum analytical line width (μm) 1 1 1 1 1 1 2 4 Photoresist pattern shape A A A A A A B C Photoresist Pattern Release A A A A A A D. B copper pattern shape A A A A A A B C LWR A A A A A A B D.

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

Except for using the polyester film (6.9 μm in thickness) described in Example 1 of JP 2000-309650 as a dummy support, Example 1 was used by the same procedure as the above [production of transfer film]. ~17 photosensitive composition to make a transfer film. For each of the obtained transfer films, the minimum analytical line width, resist pattern shape, resist pattern peelability, copper pattern shape, and LWR were evaluated in the same manner as above. A result of 1 to 17 is equivalent to a good result.

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

FIG. 1 is a schematic diagram showing an example of the structure of a transfer film.

none.

Claims (21)

A transfer film, which has a pseudo-support and a photosensitive composition layer, wherein The photosensitive composition layer includes resin A, a polymerizable compound, and a polymerization initiator, The said resin A contains the structural unit a which has the base which forms an alkali-soluble group by the action of a base, and the structural unit b which has an acidic group. The transfer film as described in claim 1, wherein The aforementioned structural unit a includes a structural unit having an alkali-decomposable group. The transfer film as described in claim 1 or claim 2, wherein The aforementioned structural unit a includes a structural unit having a group that generates an acidic group by the action of a base. The transfer film as described in claim 1 or claim 2, wherein The aforementioned structural unit a includes 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. The transfer film as described in claim 1 or claim 2, wherein The content of the aforementioned structural unit a is 5 to 50% by mass relative to all the structural units of the aforementioned resin A, Content of the said structural unit b is 10-30 mass % with respect to all the structural units of the said resin A. A transfer film, which has a pseudo-support and a photosensitive composition layer, wherein The photosensitive composition layer includes a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B, The aforementioned resin B includes a structural unit b having an acid group, The aforementioned compound D has a base that generates an alkali-soluble group through the action of a base, Content of the said compound D is 5-50 mass % with respect to the gross mass of a photosensitive composition layer. The transfer film as described in claim 6, wherein The aforementioned compound D includes a constituent unit having an alkali-decomposable group. The transfer film as described in Claim 6 or Claim 7, wherein The aforementioned compound D includes a structural unit having a group that generates an acid group by the action of a base. The transfer film as described in Claim 6 or Claim 7, wherein The aforementioned 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. The transfer film according to claim 1, claim 2, claim 6, or claim 7, further comprising an intermediate layer between the dummy support and the photosensitive composition layer. The transfer film as described in claim 10, wherein The aforementioned intermediate layer contains a water-soluble resin. The transfer film as described in Claim 11, wherein The aforementioned water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, and polyamides. at least one of the group of amine resins. A method of manufacturing a laminate with a conductor pattern, comprising: Bonding step, in such a way that the photosensitive composition layer side of the transfer film described in any one of Claim 1 to Claim 12 is in contact with the aforementioned conductive layer of the substrate having a conductive layer on the surface, the aforementioned transfer film Bonding with the aforementioned substrate; Exposure step, exposing the aforementioned photosensitive composition layer; A photoresist pattern forming step, performing a development treatment on the exposed photosensitive composition layer to form a photoresist pattern; Any one of the etching step of performing etching treatment and the electroplating treatment step of performing electroplating treatment on the aforementioned conductive layer located in the region where the aforementioned photoresist pattern is not arranged; and Photoresist pattern stripping step, stripping the aforementioned photoresist pattern, When there is the aforementioned electroplating treatment step, there is further a removal step of removing the aforementioned conductive layer exposed due to the aforementioned photoresist pattern stripping step and forming a conductive pattern on the aforementioned substrate, wherein Between the laminating step and the exposing step or between the exposing step and the developing step, there is further a dummy support peeling step for peeling off the dummy support. The method of manufacturing a laminate having a conductor pattern according to claim 13, wherein The aforementioned photoresist pattern stripping step is a step of stripping the aforementioned photoresist pattern using a stripping solution, The pH of the stripping solution is 13 or higher. The method of manufacturing a laminate having a conductor pattern according to claim 13, wherein The aforementioned step of forming a photoresist pattern is a step of performing a development process using a developer to form a photoresist pattern, The pH of the developer was less than 13. The method of manufacturing a laminate having a conductor pattern according to claim 13, wherein The exposure method in the foregoing exposure step is any one of mask exposure, direct imaging exposure and projection exposure. The method of manufacturing a laminate having a conductor pattern according to claim 13, wherein The thickness of the aforementioned pseudo-support was less than 16 μm. The method for manufacturing a laminate with a conductor pattern according to any one of claim 13 to claim 17, which includes the dummy support stripping step between the laminating step and the exposing step, The photosensitive composition layer is exposed by bringing the exposed surface exposed in the dummy support peeling step into contact with a mask. A photosensitive composition comprising a resin C, a polymerizable compound and a polymerization initiator, The said resin C contains the structural unit which has a lactone group, and the structural unit b which has an acidic group. The photosensitive composition as described in Claim 19, wherein The content of the structural unit having a lactone group is 5 to 50% by mass relative to all the structural units of the resin C, and the content of the structural unit b is 10 to 30% by mass relative to all the structural units of the resin C. A photosensitive composition comprising resin B, a polymerizable compound, a polymerization initiator and a compound DA different from resin B, The aforementioned resin B includes a structural unit b having an acid group, The aforementioned compound DA contains a base with a lactone group, Content of the said compound DA is 5-50 mass % with respect to the total solid content of a photosensitive composition.

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