WO2023119998A1

WO2023119998A1 - Method for producing laminate having conductor pattern, photosensitive composition, and transfer film

Info

Publication number: WO2023119998A1
Application number: PCT/JP2022/043073
Authority: WO
Inventors: 邦彦児玉; 壮二石坂; 悠鬼塚
Original assignee: 富士フイルム株式会社
Priority date: 2021-12-24
Filing date: 2022-11-21
Publication date: 2023-06-29
Also published as: TW202331751A

Abstract

This invention provides a method for producing a laminate having a conductor pattern, said method comprising, in the following order: preparing a laminate including a substrate and a conductive layer in that order; providing on the conductive layer a photosensitive composition layer containing a resin that includes a structural unit represented by formula B1 and a structural unit having an alkali-soluble group; exposing the photosensitive composition layer; performing a development process on the photosensitive composition layer to form a resist pattern; plating the conductive layer in a region where the resist pattern is not located; removing the resist pattern; and forming a conductor pattern by removing the conductive layer exposed by removing the resist pattern. This invention also provides technology related to said method.

Description

Method for producing laminate having conductor pattern, photosensitive composition and transfer film

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

Conductor patterns are applied to various articles such as printed circuit boards and display devices. For example, a conductor pattern is formed at a desired position by plating using a resist pattern (see, for example, JP-A-2016-139154).

In the conventional method of manufacturing a conductive pattern by plating using a resist pattern, there is a demand for improving the resolution of the resist pattern. In the present disclosure, "resolution" means the minimum resolvable line width (hereinafter sometimes referred to as "minimum resolution line width").

An object of an embodiment of the present disclosure is to provide a method for manufacturing a laminate having a conductor pattern with improved resolution of a resist pattern used for forming the conductor pattern. An object of another embodiment of the present disclosure is to provide a photosensitive composition that forms a resist pattern with excellent resolution. An object of another embodiment of the present disclosure is to provide a transfer film that forms a resist pattern with excellent resolution.

The present disclosure includes the following aspects.
<1> Prepare a laminate containing a substrate and a conductive layer in this order, and prepare a photosensitive composition layer containing a resin containing a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group. , providing on the conductive layer, exposing the photosensitive composition layer, developing the photosensitive composition layer to form a resist pattern, and disposing the resist pattern. performing a plating process on the conductive layer in a region not exposed to the conductive layer; removing the resist pattern; and removing the conductive layer exposed by removing the resist pattern to form a conductive pattern. , in this order.

In formula B1, X ^B1 and X ^B2 each independently represent —O— or —NR ^N —, R ^N represents a hydrogen atom or an alkyl group, and L is a divalent group containing no hydroxy group. and R ^B1 and R ^B2 each independently represent a hydrogen atom or an alkyl group.

<2> Providing the photosensitive composition layer includes preparing a transfer film containing a temporary support and the photosensitive composition layer in this order, and the photosensitive composition layer and the conductive layer of the transfer film. A method for producing a laminate having a conductor pattern according to <1>, comprising:
<3> Further comprising peeling the temporary support between bonding the photosensitive composition layer and the conductive layer and exposing the photosensitive composition layer, <2> A method for producing a laminate having the conductor pattern according to 1.
<4> The method for producing a laminate having a conductor pattern according to <2> or <3>, wherein the transfer film further includes an intermediate layer between the temporary support and the photosensitive composition layer.
<5> The method for producing a laminate having a conductor pattern according to any one of <1> to <4>, wherein the photosensitive composition layer further contains a photopolymerization initiator and a polymerizable compound. .
<6> The method for producing a laminate having a conductive conductor pattern according to <5>, wherein the photopolymerization initiator is a hexaarylbiimidazole compound.
<7> The method for producing a laminate having a conductor pattern according to <5> or <6>, wherein the polymerizable compound contains a radically polymerizable compound having at least two polymerizable groups.
<8> The polymerizable compound contains a radically polymerizable compound having two polymerizable groups, and the ratio of the content of the radically polymerizable compound having two polymerizable groups to the content of the polymerizable compound is A method for producing a laminate having the conductor pattern according to <5> or <6>, which is 80% by mass or more.
<9> The method for producing a laminate having a conductor pattern according to any one of <5> to <8>, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure.
<10> The polymerizable compound contains a polymerizable compound having a bisphenol structure, and the ratio of the content of the polymerizable compound having a bisphenol structure to the content of the polymerizable compound is 50% by mass or more. 5> A method for producing a laminate having a conductor pattern according to any one of <8>.
<11> A resin containing a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group, a photopolymerization initiator, and a polymerizable compound, wherein the photopolymerization initiator is hexaarylbiimidazole A photosensitive composition, which is a compound.

<12> The photosensitive composition according to <11>, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure.
<13> The polymerizable compound contains a polymerizable compound having a bisphenol structure, and the ratio of the content of the polymerizable compound having the bisphenol structure to the content of the polymerizable compound is 50% by mass or more. 11>, the photosensitive composition.
<14> A resin containing a temporary support and a photosensitive composition layer in this order, wherein the photosensitive composition layer includes a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group; A transfer film comprising a photopolymerization initiator and a polymerizable compound, wherein the photopolymerization initiator comprises a hexaarylbiimidazole compound.

<15> The transfer film according to <14>, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure.
<16> The polymerizable compound contains a polymerizable compound having a bisphenol structure, and the ratio of the content of the polymerizable compound having a bisphenol structure to the content of the polymerizable compound is 50% by mass or more. 14> The transfer film described in 14>.
<17> A temporary support and a photosensitive composition layer are included in this order, and the photosensitive composition layer includes a resin including a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group. , Transfer film for plating wiring formation.

<18> The transfer film for forming plated wiring according to <17>, further comprising an intermediate layer between the temporary support and the photosensitive composition layer.

According to one embodiment of the present disclosure, there is provided a method for manufacturing a laminate having a conductor pattern in which the resolution of the resist pattern used for forming the conductor pattern is improved. Another embodiment of the present disclosure provides a photosensitive composition that forms a resist pattern with excellent resolution. Another embodiment of the present disclosure provides a transfer film that forms a resist pattern with excellent resolution.

FIG. 1 is a schematic cross-sectional view of a transfer film according to one embodiment.

In the present disclosure, a numerical range represented using "~" means a range including the numerical values described before and after "~" as lower and upper limits.

In the stepwise numerical ranges shown in the present disclosure, the upper limit or lower limit stated in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range. In the present disclosure, upper or lower limits stated in certain numerical ranges may be replaced with values shown in Examples.

In the present disclosure, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended purpose is achieved.

"Transparent" in the present disclosure means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more. The average transmittance of visible light with a wavelength of 400 nm to 700 nm is preferably 90% or more.

In the present disclosure, the average transmittance of visible light is measured using a spectrophotometer. Spectrophotometers include, for example, spectrophotometer U-3310 manufactured by Hitachi, Ltd.

In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are converted using polystyrene as a standard substance by a gel permeation chromatography (GPC) analyzer based on the following conditions. is the value
Column: TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (Tosoh Corporation)
Eluent: Tetrahydrofuran (THF)
Detector: Differential Refractometer

In the present disclosure, unless otherwise specified, the molecular weight of compounds having a molecular weight distribution is the weight average molecular weight (Mw).

In the present disclosure, unless otherwise specified, the content of metal elements is measured using an inductively coupled plasma (ICP) spectroscopic analyzer.

"(Meth)acrylic" in the present disclosure is a concept that includes both acrylic and methacrylic.

In the present disclosure, "(meth)acryloyloxy group" is a concept that includes both acryloyloxy groups and methacryloyloxy groups.

"(Meth)acrylate" in the present disclosure is a concept that includes both acrylate and methacrylate.

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

In the present disclosure, "water-soluble" means the property of having a solubility of 0.1 g or more in 100 g of water having a pH of 7.0 and a liquid temperature of 22°C.

"Solid content" in the present disclosure means all components excluding solvent.

<Method for producing a laminate having a conductor pattern>
A method for manufacturing a laminate having a conductor pattern according to an embodiment of the present disclosure includes the following (1) to (7) in this order.
(1) Preparing a laminate including a substrate and a conductive layer in this order (hereinafter referred to as "laminate preparation step").
(2) Providing a photosensitive composition layer containing a resin containing a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group on the conductive layer (hereinafter referred to as "formation of a photosensitive composition layer process”).
(3) exposing the photosensitive composition layer (hereinafter referred to as "exposure step");
(4) Developing the photosensitive composition layer to form a resist pattern (hereinafter referred to as "development step").
(5) Plating the conductive layer in the region where the resist pattern is not arranged (hereinafter referred to as "plating process").
(6) removing the resist pattern (hereinafter referred to as "resist pattern removing step");
(7) removing the conductive layer exposed by removing the resist pattern to form a conductive pattern (hereinafter referred to as "the step of removing the conductive layer");

Hereinafter, "resin containing a structural unit represented by formula B1 and a structural unit having an alkali-soluble group" may be referred to as "resin (A)".

According to the above-described embodiments, there is provided a method for manufacturing a laminate having a conductor pattern in which the resolution of the resist pattern used for forming the conductor pattern is improved. It is presumed that the improvement in resist pattern resolution is due to the chemical structure of the structural unit represented by formula B1 contained in the resin (A). In particular, it is presumed that the divalent group not containing a hydroxy group represented by L in Formula B1 contributes to the improvement of the resolution of the resist pattern. L in formula B1 does not contain a hydroxy group. Therefore, according to the photosensitive composition layer containing the resin (A), expansion of the photosensitive composition layer due to permeation of the developer is reduced or prevented, and the resolution of the resist pattern is improved.

[Laminate preparation process]
The laminate preparation step is to prepare a laminate including a substrate and a conductive layer in this order. The laminate may be a commercially available product. The laminate may be manufactured by a process independent of the method of manufacturing the laminate having the conductor pattern. The laminate may be manufactured in a laminate preparation process.

Examples of substrates include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates. Preferred substrates include, for example, those described in paragraph [0140] of WO2018/155193.

The substrate is preferably a resin substrate. The resin substrate preferably contains polyethylene terephthalate, cycloolefin polymer or polyimide.

The average thickness of the substrate is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm. The average thickness of the substrate is determined by arithmetically averaging the thickness of the substrate measured at five locations.

Examples of conductive layers include metal layers. A metal layer is a layer containing a metal. Main components of the metal layer include, for example, copper, chromium, lead, nickel, gold, silver, tin and zinc. A "main component" means the metal with the maximum content among the metals contained in the object. The conductive layer is preferably a layer containing copper as a main component.

The average thickness of the conductive layer is preferably 50 nm or more, more preferably 100 nm or more. The average thickness of the conductive layer is preferably 2 μm or less. The average thickness of the conductive layer is obtained by a method according to the above-described method for calculating the average thickness of the substrate.

The laminate may include multiple conductive layers. For example, the laminate may include a conductive layer on each side of the substrate. In other words, the laminate may include the first conductive layer, the substrate, and the second conductive layer in this order.

Examples of methods for forming the conductive layer include a method of sintering a coating film formed by applying a dispersion liquid containing fine metal particles, sputtering, and vapor deposition.

The laminate may further include other layers within the scope of the present disclosure.

[Step of forming photosensitive composition layer]
The step of forming the photosensitive composition layer is to provide the photosensitive composition layer on the conductive layer. The photosensitive composition layer contains a resin containing a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group, that is, resin (A).

(Resin (A))
The photosensitive composition layer contains resin (A). As described above, the photosensitive composition layer containing the resin (A) reduces or prevents swelling of the photosensitive composition layer due to permeation of the developer, and improves the resolution of the resist pattern. Furthermore, the photosensitive composition layer containing the resin (A) can contribute to formation of a resist pattern having an excellent shape. The term "excellent shape" means that the cross-sectional shape of the object has a small difference between the line width at the upper end of the object and the line width at the lower end of the object. For example, the use of a photosensitive composition layer containing resin (A) tends to suppress the formation of a flared resist pattern.

In formula B1, R ^{3 N} is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, even more preferably a hydrogen atom.

In formula B1, X ^B1 and X ^B2 are preferably -O-.

In Formula B1, L is preferably a divalent group consisting only of carbon atoms and hydrogen atoms, ie, a divalent unsubstituted hydrocarbon group. Furthermore, L is preferably an unsubstituted alkylene group or an unsubstituted arylene group, more preferably an unsubstituted alkylene group. The unsubstituted alkylene group may be an unsubstituted linear alkylene group. The unsubstituted alkylene group may be an unsubstituted branched alkylene group. The unsubstituted alkylene group may be an unsubstituted cyclic alkylene group. The unsubstituted alkylene group preferably has 2 to 8 carbon atoms. The unsubstituted alkylene group is preferably an unsubstituted ethylene group, an unsubstituted propylene group, an unsubstituted butylene group, an unsubstituted hexylene group or an unsubstituted cyclohexylene group, and is -CH ₂ CH ₂ - or -CH(CH ₃ ). CH ₂ — is more preferred. The unsubstituted arylene group is preferably an unsubstituted phenylene group.

In formula B1, the number of carbon atoms in the alkyl group represented by R ^{1 B1} is preferably 1 to 3, more preferably 1 or 2. In formula B1, the number of carbon atoms in the alkyl group represented by R ^{2 B2} is preferably 1 to 3, more preferably 1 or 2. R ^B1 and R ^B2 are each independently preferably a hydrogen atom or a methyl group.

Examples of the monomer forming the structural unit represented by Formula B1 include a monomer represented by Formula B2 below and a monomer represented by Formula B3 below. For example, a monomer represented by formula B2 or formula B3 below forms a structural unit represented by formula B1 through polymerization and an elimination reaction using a basic compound. An elimination reaction using a basic compound forms an ethylenically unsaturated group in a structural unit derived from a monomer represented by the following formula B2 or the following formula B3.

R ^B1 , X ^B1 , X ^B2 and L in formulas B2 and B3 are synonymous with R ^B1 , X ^B1 , X ^B2 and L in formula B1, respectively. R ^B4 and R ^B5 in formulas B2 and B3 are synonymous with R ^B2 in formula B1. In formulas B2 and B3, A ^B1 and A ^B2 each independently represent a halogen atom. A ^B1 and A ^B2 are each independently preferably a chlorine atom, a bromine atom or an iodine atom

Examples of basic compounds used in the elimination reaction include inorganic base compounds and organic base compounds. Inorganic base compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate. Organic base compounds include, for example, metal alkoxides (eg, sodium methoxide, sodium ethoxide and potassium tert-butoxide), triethylamine, pyridine and diazabicycloundecene (DBU).

Specific examples of the monomer represented by Formula B2 or Formula B3 are shown below. However, the types of monomers represented by Formula B2 or Formula B3 are not limited to the following specific examples.

Specific examples of the structural unit represented by Formula B1 are shown below. However, the type of structural unit represented by formula B1 is not limited to the following specific examples. Each R in the structural units below independently represents a hydrogen atom or a methyl group. Among the following specific examples, structural units represented by formula B1-1 are preferred.

The resin (A) may contain one or more structural units represented by Formula B1.

The content of the structural unit represented by formula B1 is preferably 15% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, relative to the total mass of the resin (A). , more preferably 25% by mass to 60% by mass

Examples of alkali-soluble groups include acid groups. Acid groups include, for example, carboxy groups, sulfo groups, phosphoric acid groups and phosphonic acid groups. The acid group is preferably a carboxy group.

The constituent unit having an alkali-soluble group is preferably a constituent unit derived from a monomer having a carboxy group. Examples of monomers having a carboxy group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid and 4-vinylbenzoic acid. The structural unit derived from the monomer having a carboxy group is preferably a structural unit derived from acrylic acid or a structural unit derived from methacrylic acid.

The structural unit having an alkali-soluble group is preferably a structural unit represented by the following formula (B).

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

The resin (A) may contain one or more structural units having an alkali-soluble group.

The content of the structural unit having an alkali-soluble group is preferably 5% by mass to 50% by mass, more preferably 8% by mass to 40% by mass, relative to the total mass of the resin (A). It is more preferably 10% by mass to 30% by mass, and particularly preferably 14% by mass to 25% by mass.

The resin (A) may further contain other structural units in addition to the structural unit represented by Formula B1 and the structural unit having an alkali-soluble group.

From the viewpoint of suppressing line width thickening and deterioration of resolution when the focus position shifts during exposure, the resin (A) should further contain a structural unit derived from a monomer having an aromatic hydrocarbon group. is preferred. Aromatic hydrocarbon groups include, for example, phenyl groups and aralkyl groups.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimers and styrene trimers). A monomer having an aralkyl group or styrene is preferred, and styrene is more preferred.

When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units derived from styrene is preferably 10% by mass to 80% by mass with respect to the total mass of the resin (A). , more preferably 20% by mass to 60% by mass, and even more preferably 25% by mass to 55% by mass. When the photosensitive composition layer contains two or more resins (A), the mass average content of structural units having an aromatic hydrocarbon group is preferably within the above range.

The aralkyl group includes, for example, a phenylalkyl group, preferably a benzyl group.

Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group (eg, benzyl (meth)acrylate and chlorobenzyl (meth)acrylate). Examples of monomers having a benzyl group include vinyl monomers having a benzyl group (eg, vinylbenzyl chloride and vinylbenzyl alcohol). The monomer having a benzyl group is preferably a (meth)acrylate having a benzyl group, more preferably a benzyl (meth)acrylate.

When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of structural units derived from benzyl (meth)acrylate is from 10% by mass to the total mass of the resin (A). It is preferably 80% by mass, more preferably 20% to 60% by mass, even more preferably 25% to 55% by mass.

The content of structural units derived from a monomer having an aromatic hydrocarbon group is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the resin (A). It is preferably 25% by mass or more, and more preferably 25% by mass or more. The content of structural units derived from a monomer having an aromatic hydrocarbon group is preferably 80% by mass or less, more preferably 60% by mass or less, relative to the total mass of the resin (A). It is preferably 55% by mass or less, and more preferably 55% by mass or less. When the photosensitive composition layer contains two or more resins (A), the mass average content of structural units derived from the monomer having an aromatic hydrocarbon group is preferably within the above range. .

The resin (A) may further contain a structural unit derived from a monomer having no acid group and having a polymerizable group. The polymerizable group may be selected from the polymerizable groups of the polymerizable compounds described below.

Examples of monomers having no acid group and having a polymerizable group include (meth)acrylate compounds. (Meth)acrylate compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.

Examples of monomers having no acid group and having a polymerizable group include ester compounds of vinyl alcohol. Vinyl alcohol ester compounds include, for example, vinyl acetate.

Examples of monomers having no acid group and having a polymerizable group include (meth)acrylonitrile.

The monomer having no acid group and having a polymerizable group is methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate or n-butyl (meth)acrylate. is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

The content of structural units derived from a monomer having no acid group and having a polymerizable group is 1% by mass to 80% by mass with respect to the total mass of the resin (A). is preferred, more preferably 1% by mass to 60% by mass, and even more preferably 1% by mass to 50% by mass.

The side chain of the resin (A) may have a linear structure, branched structure or alicyclic structure. Examples of the method for introducing a linear structure into the side chain of the resin (A) include a method using a monomer having a group having a linear structure. Examples of the method for introducing a branched structure into the side chain of the resin (A) include a method using a monomer having a group having a branched structure. Examples of the method for introducing an alicyclic structure into the side chain of the resin (A) include a method using a monomer having a group having an alicyclic structure. Alicyclic structures may be monocyclic or polycyclic.

In the present disclosure, "side chain" means an atomic group branched from the main chain. In the present disclosure, "backbone" means the longest relatively connecting chain in the molecule.

The resin (A) may further contain a structural unit derived from a monomer having a group with a branched structure. Resin (A) may further contain a structural unit derived from a monomer having a group having an alicyclic structure.

Examples of the monomer having a group having a branched structure include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and (meth)acrylate. Isoamyl acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert-octyl (meth)acrylate. be done. Isopropyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

Examples of the monomer having a group having an alicyclic structure include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Examples of monomers having a group having an alicyclic structure include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Examples of the monomer having a group having an alicyclic structure include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid -2-adamantyl, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, (meth)acrylic Acid-3-methyl-5-ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1- adamantyl, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4 (meth)acrylate, 7-menthanoinden-5-yl, (meth) octahydro-4,7-menthanoinden-1-ylmethyl acrylate, (meth) 1-menthyl acrylate, (meth) tricyclodecane acrylate, (meth) ) 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo (meth)acrylate [4.1. 0] heptyl, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate and cyclohexyl (meth)acrylate mentioned. Cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate , 1-menthyl (meth)acrylate or tricyclodecane (meth)acrylate is preferable, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid -2-adamantyl or tricyclodecane (meth)acrylate is more preferred.

The weight average molecular weight of the resin (A) is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, even more preferably 10,000 to 50,000. , 10,000 to 30,000 are particularly preferred. When the weight average molecular weight of resin (A) is 500,000 or less, resolution and developability are improved. When the weight-average molecular weight of resin (A) is 5,000 or more, the properties of development aggregates and the properties of unexposed films (for example, edge-fuse properties and cut-chip properties) are easily controlled. The term "edge fusibility" means the degree of easiness of protrusion of the photosensitive composition layer in the photosensitive composition layer wound into a roll. "Cut chip resistance" means the degree of ease of chip flying when an unexposed film is cut with a cutter.

The dispersity (that is, weight average molecular weight/number average molecular weight) of the resin (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and 1.0 It is more preferably up to 4.0, and particularly preferably 1.0 to 3.0.

The glass transition temperature (Tg) of the resin (A) is preferably 30°C to 135°C. The resin (A) having a glass transition temperature of 135° C. or less can suppress widening of the line width and deterioration of resolution when the focus position is shifted during exposure. The glass transition temperature of resin (A) is more preferably 130° C. or lower, still more preferably 120° C. or lower, and particularly preferably 110° C. or lower. A resin (A) having a glass transition temperature of 30° C. or higher can improve edge fuse resistance. The glass transition temperature of resin (A) is more preferably 40° C. or higher, still more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher.

The acid value of the resin (A) is preferably 60 mgKOH/g to 200 mgKOH/g, more preferably 70 mgKOH/g to 180 mgKOH/g, even more preferably 90 mgKOH/g to 160 mgKOH/g. "Acid number" means the mass (mg) of potassium hydroxide required to neutralize 1 g of sample. The acid value is determined by a method conforming to "JIS K0070:1992".

The photosensitive composition layer may contain one or more resins (A).

From the viewpoint of resolution and shape of the resist pattern, the content of the resin (A) is preferably 30% by mass or more, more preferably 40% by mass or more, relative to the total mass of the photosensitive composition layer. is more preferable, and 50% by mass or more is even more preferable. From the viewpoint of developability, the content of the resin (A) is preferably 95% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass, based on the total mass of the photosensitive composition layer. % or less.

(Photoinitiator)
The photosensitive composition layer preferably further contains a photopolymerization initiator.

A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photoinitiator may be a known photoinitiator. Photopolymerization initiators include, for example, radical photopolymerization initiators and cationic photopolymerization initiators. The photopolymerization initiator is preferably a photoradical polymerization initiator.

From the viewpoint of photosensitivity, visibility of exposed areas, visibility of unexposed areas, resolution, and resist pattern shape, the photopolymerization initiator (preferably a photoradical polymerization initiator) contains a hexaarylbiimidazole compound. is preferred. Furthermore, the photopolymerization initiator (preferably photoradical polymerization initiator) is preferably a hexaarylbiimidazole compound. Hexaarylbiimidazole compounds include, for example, 2,4,5-triarylimidazole dimers and derivatives thereof. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different. Derivatives of 2,4,5-triarylimidazole dimer include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di (Methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer and 2-( p-Methoxyphenyl)-4,5-diphenylimidazole dimer.

Other radical photopolymerization initiators include, for example, radical photopolymerization initiators having an oxime ester structure, radical photopolymerization initiators having an α-aminoalkylphenone structure, and radical photopolymerization initiators having an α-hydroxyalkylphenone structure. , photoradical polymerization initiators having an acylphosphine oxide structure and photoradical polymerization initiators having an N-phenylglycine structure.

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

Other photoradical polymerization initiators include, for example, ethyl dimethylaminobenzoate (DBE), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (Midori Chemical Co., Ltd.), benzophenone, 4, 4′-bis(diethylamino)benzophenone, TAZ-111 (Midori Chemical Co., Ltd.), 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (IRGACURE® ) OXE-01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (IRGACURE OXE-02, BASF Company), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) Phenyl]-1-butanone (Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Omnirad 907, IGM Resins B.V.) company), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (Omnirad 127, IGM Resins B.V. ), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1 -one (Omnirad 1173, IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (Omnirad 184, IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (Omnirad 651, IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethyl Benzoryl)phenylphosphine oxide (Omnirad 819, IGM Resins B.V.), oxime ester photoinitiator (Lunar
6, DKSH Japan), 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer isomer) (B-CIM, 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-benzoyloxime) (TR-PBG-305, Changzhou Power Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl -6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (TR-PBG-326, Changzhou Power Electronics New Materials Co., Ltd.) and 3-cyclohexyl-1- (6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

A photocationic polymerization initiator (also called a photoacid generator) is a compound that generates an acid upon receiving actinic rays. The photocationic polymerization initiator is preferably a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more (preferably a wavelength of 300 nm to 450 nm). Among the photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or longer, compounds that generate acid in response to actinic rays with a wavelength of 300 nm or longer when used in combination with a sensitizer are used in combination with the sensitizer. may

The photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less. More preferably, it is a photocationic polymerization initiator that generates an acid of 2 or less. The pKa is preferably -10.0 or higher.

Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators. Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts. Examples of ionic photocationic polymerization initiators include quaternary ammonium salts. Examples of the ionic photocationic polymerization initiator include ionic photocationic polymerization initiators described in paragraphs [0114] to [0133] of JP-A-2014-085643. Nonionic photocationic polymerization initiators include, for example, trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds and oximesulfonate compounds. Examples of trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds include compounds described in paragraphs [0083] to [0088] of JP-A-2011-221494. Oxime sulfonate compounds include, for example, compounds described in paragraphs [0084] to [0088] of WO2018/179640.

The photosensitive composition layer may contain one or more photopolymerization initiators.

The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the photosensitive composition layer. The content of the photopolymerization initiator is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less with respect to the total mass of the photosensitive composition layer. More preferred.

From the viewpoint of resolution and resist pattern shape, when the photosensitive composition layer contains a hexaarylbiimidazole compound as a photopolymerization initiator, the ratio of the content of the hexaarylbiimidazole compound to the content of the photopolymerization initiator. Is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, even more preferably 95% by mass to 100% by mass, and 100% by mass. Especially preferred.

(Polymerizable compound)
The photosensitive composition layer preferably further contains a polymerizable compound. More preferably, the photosensitive composition layer further contains a photopolymerization initiator and a polymerizable compound. The “polymerizable compound” in the present disclosure means a compound other than the resin (A) described above, which is polymerized by the action of a polymerization initiator.

The polymerizable compound may have one or more polymerizable groups. The types of the two or more polymerizable groups may be the same or different. Examples of polymerizable groups include groups having ethylenically unsaturated groups. Groups having ethylenically unsaturated groups include, for example, vinyl groups, acryloyl groups, methacryloyl groups, styryl groups and maleimide groups. Examples of polymerizable groups include cationic polymerizable groups. Cationic polymerizable groups include, for example, epoxy groups and oxetane groups.

The polymerizable compound preferably contains a radically polymerizable compound. Furthermore, the polymerizable compound is preferably a radically polymerizable compound. The radically polymerizable compound may be selected from known radically polymerizable compounds.

The polymerizable compound preferably contains a radically polymerizable compound having at least two polymerizable groups. Furthermore, the polymerizable compound is preferably a radically polymerizable compound having at least two polymerizable groups. The polymerizable group of the radical polymerizable compound is preferably an acryloyl group or a methacryloyl group.

From the viewpoint of pattern shape and peelability, when the polymerizable compound contains a radically polymerizable compound having two polymerizable groups, the content of the radically polymerizable compound having two polymerizable groups with respect to the content of the polymerizable compound The proportion is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. The ratio of the content of the radically polymerizable compound having two polymerizable groups to the content of the polymerizable compound may be 100% by mass or less.

The polymerizable compound preferably contains a polymerizable compound having a bisphenol structure. Furthermore, the polymerizable compound is preferably a polymerizable compound having a bisphenol structure. A polymerizable compound having a bisphenol structure can improve resolution by suppressing swelling of the photosensitive composition layer by a developer. The bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (ie, 2,2-bis(4-hydroxyphenyl)propane), bisphenol F (ie, 2,2-bis(4-hydroxyphenyl)methane). and bisphenol B structures derived from bisphenol B (ie, 2,2-bis(4-hydroxyphenyl)butane). The bisphenol structure is preferably a bisphenol A structure. The polymerizable compound having a bisphenol structure may be a radically polymerizable compound having a bisphenol structure.

Examples of polymerizable compounds having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Each of the two polymerizable groups may be directly attached to the end of the bisphenol structure. Each of the two polymerizable groups may be attached to the end of the bisphenol structure via one or more alkyleneoxy groups. The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of additions of alkyleneoxy groups (preferably ethyleneoxy groups) in the polymerizable compound having a bisphenol structure is preferably 2 to 60, more preferably 2 to 30, and 2 to 20. More preferred.

From the viewpoint of pattern shape and peelability, when the polymerizable compound contains a polymerizable compound having a bisphenol structure, the ratio of the content of the polymerizable compound having a bisphenol structure to the content of the polymerizable compound is 50% by mass or more. It is preferably 70% by mass or more, more preferably 80% by mass or more. The content ratio of the polymerizable compound having a bisphenol structure to the content of the polymerizable compound may be 100% by mass or less. Examples of preferred polymerizable compounds having a bisphenol structure include compounds represented by the following formula (P1).

The meaning of each symbol in formula (P1) is as follows. R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents an ethylene group. B represents a propylene group. n1 and n3 each independently represent an integer of 1 to 39; n1+n3 represents an integer of 2-40. n2 and n4 each independently represent an integer of 0 to 29; n2+n4 represents an integer of 0-30.

In formula (P1), the arrangement of -(AO)- and -(B-O)- structural units may be either random or block. In the block, -(AO)- or -(B-O)- may be on the side of the biphenyl group.

In formula (P1), n1+n2+n3+n4 is preferably 2-20, more preferably 2-16, and even more preferably 4-12.

In formula (P1), n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

Examples of polymerizable compounds having a bisphenol structure include compounds described in paragraphs [0072] to [0080] of JP-A-2016-224162. The contents of the above documents are incorporated herein by reference.

The polymerizable compound having a bisphenol structure is preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.

Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (eg, FA-324M, Hitachi Kasei Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, ethoxylated bisphenol A dimethacrylate (for example, BPE series, Shin-Nakamura Chemical Co., Ltd.), ethoxylated (10) bisphenol A diacrylate (e.g., NK Ester A-BPE-10, Shin-Nakamura Chemical Co., Ltd.) and 2,2-bis(4-(methacryloxy dodecaethoxytetrapropoxy)phenyl)propane (eg, FA-3200MY, Hitachi Chemical Co., Ltd.);

The polymerizable compound may contain a bifunctional polymerizable compound that does not have a bisphenol structure. Examples of bifunctional polymerizable compounds having no bisphenol structure include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate and trimethylolpropane diacrylate. A "bifunctional polymerizable compound" means a polymerizable compound having two polymerizable groups.

Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (e.g., A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (e.g., DCP, Shin-Nakamura Chemical Co., Ltd. Co., Ltd.), 1,9-nonanediol diacrylate (e.g., A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (e.g., A-HD-N, Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate and neopentyl glycol di(meth)acrylate.

Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate (e.g., NK Ester 4G, Shin-Nakamura Chemical Co., Ltd.), dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol diacrylate. (Meth)acrylates (eg, Aronix M-270, Toagosei Co., Ltd.).

Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, ethylene oxide-modified urethane di(meth)acrylates, and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available urethane di(meth)acrylates include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).

The polymerizable compound may contain a compound having one polymerizable group. Examples of compounds having one polymerizable group include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-(meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylates and phenoxyethyl (meth)acrylates.

The content of the compound having one polymerizable group is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, based on the content of the polymerizable compound. More preferably, it is from 3% by mass to 3% by mass.

The polymerizable compound may contain compounds having three or more polymerizable groups. Examples of compounds having three or more polymerizable groups include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) ) acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate and alkylene oxide modified products thereof. The term "(tri/tetra/penta/hexa)(meth)acrylates" includes tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates. The term "(tri/tetra)(meth)acrylates" includes tri(meth)acrylates and tetra(meth)acrylates.

Examples of alkylene oxide-modified compounds having three or more polymerizable groups include, for example, caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and Shin-Nakamura Chemical Industry A-9300-1CL manufactured by Co., Ltd.), alkylene oxide-modified (meth) acrylate compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., Shin-Nakamura Chemical Industry A-9300 manufactured by Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd.), ethoxylated glycerin triacrylate (for example, A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) ) TO-2349 (Toagosei Co., Ltd.), Aronix M-520 (Toagosei Co., Ltd.), Aronix M-510 (Toagosei Co., Ltd.) and SR454 (Tomoe Kogyo Co., Ltd.).

The content of the compound having three or more polymerizable groups is preferably 0% by mass to 20% by mass, more preferably 0% by mass to 15% by mass with respect to the content of the polymerizable compound. , more preferably 0% by mass to 10% by mass.

The polymerizable compound may be a polymerizable compound having an acid group. Examples of acid groups include carboxy groups. The acid groups may form acid anhydride groups. Examples of the polymerizable compound having an acid group include Aronix (registered trademark) TO-2349 (Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (Toagosei Co., Ltd.) and Aronix (registered trademark) M-510. (Toagosei Co., Ltd.). As the polymerizable compound having an acid group, for example, paragraphs [0025] to [0030] of JP-A-2004-239942
Polymerizable compounds described in.

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

The photosensitive composition layer may contain one or more polymerizable compounds. The photosensitive composition layer may contain three or more polymerizable compounds. When the photosensitive composition layer contains two or more polymerizable compounds, at least one polymerizable compound is preferably a polymerizable compound having a bisphenol structure.

The mass ratio of the content of the polymerizable compound to the content of the resin (A) is preferably from 0.10 to 2.00, more preferably from 0.30 to 1.50, and from 0.40 to 1.00 is more preferred.

The content of the polymerizable compound is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 70% by mass, and 20% by mass with respect to the total mass of the photosensitive composition layer. More preferably, it is up to 70% by mass.

(pigment (coloring agent))
From the viewpoint of the visibility of the exposed area, the visibility of the unexposed area, and the visibility and resolution of the resist pattern, the photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development. and may contain a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical. Hereinafter, the dye having the properties as described above may be referred to as "dye N". Dye N can improve resolution by improving adhesion between the photosensitive composition layer and other layers (for example, intermediate layer).

The aspect of "the maximum absorption wavelength changes with an acid, a base or a radical" is an aspect in which a dye in a colored state is decolored by an acid, a base or a radical, and a dye in a decolored state is colored by an acid, a base or a radical. Embodiments and embodiments in which a dye in a coloring state changes to a coloring state of another hue are included.

The dye N may be a compound that changes from a decolored state to develop color upon exposure or a compound that changes from a colored state to decolor upon exposure. The dye N may be a dye that changes its coloring or decoloring state by the action of an acid, a base or a radical generated in the photosensitive composition layer upon exposure. The dye N may be a dye that changes its coloring or decoloring state when the state (for example, pH) of the photosensitive composition layer is changed by an acid, a base, or a radical. The dye N may be a dye that changes its coloring or decoloring state by the action of an acid, a base, or a radical without exposure.

From the viewpoint of the visibility of the exposed area and the visibility and resolution of the unexposed area, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and the maximum absorption wavelength changes with radicals. A dye is more preferred.

From the viewpoint of the visibility of the exposed area and the visibility and resolution of the unexposed area, the photosensitive composition layer contains a dye whose maximum absorption wavelength changes due to radicals as the dye N, and a photoradical polymerization initiator. is preferred.

From the viewpoint of the visibility of the exposed and non-exposed areas, the dye N is preferably a dye that develops color with an acid, a base, or a radical.

From the viewpoint of the visibility of the exposed area, the visibility of the unexposed area, the visibility of the resist pattern, and the resolution, the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and a dye that develops color by radicals. is more preferable.

As for the coloring mechanism of the dye N, for example, there is a mode in which the radical-reactive dye develops color due to the radicals generated from the photoradical polymerization initiator upon exposure. As a coloring mechanism of the dye N, for example, there is a mode in which an acid-reactive dye develops color by an acid generated from a photocationic polymerization initiator upon exposure. The coloring mechanism of the dye N includes, for example, a mode in which a base-reactive dye (for example, a leuco dye) develops color with a base generated from a photobase generator upon exposure.

From the viewpoint of the visibility of the exposed and unexposed areas, the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm when the dye N develops is preferably 550 nm or more, more preferably 550 nm to 700 nm, and 550 nm. ~650 nm is more preferred.

The number of maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development of the dye N may be one or two or more. When the number of maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development of the dye N is two or more, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

The maximum absorption wavelength of Dye N is determined by measuring the transmission spectrum of a solution containing Dye N (liquid temperature: 25° C.) using a spectrophotometer (e.g., UV3100, Shimadzu Corporation) in an air atmosphere. , 400 nm to 780 nm.

Examples of the dye N that develops or decolors upon exposure include leuco compounds.

Examples of dyes N that are decolored by exposure include leuco compounds, diarylmethane-based dyes, oxazine-based dyes, xanthene-based dyes, iminonaphthoquinone-based dyes, azomethine-based dyes, and anthraquinone-based dyes.

The dye N is preferably a leuco compound in terms of visibility of the exposed and unexposed areas.

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (i.e., triarylmethane dyes), leuco compounds having a spiropyran skeleton (i.e., spiropyran dyes), and leuco compounds having a fluoran skeleton (i.e., fluoran dyes). dyes), leuco compounds having a diarylmethane skeleton (i.e., diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (i.e., rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (i.e., indolylphthalide and leuco compounds having a leuco auramine skeleton (ie, leuco auramine dyes). The leuco compound is preferably a triarylmethane-based dye or a fluoran-based dye, and more preferably a leuco compound having a triphenylmethane skeleton (that is, a triphenylmethane-based dye) or a fluoran-based dye.

The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of the exposed area and the non-exposed area. The lactone ring, sultine ring, or sultone ring reacts with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state to decolor it, or A leuco compound can be changed into a ring-opened state to develop a color.

The leuco compound is preferably a compound that has a lactone ring, sultine ring, or sultone ring, and that develops color by opening the lactone ring, sultine ring, or sultone ring with a radical or acid. The leuco compound is more preferably a compound that has a lactone ring and develops color when the lactone ring is opened by a radical or an acid.

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

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

Pigment N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate.

The photosensitive composition layer may contain one or more dyes N.

From the viewpoint of the visibility of the exposed area, the visibility of the unexposed area, the visibility of the resist pattern, and the resolution, the content of the dye N is 0.1% by mass with respect to the total mass of the photosensitive composition layer. It is preferably at least 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 1% by mass. is particularly preferred.

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

(other ingredients)
The photosensitive composition layer may further contain other components as needed. The photosensitive composition layer may contain one or more other components.

Other components include, for example, resins other than resin (A). Examples of resins other than resin (A) include acrylic resins, styrene-acrylic copolymers, polyurethanes, polyvinyl alcohol, polyvinyl formal, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, Polysiloxanes, polyethyleneimines, polyallylamines and polyalkylene glycols are included.

Other components include, for example, thermal crosslinking compounds, polymerization inhibitors, benzotriazole compounds, carboxybenzotriazole compounds, sensitizers, surfactants, plasticizers, heterocyclic compounds, pyridine compounds, and purine bases.

In the present disclosure, a thermally crosslinkable compound having an ethylenically unsaturated group is treated as a thermally crosslinkable compound rather than a polymerizable compound.

Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. The thermally crosslinkable compound may be a blocked isocyanate compound. A "blocked isocyanate compound" means a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent.

The dissociation temperature of the blocked isocyanate compound may be 100°C to 160°C. The dissociation temperature of the blocked isocyanate compound may be 130°C to 150°C. The dissociation temperature of the blocked isocyanate compound is measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter (for example, DSC6200, Seiko Instruments Inc.). In the DSC analysis, the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound is employed as the dissociation temperature of the blocked isocyanate compound.

Examples of blocked isocyanate compounds having a dissociation temperature of 100°C to 160°C include active methylene compounds (eg, malonic acid diesters) and oxime compounds. Malonic acid diesters include, for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate and di-2-ethylhexyl malonate. Examples of oxime compounds include compounds having a structure represented by -C(=N-OH)-. Specific oxime compounds include, for example, formaldoxime, acetaldoxime, acetoxime, methylethylketoxime and cyclohexanone oxime. From the viewpoint of storage stability, the blocked isocyanate compound is preferably an oxime compound.

The blocked isocyanate compound may have an isocyanurate structure. For example, a blocked isocyanate compound having an isocyanurate structure can be obtained by isocyanurating and protecting hexamethylene diisocyanate. A blocked isocyanate compound having an isocyanurate structure has an oxime structure using an oxime compound as a blocking agent, from the viewpoint of being able to adjust the dissociation temperature to a preferable range more easily than a compound having no oxime structure and to reduce development residue. A compound is preferred.

The blocked isocyanate compound may have a polymerizable group. Examples of the polymerizable group include the polymerizable groups in the polymerizable compound described above.

Examples of blocked isocyanate compounds include the Karenz series (Showa Denko KK) such as AOI-BM, MOI-BM and MOI-BP. Examples of blocked isocyanate compounds include block type Duranate series such as TPA-B80E and WT32-B75P (Asahi Kasei Chemicals Corp.).

Preferred blocked isocyanate compounds include, for example, the following compounds.

The photosensitive composition layer may contain one or more thermally crosslinkable compounds.

The content of the thermally crosslinkable compound may be 1% by mass to 50% by mass with respect to the total mass of the photosensitive composition layer. The content of the thermally crosslinkable compound may be 5% by mass to 30% by mass with respect to the total mass of the photosensitive composition layer.

From the viewpoint of resolution and resist pattern shape, it is preferable to reduce the content of the thermally crosslinkable compound in the photosensitive composition layer. The content of the thermally crosslinkable compound in the photosensitive composition layer is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, relative to the total mass of the photosensitive composition layer. is more preferable, and 0% by mass to 3% by mass is even more preferable. The content of the thermally crosslinkable compound in the photosensitive composition layer may be 0% by mass with respect to the total mass of the photosensitive composition layer. That is, a photosensitive composition layer that does not contain a thermally crosslinkable compound may be applied.

Examples of polymerization inhibitors include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784. Preferred polymerization inhibitors include, for example, phenothiazine, phenoxazine and 4-methoxyphenol.

Examples of polymerization inhibitors include radical polymerization inhibitors. Radical polymerization inhibitors include, for example, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt and diphenylnitrosamine. From the viewpoint of the sensitivity of the photosensitive composition layer, the radical polymerization inhibitor is preferably nitrosophenylhydroxyamine aluminum salt.

The content of the polymerization inhibitor is preferably 0.001% by mass to 5.0% by mass, and is 0.01% by mass to 3.0% by mass, based on the total mass of the photosensitive composition layer. is more preferable, and 0.02% by mass to 2.0% by mass is even more preferable.
The content of the radical polymerization inhibitor is preferably 0.005% by mass to 5.0% by mass, and 0.01% by mass to 3.0% by mass, based on the total mass of the polymerizable compound. is more preferable, and 0.01% by mass to 1.0% by mass is even more preferable.

Benzotriazole compounds include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

A carboxybenzotriazole compound functions, for example, as a rust inhibitor. Examples of carboxybenzotriazole compounds include carboxybenzotriazole (eg, 4-carboxy-1,2,3-benzotriazole and 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)aminoethylenecarboxybenzotriazole. mentioned. Examples of commercially available carboxybenzotriazole compounds include CBT-1 (Johoku Chemical Industry Co., Ltd.).

The total content of the polymerization inhibitor, benzotriazole compound and carboxybenzotriazole compound is preferably 0.01% by mass to 3% by mass, preferably 0.05% by mass, based on the total mass of the photosensitive composition layer. It is more preferably ~1% by mass. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is improved. The above content is 3% by mass
When it is below, the sensitivity is maintained and decolorization of the dye is suppressed.

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

From the viewpoint of improving the sensitivity to the light source and improving the curing speed due to the balance between the polymerization speed and the chain transfer, the content of the sensitizer is 0.01% by mass to 5% with respect to the total mass of the photosensitive composition layer. It is preferably 0.05% by mass to 1% by mass, more preferably 0.05% by mass to 1% by mass.

Examples of surfactants include surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362. The surfactant is preferably a fluorosurfactant, a nonionic surfactant or a silicone surfactant.

Examples of fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F manufactured by DIC Corporation. -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.

Examples of fluorine-based surfactants include Florard FC430, FC431 and FC171 manufactured by Sumitomo 3M Limited.

Examples of fluorine-based surfactants include Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S- 393 and KH-40.

Examples of fluorine-based surfactants include PolyFox PF636, PF656, PF6320, PF6520 and PF7002 manufactured by OMNOVA.

Examples of fluorine-based surfactants include Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, and 730LM manufactured by Neos Co., Ltd. , 650AC, 681 and 683.

Preferred fluorine-based surfactants include, for example, acrylic compounds that have a molecular structure that includes a functional group containing a fluorine atom, and in which the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied. is mentioned. As the fluorosurfactant as described above, for example, MegaFac DS series manufactured by DIC Corporation (for example, Chemical Daily (February 22, 2016) and Nikkei Sangyo Shimbun (February 23, 2016) See also).

Preferable fluorosurfactants include, for example, 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.

The fluorosurfactant may be a block polymer.

Preferred fluorine-based surfactants include, for example, structural units derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy or propyleneoxy and a structural unit derived from a (meth)acrylate compound.

Examples of fluorine-based surfactants include fluorine-containing polymers having ethylenically unsaturated groups in side chains. Examples of the above fluorine-based surfactants include Megafac RS-101, RS-102, RS-718K and RS-72-K manufactured by DIC Corporation.

From the viewpoint of environmental friendliness, preferred fluorine-based surfactants include compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). and surfactants derived from alternative materials of

Examples of nonionic surfactants include glycerol, trimethylolpropane and trimethylolethane. Nonionic surfactants may be ethoxylates or propoxylates of the above compounds. Nonionic surfactants include, for example, glycerol ethoxylate and glycerol propoxylate.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distea rate and sorbitan fatty acid esters.

Examples of nonionic surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 and 25R2 manufactured by BASF.

Examples of nonionic surfactants include Tetronic 304, 701, 704, 901, 904 and 150R1 manufactured by BASF.

Examples of nonionic surfactants include Solsperse 20000 manufactured by Nippon Lubrizol Co., Ltd.

Examples of nonionic surfactants include NCW-101, NCW-1001 and NCW-1002 manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

Examples of nonionic surfactants include Pionein D-6112, D-6112-W and D-6315 manufactured by Takemoto Oil Co., Ltd.

Examples of nonionic surfactants include Olfin E1010 and Surfynol 104, 400 and 440 manufactured by Nissin Chemical Industry Co., Ltd.

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

Examples of silicone-based surfactants include DOWSIL 8032 ADDITIVE manufactured by Dow Corning Toray Co., Ltd., 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 may be mentioned.

Examples of silicone surfactants include X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945 and KF manufactured by Shin-Etsu Chemical Co., Ltd. -640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002.

Examples of silicone surfactants include F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 manufactured by Momentive Performance Materials.

Examples of silicone-based surfactants include BYK307, BYK323 and BYK330 manufactured by BYK-Chemie.

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

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

Heterocyclic compounds include, for example, triazole.

Examples of pyridine compounds include isonicotinamide.

Purine bases include, for example, adenine.

Other components include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, and organic precipitates. Inhibitors and inorganic suspending agents are included.

Examples of other components include substances described in paragraphs [0165] to [0184] of JP-A-2014-085643. The contents of the above documents are incorporated herein by reference.

(impurities)
The photosensitive composition layer may contain impurities. Impurities include, for example, metal impurities, metal impurity ions, halide ions, organic solvents, monomers, and water.

　Metal impurities include, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc and tin. The form of metal impurities may be ions. However, particles contained as components of the photosensitive composition layer (for example, metal oxide particles) are excluded from metal impurities.

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

The content of metal impurities is measured by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy and ion chromatography.

Methods for adjusting the content of metal impurities include, for example, a method of selecting raw materials with a low content of metal impurities, a method of preventing contamination of metal impurities in the process of forming a photosensitive composition layer, and a method of forming a photosensitive composition layer. A method of removing metal impurities by washing during the formation process can be mentioned.

The contents of sodium ions, potassium ions, and halide ions are preferably adjusted to the same range as the metal impurity contents described above.

Examples of organic solvents include benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane.

The content of the organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive composition layer. . The lower limit of the content of the organic solvent may be 10 mass ppb or 100 mass ppb with respect to the total mass of the photosensitive composition layer.

The content of the organic solvent is measured by a known method such as gas chromatography analysis.

A method for adjusting the content of the organic solvent includes a method for adjusting the drying conditions in the process of forming the photosensitive composition layer.

The photosensitive composition layer may contain the monomer used as the raw material for the resin. From the viewpoint of patterning properties and reliability, the content of the monomer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and 500 mass ppm or less, relative to the total mass of the resin. is more preferable. The lower limit of the monomer content may be 1 mass ppm or 10 mass ppm relative to the total mass of the resin. From the viewpoint of patterning properties and reliability, the amount of the monomer forming each structural unit of the alkali-soluble resin is preferably 3000 ppm by mass or less, and 600 ppm by mass or less, relative to the total mass of the photosensitive composition layer. is more preferably 100 ppm by mass or less. The lower limit of the content of monomers forming each structural unit of the alkali-soluble resin may be 0.1 mass ppm or 1 mass ppm with respect to the total mass of the photosensitive composition layer. The content of the monomer used in synthesizing the alkali-soluble resin in the polymer reaction is preferably adjusted within the above range. For example, when an alkali-soluble resin is synthesized by reacting a carboxylic acid side chain with glycidyl acrylate, the content of glycidyl acrylate is preferably adjusted within the above range.

The content of monomers remaining in the photosensitive composition layer is measured by known methods such as liquid chromatography and gas chromatography.

A method for adjusting the content of the monomers remaining in the photosensitive composition layer includes, for example, the method for adjusting the content of metal impurities described above.

From the viewpoint of improving reliability and laminating properties in a method using a transfer film described later, the water content is 0.01% by mass to 1.0% by mass with respect to the total mass of the photosensitive composition layer. is preferred, and 0.05% by mass to 0.5% by mass is more preferred.

(thickness)
The average thickness of the photosensitive composition layer may be 0.1 μm or more. The average thickness of the photosensitive composition layer is preferably 0.2 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more. The average thickness of the photosensitive composition layer may be 300 μm or less. The average thickness of the photosensitive composition layer is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 20 μm or less, and particularly preferably 5 μm or less. When the average thickness of the photosensitive composition layer is within the above range, the developability of the photosensitive composition layer is improved, and the resolution is improved. The average thickness of the photosensitive composition layer is obtained by a method according to the above-described method for calculating the average thickness of the substrate.

(C = C valence)
The C=C value of the photosensitive composition layer is preferably 1.0 mmol/g to 5.0 mmol/g, more preferably 1.5 mmol/g to 4.0 mmol/g, and 2.0 mmol /g or more and less than 4.0 mmol/g, and particularly preferably 2.5 mmol/g or more and less than 3.5 mmol/g. The C=C value of the photosensitive composition layer means the equivalent amount (specifically, the molar amount) of double bond groups contained in 1 g of the photosensitive composition layer.

(Transmittance)
The transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 99.9% or less, more preferably 99.0% or less.

(Method for forming photosensitive composition layer)
Examples of the method of providing a photosensitive composition layer on the conductive layer include a method using a photosensitive composition. Providing the photosensitive composition layer over the conductive layer may comprise forming the photosensitive composition layer by applying the photosensitive composition over the conductive layer.

The components of the photosensitive composition are determined according to the components of the intended photosensitive composition layer. Detailed aspects of the photosensitive composition are described in the section “<Photosensitive composition>” below. A preferred embodiment of the photosensitive composition used in the method for producing a laminate having a conductor pattern may be selected from the preferred embodiments of the photosensitive composition described in the section "<Photosensitive composition>" below. .

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

The photosensitive composition applied on the conductive layer may be dried as necessary. Drying methods include, for example, drying by heating and drying under reduced pressure. The drying temperature is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 80° C. or higher. The drying temperature is preferably 130° C. or lower, more preferably 120° C. or lower. The drying temperature may be varied continuously. The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The drying time is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.

A method of providing a photosensitive composition layer on the conductive layer includes, for example, a method of using a transfer film containing a photosensitive composition layer. Providing a photosensitive composition layer on the conductive layer involves preparing a transfer film containing a temporary support and a photosensitive composition layer in this order, and attaching the photosensitive composition layer and the conductive layer of the transfer film. It preferably includes combining and. According to the method of bonding the photosensitive composition layer and the conductive layer of the transfer film together, a laminate is formed which includes the substrate, the conductive layer, the photosensitive composition layer and the temporary support in this order.

The detailed aspects of the transfer film are described in the section "<transfer film>" below. A preferred embodiment of the transfer film used in the method for producing a laminate having a conductor pattern may be selected from the preferred embodiments of the transfer film described in the section "<Transfer Film>" below.

Examples of the method of bonding the photosensitive composition layer and the conductive layer of the transfer film include a method using a known laminator such as a vacuum laminator and an autocut laminator.

The bonding of the photosensitive composition layer and the conductive layer of the transfer film may be performed under pressure conditions. The bonding of the photosensitive composition layer and the conductive layer of the transfer film may be carried out under pressure and heating conditions. The photosensitive composition layer overlying the conductive layer may be pressed and heated by rollers. The heating temperature is preferably 70°C to 130°C.

When the transfer film contains a protective film as the outermost layer, it is preferable that the photosensitive composition layer and the conductive layer of the transfer film are laminated after peeling off the protective film.

The temporary support placed on the conductive layer by using the transfer film may be peeled off before the exposure step. A temporary support placed on the conductive layer by using a transfer film may be peeled off between the exposure and development steps. In the method for producing a laminate having a conductor pattern, a temporary support is provided between bonding the photosensitive composition layer and the conductive layer and exposing the photosensitive composition layer (that is, the exposure step). Preferably, it further comprises stripping. A method for peeling off the temporary support is not limited. For example, the temporary support may be peeled off by a cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589.

[Exposure process]
The exposure step is to expose the photosensitive composition layer. The exposure process can form an exposed portion and a non-exposed portion in the photosensitive composition layer. The positional relationship between the exposed portion and the non-exposed portion is determined according to the desired shape of the resist pattern.

Examples of the method of exposing the photosensitive composition layer include a method of exposing the photosensitive composition layer by bringing a photomask into direct or indirect contact with the photosensitive composition layer. In the method of indirectly contacting the photomask with the photosensitive composition layer, the photomask may contact the intermediate layer or the temporary support. A fine resist pattern can be easily obtained as the distance between the photosensitive composition layer and the photomask becomes smaller. As a result, a fine conductor pattern can be obtained. It is also preferred to expose the photosensitive composition layer using a projection exposure apparatus.

Examples of light sources include lasers, light-emitting diodes (LEDs), ultrahigh-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The light source is preferably a light source that emits light having at least one wavelength selected from the group consisting of 365 nm and 405 nm.

The dominant wavelength of the light with which the photosensitive composition layer is irradiated is preferably 365 nm. By "dominant wavelength" is meant the wavelength with the highest intensity.

The exposure dose is preferably 5 mJ/cm ² to 200 mJ/cm ² and more preferably 10 mJ/cm ² to 200 mJ/cm ² .

The light source, exposure amount and exposure method are described, for example, in paragraphs [0146] to [0147] of WO2018/155193. The contents of the above documents are incorporated herein by reference.

[Development process]
The development step is to develop the photosensitive composition layer to form a resist pattern. According to the development step, the exposed portion or the non-exposed portion of the photosensitive composition layer is removed to form a resist pattern. The resist pattern may be a cured product of a photosensitive composition layer.

The development process is preferably carried out using a developer. Preferred developers include, for example, alkaline developers.

The alkaline developer is preferably an alkaline aqueous solution containing an alkali metal salt or an ammonium salt. The alkali metal salt is preferably a compound that dissolves in water and exhibits alkalinity. Alkali metal salts include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate. Ammonium salts include, for example, tetramethylammonium hydroxide and tetrabutylammonium hydroxide

The developer may contain one or more alkali metal salts. The developer may contain one or more ammonium salts. The developer may contain both alkali metal salts and ammonium salts.

The content of the alkali metal salt or ammonium salt is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, relative to the total mass of the developer. .

The content of water is preferably 50% by mass or more and less than 100% by mass, more preferably 90% by mass or more and less than 100% by mass, relative to the total mass of the developer.

Examples of developing methods include puddle development, shower development, spin development and dip development. A preferable developing method includes, for example, the developing method described in paragraph [0195] of WO 2015/093271.

The developer remaining after the development process may be removed by rinsing. Examples of solvents used for rinsing include water.

The liquid remaining after the developing process or rinsing process may be removed by drying process.

The position and size of the resist pattern are not limited. The line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. The line width of the resist pattern may be 0.5 μm or more.

[Plating process]
The plating process is to plate the conductive layer in the area where the resist pattern is not arranged. The “conductive layer in the region where the resist pattern is not arranged” means the conductive layer that is not covered with the resist pattern in a plan view in which the conductive layer is observed along the thickness direction of the laminate. According to the plating process, a layer is formed by plating on the conductive layer in the region where the resist pattern is not arranged. Hereinafter, a layer formed by plating may be referred to as a "plated layer".

Examples of plating treatments include electrolytic plating and electroless plating, with electrolytic plating being preferred from the viewpoint of productivity.

For example, metals can be used as components of the plating layer. Metals include, for example, copper, chromium, lead, nickel, gold, silver, tin and zinc. The metal contained in the plating layer may be an alloy. From the viewpoint of excellent conductivity of the conductive pattern, the plating layer preferably contains copper or a copper alloy. The plated layer preferably contains copper as a main component.

The average thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm or more. The average thickness of the plating layer is preferably 20 μm or less. The average thickness of the plated layer is obtained by a method according to the above-described method for calculating the average thickness of the substrate.

[Step of removing resist pattern]
The step of removing the resist pattern is to remove the resist pattern.

A method of removing the resist pattern includes, for example, a method of removing the resist pattern by chemical treatment. A method of removing the resist pattern using a stripper is preferred. The resist pattern may be removed by a spray method, a shower method, or a puddle method using a remover.

A preferred stripping solution includes, for example, a removing solution containing an alkaline compound and at least one solvent selected from the group consisting of water, dimethylsulfoxide and N-methylpyrrolidone. The alkaline compound may be selected from compounds that exhibit alkaline properties when dissolved in water. Examples of alkaline compounds include alkaline inorganic compounds (e.g. sodium hydroxide and potassium hydroxide) and alkaline organic compounds (e.g. primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium compounds). salt compounds). The solvent used in the stripper solution may be propylene glycol monomethyl ether acetate (PGMEA).

The temperature of the stripping solution is preferably 23°C to 80°C, more preferably 30°C to 80°C, and even more preferably 50°C to 80°C.

A specific example of the method of removing the resist pattern includes a method of immersing the laminate having the resist pattern in a stripper at 50°C to 80°C for 1 minute to 30 minutes.

The stripping solution preferably has a property of not dissolving the metal layer.

The stripping solution remaining after the resist pattern removal process may be removed by a rinse process. Examples of solvents used for rinsing include water.

The liquid remaining after the resist pattern removal step or rinse treatment may be removed by drying treatment.

[Step of removing conductive layer]
The step of removing the conductive layer is to remove the conductive layer exposed by removing the resist pattern to form a conductive pattern. According to the step of removing the conductive layer, the conductive layer that is not protected by the plated layer formed by plating is removed, and the remaining conductive layer and the plated layer form the conductive pattern.

A method of removing the conductive layer includes, for example, a method of removing the conductive layer using an etchant. A known etchant may be used in the step of removing the conductive layer. Examples of the etchant include ferric chloride solution, cupric chloride solution, ammonia alkali solution, sulfuric acid-hydrogen peroxide mixed solution and phosphoric acid-hydrogen peroxide mixed solution.

The etchant remaining after the step of removing the conductive layer may be removed by rinsing. Examples of solvents used for rinsing include water.

The liquid remaining after the step of removing the conductive layer or the rinsing process may be removed by a drying process.

The line width of the conductor pattern is preferably 8 μm or less, more preferably 6 μm or less. The line width of the conductor pattern may be 0.5 μm or more.

[Other processes]
The method of manufacturing a laminate having a conductor pattern may include other steps as necessary. Other steps include, for example, the following steps. However, other process types are not limited to the following specific examples.

(Post-exposure process and post-bake process)
The method of manufacturing a laminate having a conductor pattern may further include exposing the resist pattern between the developing step and the plating step. The method for manufacturing a laminate having a conductor pattern may further include exposing the resist pattern and heating the resist pattern between the developing step and the plating step. Heating of the resist pattern is preferably performed after exposure of the resist pattern.

The exposure dose is preferably 100 mJ/cm ² to 5000 mJ/cm ² and more preferably 200 mJ/cm ² to 3000 mJ/cm ² .

The heating temperature is preferably 80°C to 250°C, more preferably 90°C to 160°C.

The heating time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

(Step of forming protective layer)
The method for manufacturing a laminate having a conductor pattern may further include forming a protective layer on the plating layer between the plating process and the resist pattern removing process.

The component of the protective layer is preferably a component that is resistant to stripping solutions and etching solutions. Components of the protective layer include, for example, metals (eg, nickel, chromium, tin, zinc, magnesium, gold, silver and alloys thereof) and resins. Nickel or chromium are preferred.

Examples of methods for forming the protective layer include electroless plating and electroplating. Electroplating is preferred.

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

(Step of reducing visible light reflectance)
The method of manufacturing a laminate having a conductor pattern may further include performing a treatment for reducing the visible light reflectance of at least a portion of the conductor pattern.

　An example of a treatment that reduces the visible light reflectance is oxidation treatment. For example, when the conductor pattern contains copper, the visible light reflectance of the conductor pattern can be reduced by oxidizing the copper to form copper oxide and blackening the conductor pattern.

The treatment for reducing the visible light reflectance is, for example, paragraphs [0017] to [0025] of JP-A-2014-150118 and paragraphs [0041], [0042], [0048] of JP-A-2013-206315 and [0058]. The contents of these documents are incorporated herein by reference.

(Step of forming an insulating film and step of forming a new conductive layer on the surface of the insulating film)
A method for manufacturing a laminate having a conductor pattern includes forming an insulating film on the surface of the laminate having the conductor pattern, and forming a new conductive layer (for example, a conductor pattern) on the surface of the insulating film. It may further contain: For example, methods such as those described above can form a first conductor pattern and a second conductor pattern insulated from the first conductor pattern.

Examples of methods for forming the insulating film include methods for forming a known permanent film. As a method of forming an insulating film, a method of forming an insulating film having a desired pattern by photolithography using a photosensitive composition having an insulating property can be mentioned.

A method of forming a new conductive layer on the surface of the insulating film includes, for example, a method of forming a new conductive layer having a desired pattern by photolithography using a conductive photosensitive composition.

(Other processes)
Other steps other than the above steps include, for example, the steps described in paragraphs [0172] to [0173] of WO2019/022089.

[Use of laminate having conductor pattern]
Preferable uses of laminates having conductor patterns include, for example, production process films for interposer rewiring layers, semiconductor packages, and printed circuit boards. Laminates with conductor patterns may be used as components in various devices. Devices including laminates having conductor patterns include, for example, input devices. The input device is preferably a touch panel, more preferably a capacitive touch panel. The input device may be applied to display devices such as an organic EL display device and a liquid crystal display device.

<Photosensitive composition>
A photosensitive composition according to one embodiment of the present disclosure includes a resin (A), that is, a resin including a structural unit represented by formula B1 and a structural unit having an alkali-soluble group. According to the above embodiments, a photosensitive composition is provided that forms a resist pattern with excellent resolution.

The aspect of the resin (A) in the photosensitive composition is the same as the aspect of the resin (A) described in the above section "<Method for producing laminate having conductor pattern>". Preferred components of the photosensitive composition are the same as the preferred components of the photosensitive composition layer described in the above section "<Method for producing laminate having conductor pattern>". In the embodiment regarding the content of components other than the solvent in the photosensitive composition layer described in the section "<Method for producing a laminate having a conductor pattern>", the "total mass of the photosensitive composition layer" is replaced with "photosensitive "total mass of the solid content of the photosensitive composition" and applied to aspects relating to the content of components other than the solvent in the photosensitive composition.

The photosensitive composition may further contain a solvent. The solvent may be selected from solvents capable of dissolving or dispersing components contained in the photosensitive composition layer.

Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g. methanol and ethanol), ketone solvents (e.g. acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g. toluene), aprotic polar solvents (eg N,N-dimethylformamide), cyclic ether solvents (eg tetrahydrofuran), ester solvents (eg n-propyl acetate), amide solvents and lactone solvents.

The solvent preferably contains at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. The solvent contains at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least one solvent selected from the group consisting of ketone solvents and cyclic ether solvents. is more preferable. More preferably, the solvent contains at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and a ketone solvent.

Alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (e.g., propylene glycol monomethyl ether), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and Dipropylene glycol dialkyl ethers may be mentioned.

Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.

Examples of the solvent include the solvents described in paragraphs [0092] to [0094] of International Publication No. 2018/179640 and the solvents described in paragraph [0014] of JP-A-2018-177889. The contents of these documents are incorporated herein by reference.

The photosensitive composition may contain one or more solvents.

The content of the solvent is preferably 50 parts by mass to 1900 parts by mass, more preferably 100 parts by mass to 1200 parts by mass, with respect to 100 parts by mass of the total solid content of the photosensitive composition. parts to 900 parts by mass is more preferable.

<Transfer film>
A transfer film according to an embodiment of the present disclosure includes a temporary support and a photosensitive composition layer in this order. The photosensitive composition layer of the transfer film contains a resin (A), that is, a resin containing a structural unit represented by formula B1 and a structural unit having an alkali-soluble group. According to the above embodiments, a transfer film is provided that forms a resist pattern with excellent resolution.

A specific example of the structure of the transfer film will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view of a transfer film according to one embodiment. The transfer film 10 shown in FIG. 1 includes a temporary support 11, an intermediate layer 13, a photosensitive composition layer 15, and a protective film 19 in this order. The intermediate layer 13 and the photosensitive composition layer 15 constitute a transfer layer 17 . For example, the transfer layer 17 of the transfer film 10 is arranged on the substrate by laminating the transfer film 10 and the substrate. The structure of the transfer film 10 may be a structure without the protective film 19 .

[Temporary support]
The temporary support supports the photosensitive composition layer on the transfer film.

The temporary support is preferably a film, more preferably a resin film. Preferred temporary supports include, for example, films that are flexible and do not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat. A preferred temporary support includes, for example, a film free from deformation such as wrinkles and flaws.

Examples of films include polyethylene terephthalate film (eg, biaxially stretched polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film and polycarbonate film. Preferably the film is a polyethylene terephthalate film.

The temporary support preferably has transparency. A temporary support having transparency allows exposure of the photosensitive composition layer through the temporary support. The transmittance of the temporary support at a wavelength of 365 nm is preferably 60% or more, more preferably 70% or more. The transmittance of the temporary support at a wavelength of 365 nm is preferably less than 100%.

From the viewpoint of pattern formability by exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. The haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The haze of the temporary support may be 0% or more.

From the viewpoint of pattern formability by exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matters and defects in the temporary support is small. The number of fine particles (for example, fine particles having a diameter of 1 μm), foreign matter and defects in the temporary support is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, and 3 It is more preferably less than 1 piece/10 mm ² , and particularly preferably less than 1 piece/10 mm ² . The number of fine particles, foreign matter and defects in the temporary support may be 0/10 mm ² or more.

The temporary support may have a single-layer structure and a multilayer structure.

The average thickness of the temporary support is preferably 5 μm to 200 μm. The average thickness of the temporary support is preferably 5 μm to 150 μm, more preferably 5 μm to 50 μm, even more preferably 5 μm to 25 μm, from the viewpoints of ease of handling and versatility. The average thickness of the temporary support is obtained by a method according to the above-described method for calculating the average thickness of the substrate.

From the viewpoint of handling, a layer containing fine particles (hereinafter referred to as "lubricant layer") may be arranged on one or both sides of the temporary support. The fine particles contained in the lubricant layer preferably have a diameter of 0.05 μm to 0.8 μm. The average thickness of the lubricant layer is preferably 0.05 μm to 1.0 μm. The average thickness of the lubricant layer is obtained by a method according to the above-described method for calculating the average thickness of the substrate.

From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support in contact with the photosensitive composition layer may be modified. Modification treatments include, for example, ultraviolet irradiation, corona discharge, and plasma treatment.

The exposure amount in ultraviolet irradiation is preferably 10 mJ/cm ² to 2000 mJ/cm ² , more preferably 50 mJ/cm ² to 1000 mJ/cm ² .

A light source for ultraviolet irradiation includes, for example, a light source that emits light in the wavelength range of 150 nm to 450 nm. Examples of light sources include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps and light emitting diodes (LEDs).

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

As the temporary support, for example, paragraphs [0017] to [0018] of JP-A-2014-085643, paragraphs [0019] to [0026] of JP-A-2016-027363, International Publication No. 2012/081680 Paragraphs [0041] to [0057] and the temporary supports described in paragraphs [0029] to [0040] of WO 2018/179370. The contents of these documents are incorporated herein by reference.

Examples of commercially available temporary supports include Lumirror 16KS40 and Lumirror 16FB40 manufactured by Toray Industries, Inc. Commercial products of the temporary support include, for example, Cosmoshine A4100, Cosmoshine A4300 and Cosmoshine A8300 manufactured by Toyobo Co., Ltd.

[Photosensitive composition layer]
The aspect of the photosensitive composition layer in the transfer film is the same as the aspect of the photosensitive composition layer described in the above section "<Method for producing laminate having conductor pattern>". Examples of the method for forming the photosensitive composition layer include a method using a photosensitive composition. For example, a photosensitive composition layer is formed by applying a photosensitive composition onto a temporary support. The aspect of the photosensitive composition and the method of applying the photosensitive composition are described in the above section "<Method for producing a laminate having a conductor pattern>" and the above "<Photosensitive composition>".

[Middle layer]
The transfer film preferably further comprises an intermediate layer between the temporary support and the photosensitive composition layer.

An example of the intermediate layer is a water-soluble resin layer. Examples of the intermediate layer include an oxygen-blocking layer having an oxygen-blocking function described as a "separation layer" in JP-A-5-072724.

A preferred intermediate layer includes, for example, an oxygen blocking layer. The oxygen barrier layer can reduce the time load of the exposing machine by improving the sensitivity during exposure. As a result, productivity is improved. The oxygen-blocking layer is preferably an oxygen-blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (for example, a 1% by weight sodium carbonate aqueous solution at 22° C.).

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-based resins.

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

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

Examples of polyamide-based resins include acrylamide-based resins, vinylamide-based resins, and allylamide-based resins.

Examples of water-soluble resins include copolymers of (meth)acrylic acid and vinyl compounds. The copolymer of (meth)acrylic acid and the vinyl compound is preferably a copolymer of (meth)acrylic acid and allyl (meth)acrylate, and is a copolymer of methacrylic acid and allyl methacrylate. is more preferable.

When the water-soluble resin is a copolymer of (meth)acrylic acid and a vinyl compound, the ratio of (meth)acrylic acid mol%/vinyl compound mol% is preferably 90/10 to 20/80, It is more preferably 80/20 to 30/70.

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

The degree of dispersion of the water-soluble resin is preferably 1-10, more preferably 1-5, even more preferably 1-3.

The intermediate layer may contain one or more water-soluble resins.

The content of the water-soluble resin is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of the intermediate layer. The content of the water-soluble resin is preferably 100% by mass or less, more preferably 99.99% by mass or less, and preferably 99.9% by mass or less with respect to the total mass of the intermediate layer. More preferred.

The intermediate layer may contain other ingredients. Other components are preferably polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds, more preferably polyhydric alcohols, phenol derivatives or amide compounds.

Examples of polyhydric alcohols include glycerin, diglycerin and diethylene glycol. The number of hydroxy groups in the polyhydric alcohols is preferably 2-10.

Examples of alkylene oxide adducts of polyhydric alcohols include compounds obtained by adding ethyleneoxy groups to polyhydric alcohols and compounds obtained by adding propyleneoxy groups to polyhydric alcohols. The average number of alkyleneoxy groups to be added is preferably 1-100, preferably 2-50, more preferably 2-20.

Examples of phenol derivatives include bisphenol A and bisphenol S.

Examples of amide compounds include N-methylpyrrolidone.

The molecular weight of the other component is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, and particularly preferably 2,000 or less, Most preferably, it is 1,500 or less. The molecular weight of other components is preferably 60 or more.

The intermediate layer may contain one or more other components.

The content of other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 1% by mass or more, relative to the total mass of the intermediate layer. More preferred. The content of other components is preferably less than 30% by mass, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to the total mass of the intermediate layer.

The intermediate layer comprises water-soluble cellulose derivatives, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, polyether resins, polyamide resins, polyvinylamide resins, polyallylamide resins, phenol derivatives and amide compounds. It preferably contains at least one compound selected from the group consisting of:

The intermediate layer may contain impurities. Impurities include, for example, the impurities described in the above section “<Method for producing laminate having conductor pattern>”.

The average thickness of the intermediate layer is preferably 3.0 µm or less, more preferably 2.0 µm or less. The average thickness of the intermediate layer is preferably 0.3 μm or more, more preferably 1.0 μm or more. The average thickness of the intermediate layer is obtained by a method according to the above-described method for calculating the average thickness of the substrate.

Examples of methods for forming the intermediate layer include a method using a composition for forming an intermediate layer. The intermediate layer may be formed by applying an intermediate layer-forming composition onto the temporary support.

The components of the intermediate layer-forming composition are selected according to the target intermediate layer components. The intermediate layer-forming composition may contain a solvent. The solvent may be selected from solvents capable of dissolving or dispersing components contained in the intermediate layer. The solvent is preferably at least one solvent selected from the group consisting of water and water-miscible organic solvents, more preferably a solvent containing water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

The intermediate layer-forming composition may contain one or more solvents.

The content of the solvent is preferably 50 parts by mass to 2500 parts by mass, more preferably 50 parts by mass to 1900 parts by mass, based on 100 parts by mass of the total solid content of the composition for forming an intermediate layer. It is more preferably 100 parts by mass to 900 parts by mass.

Examples of methods for applying the intermediate layer forming composition include slit coating, spin coating, curtain coating and inkjet coating.

The applied intermediate layer forming composition may be dried as necessary. The drying method is preferably heat drying or reduced pressure drying. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher, and even more preferably 100° C. or higher. The drying temperature is preferably 130° C. or lower, more preferably 120° C. or lower. The drying temperature may be varied continuously. The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. The drying time is preferably 600 seconds or less, more preferably 450 seconds or less, and even more preferably 300 seconds or less.

[Other layers]
The transfer film may further contain other layers. Other layers include, for example, protective films.

Examples of protective films include resin films. The resin film preferably has heat resistance and solvent resistance. Examples of resin films include polyolefin films (eg polypropylene films and polyethylene films), polyester films (eg polyethylene terephthalate films), polycarbonate films and polystyrene films. The protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film. The protective film may be a resin film having the same composition as the temporary support.

The average thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, even more preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm. From the viewpoint of mechanical strength, the average thickness of the protective film is preferably 1 μm or more. From the viewpoint of relatively low cost, the average thickness of the protective film is preferably 100 μm or less. The average thickness of the protective film is obtained by a method according to the above-described method for calculating the average thickness of the substrate.

The number of fish eyes with a diameter of 80 μm or more contained in the protective film is preferably 5/m ² or less. The number of fish eyes with a diameter of 80 μm or more contained in the protective film may be 0/m ² or more. "Fish eye" refers to foreign matter, undissolved matter, and oxidatively deteriorated materials taken into the film in the process of producing the film by methods such as heat melting, kneading, extrusion, biaxial stretching, and casting. Denotes a formed defect.

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

From the viewpoint of windability, the surface arithmetic mean roughness Ra of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. . The arithmetic mean roughness Ra of the surface of the protective film is preferably less than 0.50 μm, more preferably 0.40 μm or less, even more preferably 0.30 μm or less.

A method of introducing a protective film into a transfer film includes, for example, a method of bonding a protective film and a photosensitive composition layer together. Apparatuses for bonding the protective film and the photosensitive composition layer include, for example, known laminators such as a vacuum laminator and an autocut laminator. The laminator preferably includes a heatable roller, such as a rubber roller, and has the function of applying pressure and heat to the object to be treated.

[Waviness of transfer film]
From the viewpoint of suppressing the generation of air bubbles in bonding using a transfer film, the maximum width of the undulation of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less. . The maximum width of the undulations of the transfer film is preferably 0 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more.

The maximum width of the undulation of the transfer film is measured by the following procedure. The transfer film is cut in a direction perpendicular to the main surface of the transfer film to prepare a sample having a size of 20 cm long and 20 cm wide. When the transfer film contains a protective film, the protective film is peeled off. Place the sample on a smooth and horizontal platform. When the sample is placed on the table, the surface of the temporary support of the sample faces the table. Using a laser microscope (eg, VK-9700SP manufactured by KEYENCE CORPORATION), a 10 cm square range in the central portion of the surface of the sample is scanned to obtain a three-dimensional surface image. Subtract the minimum concave height from the maximum convex height observed in the three-dimensional surface image. The above operation is performed using 10 samples, and the arithmetic average of the measured values is taken as the maximum waviness width of the transfer film.

[Use]
Preferred uses of the transfer film include, for example, a method for producing a conductor pattern using a resist pattern. Examples of the method for producing the conductor pattern include the method for producing the laminate having the already-described conductor pattern. The transfer film is preferably used for forming plated wiring. That is, the transfer film is preferably a transfer film for forming plated wiring. The plated wiring may be the already-described conductor pattern.

Hereinafter, the present disclosure will be described in further detail based on examples. However, the content of the present disclosure is not limited to the following examples. Matters shown in the following examples (eg, materials, usage amounts, proportions, processing details, and processing procedures) may be changed as appropriate without departing from the gist of the present disclosure. In the following examples, the weight average molecular weight of the resin is the weight average molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene.

<Examples 1 to 23 and Comparative Examples 1 to 2>
[Preparation of resins A1 to A9]
The following resins A1 to A9 were synthesized according to the following procedure. Each resin corresponds to the resin (A) described above. The numerical value attached to each structural unit of each resin represents the content of the structural unit (unit: % by mass). Table 1 shows the weight average molecular weight (Mw), dispersity (Mw/Mn) and acid value of each resin.

(Synthesis of Resin A1)
Under a nitrogen stream, N-methylpyrrolidone (21.5 g) heated to 90° C. was charged with the aforementioned monomer (ii-1) (19.2 g), methacrylic acid (11.7 g), methyl methacrylate ( 0.8 g), styrene (33.17 g), polymerization initiator V-601 (Fuji Film Wako Chemical Co., Ltd., 2.5 g) and N-methylpyrrolidone (27.8 g) was added dropwise over 2 hours. . After dropping the solution, 0.5 g of V-601 was added three times at intervals of 1 hour. The mixture was reacted at 90° C. for 3 hours and then cooled to room temperature. The reaction was diluted with N-methylpyrrolidone (39.5 g), triethylamine (31.4 g) and 4-methoxyphenol (0.25 g) were added and stirred at room temperature for 12 hours. The reaction was diluted with methanol (50 mL), then the diluted solution was added dropwise to a mixture of concentrated hydrochloric acid (22 g) and distilled water (1050 g). The precipitated powder was collected by filtration. The powder was stirred in distilled water (1000 g) and then the filtration was repeated three times until the filtrate was neutral. The obtained powder was dried with a blower dryer at 50° C. to obtain Resin A1.

(Synthesis of resin A4)
Under a nitrogen stream, N,N-dimethylacetamide (16.5 g) heated to 90° C. was charged with the above monomer (i-1) (13.6 g), methacrylic acid (6.5 g), methacrylic acid A solution containing methyl (0.45 g), styrene (17.8 g), polymerization initiator V-601 (FUJIFILM Wako Chemical Co., Ltd., 1.4 g) and N,N-dimethylacetamide (12.8 g) for 2 hours. dripped over. After the dropwise addition of the solution was completed, 0.25 g of V-601 was added three times at intervals of 1 hour. The mixture was reacted at 90° C. for 3 hours and then cooled to room temperature. The reaction was diluted with N,N-dimethylacetamide (49.0 g), diazabicycloundecene (26.4 g) and 4-methoxyphenol (0.25 g) were added, and stirred at room temperature for 12 hours. The reaction was diluted with methanol (50 mL), then the diluted solution was added dropwise to a mixture of concentrated hydrochloric acid (12.3 g) and distilled water (780 g). The precipitated powder was collected by filtration. The powder was stirred in distilled water (1000 g) and then the filtration was repeated three times until the filtrate was neutral. The obtained powder was dried with a blower dryer at 50° C. to obtain Resin A4.

(Synthesis of resins A2, A3, A5 to A9)
Resins A2 and A3 were obtained by the same method as that for synthesizing resin A1, except that the types and amounts of monomers added were appropriately changed according to the structure of the target resin. Resins A5 to A9 were obtained by the same method as that for synthesizing resin A4, except that the types and amounts of monomers added were appropriately changed according to the structure of the target resin.

[Preparation of comparative resins X1 to X2]
The following comparative resins X1 to X2 were prepared. The numerical value attached to each structural unit of each resin represents the content of the structural unit (unit: % by mass). Table 1 shows the weight average molecular weight (Mw), dispersity and acid value of each resin.

[Preparation of photosensitive composition]
A photosensitive composition was prepared according to the description in Table 2. In preparing the photosensitive composition, the resins listed in Table 2 were dissolved in an organic solvent and used. The organic solvent used to dissolve the resin contains propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate in a weight ratio of 1:1. The proportion of the resin in the solution containing the resin and the organic solvent was 30% by mass. In Table 2, the numerical value described in the component column indicates the content (unit: parts by mass).

[Preparation of Intermediate Layer Forming Composition]
A composition for forming an intermediate layer was prepared according to the description in Table 2. In Table 2, the numerical value described in the component column indicates the content (unit: parts by mass).

[Production of transfer film]
A transfer film including a temporary support, an intermediate layer and a photosensitive composition layer was produced according to the following procedure. On a temporary support (polyethylene terephthalate film having a thickness of 16 μm, Lumirror 16KS40, Toray Industries, Inc.), the intermediate layer-forming composition was applied using a bar coater so that the thickness after drying was 1.0 μm. It was applied and dried at 90° C. using an oven to form an intermediate layer. On the intermediate layer, a photosensitive composition is applied using a bar coater so that the thickness after drying is 3.0 μm, dried at 80° C. using an oven, and a photosensitive composition layer (specifically was formed with a negative photosensitive composition layer). A protective film (polyethylene terephthalate having a thickness of 16 μm, 16KS40, Toray Industries, Inc.) was crimped onto the photosensitive composition layer.

[Preparation of laminate having resist pattern]
A copper layer with a thickness of 500 nm was formed by sputtering on a polyethylene terephthalate film with a thickness of 188 μm to prepare a PET substrate with a copper layer. After cutting the transfer film into 50 cm squares, the protective film was peeled off. The photosensitive composition layer of the transfer film and the copper layer of the PET substrate with the copper layer were laminated under the conditions of a roller temperature of 90° C., a linear pressure of 0.8 MPa and a linear velocity of 3.0 m/min. A laminate obtained by laminating the transfer film and the PET substrate with the copper layer has a structure of "polyethylene terephthalate film/copper layer/photosensitive composition layer/intermediate layer/temporary support".

The intermediate layer was exposed by peeling the temporary support from the laminate. A photomask was brought into intimate contact with the intermediate layer of the laminate. In the line-and-space pattern formed on the photomask, the line width ([mu]m)/space width ([mu]m) is set to 1/2, and the line width is designed from 1 [mu]m to 10 [mu]m in increments of 1 [mu]m. Using a high-pressure mercury lamp exposure machine (MAP-1200L, Dai Nippon Kaken Co., Ltd., dominant wavelength: 365 nm), the photosensitive composition layer was irradiated with light through the intermediate layer. In the exposure, the exposure amount was adjusted so that the line width of the resist pattern corresponding to the 5 μm line formed on the photomask was 5 μm.

Development was performed using a 1.0% sodium carbonate aqueous solution (pH 11.4) at 28°C as a developer to form a resist pattern. Specifically, a developer was used to perform a shower process for 30 seconds, and then an AirKnife process was performed to remove the developer. Further, a shower treatment was performed using pure water for 30 seconds, and then an AirKnife treatment was performed.

A laminate having a resist pattern was obtained by the above procedure. A laminate having a resist pattern has a structure of "polyethylene terephthalate film/copper layer/resist pattern". The ratio of line width to space width in the resist pattern is 1:2. The copper layer not covered with the resist pattern functions as a seed layer in the copper plating process described below.

[Evaluation: minimum resolution line width]
The minimum line width of a resist pattern formed without development residue and collapse was adopted as the minimum resolution line width. Table 2 shows the evaluation results.

[Evaluation: resist pattern shape]
A cross-sectional shape of a resist pattern having a line width/space width of 3 μm/6 μm was observed using a scanning electron microscope. A value of (line width at the bottom end of the line)/(line width at the top end of the line) was calculated, and the resist pattern shape was evaluated according to the following criteria. The bottom end of the line means the end of the line located on the copper layer side in cross-sectional observation. As the value of (line width at bottom end of line)/(line width at top end of line) is closer to 1, the difference between the line width at the bottom end of the line and the line width at the top end of the line is smaller, and the pattern skirting is less. Table 2 shows the evaluation results.
A: The value of (line width at bottom end of line)/(line width at top end of line) is less than 1.05.
B: The value of (line width at bottom end of line)/(line width at top end of line) is 1.05 or more and less than 1.1.
C: The value of (line width at bottom end of line)/(line width at top end of line) is 1.1 or more and less than 1.2.
D: The value of (line width at bottom end of line)/(line width at top end of line) is 1.2 or more.

[Evaluation: Copper pattern shape]
A laminate having a resist pattern was placed in a copper sulfate plating solution (copper sulfate: 75 g/L, sulfuric acid: 190 g/L, chloride ion: 50 mass ppm, "Coppergleam PCM", Meltex Inc., 5 mL/L). , 1 A/dm ² . The copper-plated laminate was washed with water and then dried. The resist pattern was removed by immersing the laminate in a monoethanolamine stripping solution at 50°C. The copper layer (that is, the seed layer) exposed by removing the resist pattern was removed using an aqueous solution containing 0.1% by mass of sulfuric acid and 0.1% by mass of hydrogen peroxide to obtain a copper pattern. A cross-sectional shape of a copper pattern formed in a space region of a resist pattern having a line width/space width of 3 μm/6 μm was observed using a scanning electron microscope. A value of (line width at the bottom end of the line)/(line width at the top end of the line) was calculated, and the copper pattern shape was evaluated according to the following criteria. The closer the value of (line width at line bottom end)/(line width at line top end) to 1, the smaller the difference between the line width at line bottom end and the line width at line top end, and the less undercut. Table 2 shows the evaluation results.
A: The value of (line width at bottom end of line)/(line width at top end of line) is 0.95 or more.
B: The value of (line width at bottom end of line)/(line width at top end of line) is 0.9 or more and less than 0.95.
C: The value of (line width at bottom end of line)/(line width at top end of line) is 0.8 or more and less than 0.9.
D: The value of (line width at bottom end of line)/(line width at top end of line) is less than 0.8.

Details of the abbreviations of the ingredients listed in Table 2 are as follows.

[Polymerizable compound]
・SR454: Ethoxylated (3) trimethylolpropane triacrylate, Tomoe Kogyo Co., Ltd. ・BPE-500: Ethoxylated bisphenol A dimethacrylate, Shin-Nakamura Chemical Co., Ltd. ・BPE-100: Ethoxylated bisphenol A dimethacrylate, Shin-Nakamura Kagaku Kogyo Co., Ltd. M270: Aronix M-270, polypropylene glycol diacrylate (n ≈ 12), Toagosei Co., Ltd. A-DCP: Tricyclodecanedimethanol diacrylate, Shin-Nakamura Chemical Industry Co., Ltd.)

[Polymerization initiator]
・IRGACURE OXE-02: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime, BASF ・Omnirad 907: 2-methyl- 1-(4-methylthiophenyl)-2-morpholinopropan-1-one, IGM Resins B.V. ・Omnirad 184: 1-hydroxycyclohexylphenyl ketone, IGM Resins B.V. ・Omnirad 819: Bis( 2,4,6-trimethylbenzolyl)phenylphosphine oxide, IGM Resins B.V.

[anti-rust]
・CBT-1: Carboxybenzotriazole, Johoku Chemical Industry Co., Ltd.

[Surfactant]
・F-552: Fluorine-based surfactant, Megafac F-552, DIC Corporation ・F-444: Fluorine-based surfactant, Megafac F-444, DIC Corporation

[solvent]
・MMPGAc: 1-methoxy-2-propyl acetate ・MEK: methyl ethyl ketone

[resin]
・PVA: Polyvinyl alcohol, Kuraray Poval PVA-205, Kuraray Co., Ltd. ・PVP: Polypyrrolidone, Polyvinylpyrrolidone K-30, Nippon Shokubai Co., Ltd. ・HPMC: Hydroxypropyl methylcellulose, Metolose 60SH-03, Shin-Etsu Chemical Co., Ltd.

Table 2 shows that the resolution of the resist patterns in Examples 1-23 is superior to the resolution of the resist patterns in Comparative Examples 1-2.

<Examples 1A to 23A>
In each of Examples 1 to 23, a resist pattern and a copper pattern were formed by the method described above, except that an i-line stepper was used to project and expose the photosensitive composition layer. As a result, a resist pattern with excellent resolution was obtained and a copper pattern with less undercut was obtained.

(Description of symbols)
10: Transfer film 11: Temporary support 13: Intermediate layer 15: Photosensitive composition layer 17: Transfer layer 19: Protective film

The disclosure of Japanese Patent Application No. 2021-210879 filed on December 24, 2021 is incorporated herein by reference in its entirety. In addition, all publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. , incorporated herein by reference.

Claims

preparing a laminate including, in that order, a substrate and a conductive layer;
Providing a photosensitive composition layer containing a resin containing a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group on the conductive layer;
exposing the photosensitive composition layer;
Forming a resist pattern by performing a development process on the photosensitive composition layer;
performing a plating process on the conductive layer in a region where the resist pattern is not arranged;
removing the resist pattern;
forming a conductor pattern by removing the conductive layer exposed by removing the resist pattern, in this order;
A method for manufacturing a laminate having a conductor pattern.

In formula B1, X B1 and X B2 each independently represent —O— or —NR N —, R N represents a hydrogen atom or an alkyl group, and L is a divalent group containing no hydroxy group. and R B1 and R B2 each independently represent a hydrogen atom or an alkyl group.
Providing the photosensitive composition layer includes preparing a transfer film containing a temporary support and the photosensitive composition layer in this order, and attaching the photosensitive composition layer and the conductive layer of the transfer film. A method of manufacturing a laminate having a conductor pattern according to claim 1, comprising:
3. The method of claim 2, further comprising peeling off the temporary support between laminating the photosensitive composition layer and the conductive layer and exposing the photosensitive composition layer. A method for manufacturing a laminate having a conductor pattern.
The method for producing a laminate having a conductor pattern according to Claim 2 or Claim 3, wherein the transfer film further includes an intermediate layer between the temporary support and the photosensitive composition layer.
The method for producing a laminate having a conductor pattern according to any one of claims 1 to 4, wherein the photosensitive composition layer further contains a photopolymerization initiator and a polymerizable compound.
The method for producing a laminate having a conductive conductor pattern according to claim 5, wherein the photopolymerization initiator is a hexaarylbiimidazole compound.
The method for producing a laminate having a conductor pattern according to claim 5 or claim 6, wherein the polymerizable compound contains a radically polymerizable compound having at least two polymerizable groups.
The polymerizable compound contains a radically polymerizable compound having two polymerizable groups, and the ratio of the content of the radically polymerizable compound having two polymerizable groups to the content of the polymerizable compound is 80% by mass. 7. The method for manufacturing a laminate having a conductor pattern according to claim 5 or 6, which is the above.
The method for producing a laminate having a conductor pattern according to any one of claims 5 to 8, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure.
The polymerizable compound contains a polymerizable compound having a bisphenol structure, and the content ratio of the polymerizable compound having a bisphenol structure to the content of the polymerizable compound is 50% by mass or more, claims 5- A method for manufacturing a laminate having the conductor pattern according to claim 8 .
a resin comprising a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group;
a photoinitiator;
and a polymerizable compound,
The photopolymerization initiator is a hexaarylbiimidazole compound,
Photosensitive composition.

In formula B1, X B1 and X B2 each independently represent —O— or —NR N —, R N represents a hydrogen atom or an alkyl group, and L is a divalent group containing no hydroxy group. and R B1 and R B2 each independently represent a hydrogen atom or an alkyl group.
The photosensitive composition according to claim 11, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure.
12. According to claim 11, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure, and the ratio of the content of the polymerizable compound having a bisphenol structure to the content of the polymerizable compound is 50% by mass or more. A photosensitive composition as described.
Including a temporary support and a photosensitive composition layer in this order,
The photosensitive composition layer contains a resin containing a structural unit represented by the following formula B1 and a structural unit having an alkali-soluble group, a photopolymerization initiator, and a polymerizable compound,
The photoinitiator comprises a hexaarylbiimidazole compound,
transfer film.

In formula B1, X B1 and X B2 each independently represent —O— or —NR N —, R N represents a hydrogen atom or an alkyl group, and L is a divalent group containing no hydroxy group. and R B1 and R B2 each independently represent a hydrogen atom or an alkyl group.
The transfer film according to claim 14, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure.
15. According to claim 14, wherein the polymerizable compound contains a polymerizable compound having a bisphenol structure, and the ratio of the content of the polymerizable compound having a bisphenol structure to the content of the polymerizable compound is 50% by mass or more. Transfer film as described.
Including a temporary support and a photosensitive composition layer in this order,
The photosensitive composition layer contains a resin containing a structural unit having a structural unit represented by the following formula B1 and an alkali-soluble group,
Transfer film for plating wiring formation.

In formula B1, X B1 and X B2 each independently represent —O— or —NR N —, R N represents a hydrogen atom or an alkyl group, and L is a divalent group containing no hydroxy group. and R B1 and R B2 each independently represent a hydrogen atom or an alkyl group.
The transfer film for forming plated wiring according to claim 17, further comprising an intermediate layer between the temporary support and the photosensitive composition layer.