JP2023043527A - Photosensitive composition, transfer film, and manufacturing method of laminate having conductor pattern - Google Patents

Abstract

To provide a photosensitive composition capable of forming a resist pattern excellent in acid tolerance.SOLUTION: A photosensitive composition contains an alkali-soluble resin, a polymerizable compound having an ethylenic unsaturated group, and a photoinitiator. The polymerizable compound contains a polymerizable compound A which satisfies a requirement (X1) as follows: the requirement (X1): a contact angle of water of a film which is obtained by applying a composition comprising 100 pts.mass of the polymerizable compound A, 1.0 pt.mass of 1-[9-ethyl-6-(2- methylbenzoyl)-9H- carbazole-3-yl] ethanone-1-(O-acetyloxime), and 9 pts.mass of methyl ethyl ketone so as to form a film with 2.0 μm, and irradiating the film with i-line beams at an exposure value of 500 mJ/cm2 in a nitrogen atmosphere followed by heating at 150°C for 30 minutes is 74 degrees or more.SELECTED DRAWING: None

Description

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

As a method for obtaining circuit wiring and the like, it is common to employ a method of performing an etching treatment using a resist pattern formed from a photosensitive composition. Specifically, for example, a photosensitive composition layer is formed on a substrate having a conductive layer, the photosensitive composition layer is pattern-exposed, and then developed to form a pattern on the conductive layer, and the pattern is formed. A method of etching a portion of the conductive layer that is not covered and is exposed is exemplified.

For example, Patent Document 1 discloses a photosensitive resin composition containing a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. Further, it is also disclosed that etching treatment is performed using a resist pattern formed from the photosensitive resin composition.

JP 2018-159841 A

Here, the etchant used for the etching process is often acidic.

The present inventors formed a resist pattern using the photosensitive composition (photosensitive resin composition) described in Patent Document 1, and etched the conductive layer. Denaturation due to the etchant was observed in the conductive layer of . In addition, the present inventors have found that such denaturation of the conductive layer occurs due to insufficient acid resistance of the resist pattern.
As the conductive layer, a conductive layer containing silver is sometimes used because of its high conductivity. Silver is more difficult to etch than other materials used in conductive layers (eg, copper), and the etchant used often has a lower pH. Therefore, resist patterns used for etching conductive layers containing silver are required to have further improved acid resistance.

Accordingly, an object of the present invention is to provide a photosensitive composition capable of forming a resist pattern having excellent acid resistance.
Another object of the present invention is to provide a transfer film and to provide a method for producing a laminate having a conductor pattern.

The present inventors have completed the present invention as a result of earnest investigations to solve the above problems. That is, the inventors have found that the above problems can be solved by the following configuration.

[1] an alkali-soluble resin;
a polymerizable compound having an ethylenically unsaturated group;
and a photopolymerization initiator,
The photosensitive composition, wherein the polymerizable compound contains a polymerizable compound A that satisfies the following requirement (X1).
Requirement (X1): 100 parts by mass of the polymerizable compound A and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 74 degrees or more.
[2] The photosensitive composition according to [1], wherein the polymerizable compound A is a polymerizable compound A1 represented by the following formula (A).
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
[3] The photosensitive composition according to [1] or [2], wherein the polymerizable compound contains a polymerizable compound B that satisfies the following requirements (X2).
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less.
[4] The photosensitive composition of [3], wherein the polymerizable compound B has a bisphenol A structure.
[5] The photosensitive composition according to [3] or [4], wherein the mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00. .
[6] The photosensitizer according to any one of [1] to [5], wherein the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30. sex composition.
[7] the polymerizable compound A is a polymerizable compound A1 represented by the following formula (A),
The photosensitive composition according to [1], wherein the polymerizable compound satisfies the following requirement (X2) and contains a polymerizable compound B having a bisphenol A structure.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less.
[8] the polymerizable compound A is a polymerizable compound A1 represented by the following formula (A),
The polymerizable compound contains a polymerizable compound B that satisfies the following requirements (X2) and has a bisphenol A structure,
The mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00,
The photosensitive composition according to [1], wherein the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less.
[9] The photosensitive composition according to any one of [1] to [8], wherein the alkali-soluble resin is a resin A1 that satisfies requirement (X3) below.
Requirement (X3): The contact angle of water on the film obtained by forming a 2.0 μm film made of the resin A1 and then heating it at 150° C. for 30 minutes is 65 degrees or more.
[10] the alkali-soluble resin contains a structural unit derived from styrene,
The photosensitive composition according to any one of [1] to [9], wherein the content of structural units derived from styrene is 20% by mass or more relative to the total mass of the alkali-soluble resin.
[11] The photosensitive composition according to any one of [1] to [10], wherein the alkali-soluble resin has an acid value of 100 mgKOH/g or more.
[12] The photosensitive composition according to any one of [1] to [11], which satisfies the following requirement (X4).
Requirement (X4): A 2.0 μm film formed using the above photosensitive composition was irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere, and heated at 150° C. for 30 minutes. The resulting film has a water contact angle of 60 degrees or more.
[13] a temporary support;
[1] A transfer film having a photosensitive composition layer formed using the photosensitive composition according to any one of [1] to [12].
[14] The transfer film of [13], wherein the photosensitive composition layer has a thickness of 1 to 10 μm.
[15] a preparation step of preparing a laminate having a substrate, a conductive layer containing silver, and a photosensitive composition layer in this order;
An exposure step of pattern-exposing the photosensitive composition layer;
a developing step of developing the exposed photosensitive composition layer to form a resist pattern;
A method for manufacturing a laminate having a conductor pattern, comprising an etching step of etching the conductive layer in a region where the resist pattern is not formed, with an etchant having a pH of less than 2.0,
The photosensitive composition layer is
an alkali-soluble resin;
a polymerizable compound having an ethylenically unsaturated group;
and a photopolymerization initiator,
A method for producing a laminate having a conductor pattern, wherein the polymerizable compound contains a polymerizable compound A that satisfies the following requirement (X1).
Requirement (X1): 100 parts by mass of the polymerizable compound A and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 74 degrees or more.
[16] The method for producing a laminate having a conductor pattern according to [15], wherein the polymerizable compound A is a polymerizable compound A1 represented by the following formula (A).
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
[17] The method for producing a laminate having a conductor pattern according to [15] or [16], wherein the polymerizable compound contains a polymerizable compound B that satisfies requirement (X2) below.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less.
[18] The method for producing a laminate having a conductor pattern according to [17], wherein the polymerizable compound B is a polymerizable compound B1 having a bisphenol A structure.
[19] The conductive pattern according to [17] or [18], wherein the mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00. A method for manufacturing a laminate.
[20] The conductor according to any one of [15] to [19], wherein the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30. A method for manufacturing a laminate having a pattern.
[21] The polymerizable compound A contains a polymerizable compound A1 represented by the following formula (A),
The method for producing a laminate having a conductor pattern according to [15], wherein the polymerizable compound satisfies the following requirement (X2) and contains a polymerizable compound B having a bisphenol A structure.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less.
[22] The polymerizable compound A contains a polymerizable compound A1 represented by the following formula (A),
A photosensitive composition in which the polymerizable compound satisfies the following requirements (X2) and contains a polymerizable compound B having a bisphenol A structure,
The mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00,
The method for producing a laminate having a conductor pattern according to [15], wherein the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less.
[23] The method for producing a laminate having a conductor pattern according to any one of [15] to [22], wherein the alkali-soluble resin is a resin A1 that satisfies requirement (X3) below.
Requirement (X3): The contact angle of water on the film obtained by forming a 2.0 μm film made of the resin A1 and then heating it at 150° C. for 30 minutes is 65 degrees or more.
[24] the alkali-soluble resin contains a structural unit derived from styrene,
Manufacture of a laminate having a conductor pattern according to any one of [15] to [23], wherein the structural unit derived from styrene is 20% by mass or more with respect to the total mass of the alkali-soluble resin. Method.
[25] The method for producing a laminate having a conductor pattern according to any one of [15] to [24], wherein the alkali-soluble resin has an acid value of 100 mgKOH/g or more.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition which can form the resist pattern which is excellent in acid resistance can be provided.
Further, according to the present invention, it is possible to provide a transfer film and a method for producing a laminate having a conductor pattern.

It is the schematic which shows an example of a structure of the transfer film used for the manufacturing method of this invention. 1 is a schematic diagram of a photomask used in Examples. FIG.

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

Hereinafter, the meaning of each description in this specification is expressed.
In this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
In the present specification, in the numerical ranges described in stages, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. . Moreover, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.

In this specification, the term "process" is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term as long as the intended purpose of the process is achieved. .

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

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). ), using THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, a value converted using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer. be.
In this specification, unless otherwise specified, the ratio of polymer constitutional units is the mass ratio.
In this specification, unless otherwise specified, the molecular weight of compounds having a molecular weight distribution is the weight average molecular weight (Mw).
In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer.
In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

As used herein, "(meth)acryl" is a concept that includes both acryl and methacryl, and "(meth)acryloxy group" is a concept that includes both acryloxy and methacryloxy.

In this specification, the term “alkali-soluble” means that the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at 22° C. is 0.1 g or more.

As used herein, the term “water-soluble” means that the solubility in 100 g of water having a liquid temperature of 22° C. and a pH of 7.0 is 0.1 g or more. Thus, for example, by water-soluble resin is intended a resin that satisfies the solubility conditions set forth above.

As used herein, "pH" refers to the value measured by a method conforming to JIS Z8802-1984 using a known pH meter. The pH measurement temperature is 25°C.

As used herein, the “solid content” of the composition means a component that forms a composition layer formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), the solvent means all ingredients except In addition, as long as it is a component that forms a composition layer, a liquid component is also regarded as a solid content.

<Photosensitive composition>
The photosensitive composition of the present invention comprises an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, and the polymerizable compound satisfies the following requirement (X1): a polymerizable compound Including A.
Requirement (X1): 100 parts by mass of polymerizable compound A and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) 1.0 A composition consisting of parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere for 30 minutes at 150°C. The contact angle of water on the film obtained by heating is 74 degrees or more.
Details of the requirement (X1) will be described later.

The resist pattern formed using the photosensitive composition of the present invention is used as a resist pattern for etching the conductive layer on which the resist pattern is arranged, and when an acidic etchant is used, the resist pattern is coated. Denaturation of the conductive layer of the part is hard to occur. That is, the resist pattern formed using the photosensitive composition of the present invention is excellent in acid resistance. In addition, the resist pattern has acid resistance that can withstand an etchant (for example, an etchant having a pH of less than 2.0) used for etching a conductive layer containing silver.
Although the mechanism by which the resist pattern formed by the photosensitive composition is excellent in acid resistance is not necessarily clear, the present inventors presume as follows.
The resist pattern formed by the photosensitive composition is difficult for the etchant used in the etching treatment to penetrate because the photosensitive composition satisfies the feature points, and the conductive layer in the portion covered with the resist pattern is etched. Since it is difficult for the liquid to reach there, it is thought that as a result, the conductive layer in the portion covered with the resist pattern is unlikely to be denatured. Therefore, the resist pattern formed from the photosensitive composition is considered to have excellent acid resistance.

The photosensitive composition layer formed from the photosensitive composition is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to the cured layer.

Components that may be included in the photosensitive composition of the present invention are described below.
In addition, hereinafter, the resist pattern formed by the photosensitive composition of the present invention is used as a resist pattern for etching the conductive layer on which the resist pattern is arranged, and when an acidic etchant is used, the resist pattern is coated. It is also called "excellent in acid resistance" that the denaturation of the conductive layer in the exposed portion is unlikely to occur.

[Alkali-soluble resin]
The photosensitive composition contains an alkali-soluble resin (hereinafter also referred to as "resin A").
Examples of resin A include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, and reaction of epoxy acrylate resins with acid anhydrides. Acid-modified epoxy acrylate resin obtained in, but not limited to.

As the resin A, a (meth)acrylic resin is preferred. In addition, in this specification, (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound. In the (meth)acrylic resin, the content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total structural units of the (meth)acrylic resin. 60% by mass or more is more preferable.
As the resin A, a polymer having a structural unit derived from a (meth)acrylic compound and a structural unit derived from a styrene compound is also preferable.

The acid value of Resin A is 220 mgKOH/g from the viewpoint that the resolution of the photosensitive composition layer formed by the photosensitive composition is more excellent by suppressing swelling of the negative photosensitive composition by the developer. The following is preferred, less than 200 mgKOH/g is more preferred, and less than 190 mgKOH/g is even more preferred.
The lower limit of the acid value of Resin A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 100 mgKOH/g or more, still more preferably 120 mgKOH/g or more, and particularly 150 mgKOH/g or more. Preferably, 170 mgKOH/g or more is most preferred.
The acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. The acid value can be calculated, for example, from the average content of acid groups in the compound. The acid value of Resin A may be adjusted according to the type of structural units constituting Resin A and the content of structural units containing acid groups, which will be described later.
Hereinafter, the resolution of the photosensitive composition layer formed from the photosensitive composition is also simply referred to as "resolution".

The weight average molecular weight of Resin A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, even more preferably 60,000 or less. On the other hand, when the weight-average molecular weight is 5,000 or more, from the viewpoint of controlling the properties of development aggregates and the properties of unexposed films such as edge fuse properties and cut chip properties in the case of negative photosensitive resin laminates. preferred from The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fuseability refers to the extent to which the negative photosensitive composition layer tends to protrude from the end face of the roll when the negative photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree of easiness of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the negative photosensitive resin laminate, etc., it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products. The dispersity of resin A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

Moreover, it is also preferable that the resin A is a resin A1 that satisfies the following requirement (X3).
Requirement (X3): After forming a 2.0 μm film made of resin A1, the film obtained by heating at 150° C. for 30 minutes has a water contact angle of 65 degrees or more.
As a method of forming a film made of resin A1, a method of forming a film by applying a composition obtained by dissolving resin A1 in methyl ethyl ketone can be mentioned. In addition, when the resin A1 is difficult to dissolve in methyl ethyl ketone, it is preferable to select a solvent having a boiling point of 150° C. or less in which the resin A1 dissolves.
The method for measuring the contact angle is the same as the method for measuring requirement (X1) described later.
The contact angle of water is preferably 68 degrees or more, more preferably 71 degrees or more. Although the upper limit is not particularly limited, it may be 180 degrees or less, preferably 90 degrees or less.
The contact angle of water can be adjusted by the type of the structural unit constituting the resin A and the content of the structural unit having a carboxyl group, which will be described later.

The structural units that the resin A can contain are described in detail below.

(Structural Unit Having Aromatic Hydrocarbon Group)
Moreover, from the viewpoint of suppressing thickening of line width and deterioration of resolution when the focus position during exposure is shifted, the resin A preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
The content of structural units derived from a monomer having an aromatic hydrocarbon group in Resin A is preferably 20% by mass or more, more preferably 30% by mass or more, relative to the total mass of Resin A. Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of resin A are included, the average content of structural units derived from monomers having aromatic hydrocarbon groups is preferably within the above range.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred.
When the monomer having an aromatic hydrocarbon group is styrene, the content of structural units based on styrene is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, based on the total mass of Resin A. Preferably, 30 to 60% by mass is more preferable, and 40 to 60% by mass is particularly preferable. In addition, when the photosensitive composition contains a plurality of types of resins A, the content of structural units having an aromatic hydrocarbon group is obtained as a weight average value.

The aralkyl group includes an optionally substituted phenylalkyl group, and an optionally substituted benzyl group is preferred.

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

Examples of monomers having a benzyl group which may have a substituent include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinylbenzyl chloride and vinylbenzyl Examples thereof include vinyl monomers having a benzyl group such as alcohol, preferably (meth)acrylates having a benzyl group, more preferably benzyl (meth)acrylates.
When the monomer having an aromatic hydrocarbon group is benzyl (meth)acrylate, the content of structural units based on benzyl (meth)acrylate is preferably 50 to 95% by mass with respect to the total mass of Resin A. , more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass.

Further, the resin A containing a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one monomer having a carboxy group described later and/or Alternatively, it is preferably obtained by polymerizing at least one non-acidic monomer described later.

The resin A that does not contain a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one monomer having a carboxy group, and has a carboxy group. More preferably, it is obtained by copolymerizing at least one monomer and at least one non-acidic monomer described later.

(Structural Unit Having Carboxy Group)
Resin A preferably contains a structural unit having a carboxy group.
A structural unit having a carboxy group is derived from a monomer having a carboxy group in the molecule.
Examples of monomers having a carboxy group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. be done. Among these, (meth)acrylic acid is preferred.
The content of structural units having a carboxy group in Resin A is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass, relative to the total mass of Resin A.
Setting the content to 5% by mass or more is preferable from the viewpoint of exhibiting good developability, controlling edge fuse properties, and the like. Setting the content to 50% by mass or less is preferable from the viewpoint of high resolution of the resist pattern and the groove shape, and further from the viewpoint of acid resistance.

(Non-acidic structural unit)
Resin A may contain non-acidic structural units.
The non-acidic structural unit is derived from a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
Examples of the above monomers (non-acidic monomers) include 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, cyclohexyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic Isobutyl acid, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, (meth)acrylic acid (meth)acrylates such as 2-octyl acid, 3-octyl (meth)acrylate, tert-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred.
The content of non-acidic structural units in Resin A is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 1 to 30% by mass, relative to the total mass of Resin A.

(Other structural units)
Resin A may have a structural unit having any one of a linear structure, a branched structure, and an alicyclic structure in the side chain.
As used herein, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branched from the main chain. show.
By using a monomer containing a group having a linear structure in the side chain, a monomer containing a group having a branched structure in the side chain, or a monomer containing a group having an alicyclic structure in the side chain , a linear structure, a branched structure, or an alicyclic structure can be introduced into the side chain of the resin A. The alicyclic structure may be monocyclic or polycyclic.
Specific examples of the monomer containing a group having a branched structure in its side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. , isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert (meth)acrylate - octyl and the like. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate and tert-butyl methacrylate are more preferred.
Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. mentioned. (Meth)acrylates having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are also included. More specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl, (meth) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-(meth)acrylate Ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2 -methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5- (meth)acrylate yl, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-(meth)acrylate 2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl, (meth)acryl (nor)bornyl acid, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these (meth)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylic acid -2-adamantyl, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, Isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are more preferred.

Resin A may be used alone or in combination of two or more.
When two or more types are used, two types of resin A containing a structural unit derived from a monomer having an aromatic hydrocarbon group are mixed and used, or a monomer having an aromatic hydrocarbon group It is preferable to use a mixture of the resin A containing structural units derived from an aromatic hydrocarbon group and the resin A containing no structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of resin A used containing structural units derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of resin A. Preferably, 80% by mass or more is more preferable, and 90% by mass or more is particularly preferable.

Synthesis of Resin A involves combining one or more of the monomers described above with radicals such as a peroxide polymerization initiator (e.g. benzoyl peroxide) and an azo polymerization initiator (e.g. azobisisobutyronitrile). It can be carried out by polymerizing using a polymerization initiator.
As a polymerization method, a monomer solution and a radical polymerization initiator solution are added dropwise to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and isopropanol) under a nitrogen stream. It is preferably carried out by heating and stirring. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a synthetic means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

(Properties of alkali-soluble resin (resin A))
The glass transition temperature (Tg) of Resin A is preferably 30 to 135°C. By using the resin A having a Tg of 135° C. or lower, thickening of the line width and degradation of resolution when the focal point shifts during exposure can be suppressed. From this point of view, the Tg of Resin A is preferably 130° C. or lower, more preferably 120° C. or lower, and particularly preferably 110° C. or lower. Moreover, it is preferable to use the resin A having a Tg of 30° C. or more from the viewpoint of improving the edge fuse resistance. From this point of view, the Tg 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 dispersity of resin A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In this disclosure, dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight). In the present disclosure, the weight average molecular weight and number average molecular weight are values measured using gel permeation chromatography.

The photosensitive composition may contain other resins than the resin A described above.
Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

The content of resin A is preferably 10 to 95% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and 40 to 60% by mass with respect to the total mass of the photosensitive composition. Especially preferred. It is preferable from the viewpoint of controlling the developing time that the content of the resin A is 95% by mass or less. On the other hand, setting the content of resin A to 10% by mass or more is preferable from the viewpoint of improving edge fuse resistance.

[Polymerizable compound]
The photosensitive composition contains a polymerizable compound having an ethylenically unsaturated group.
The polymerizable compound includes a polymerizable compound A that satisfies requirement (X1) described later.
Moreover, the polymerizable compound preferably contains a polymerizable compound B that satisfies the requirement (X2) described later.
By including the polymerizable compound A and the polymerizable compound B, it is considered that the peelability of the resist pattern formed by the photosensitive composition is more excellent. Hereinafter, the releasability of a resist pattern formed from a photosensitive composition is also simply referred to as "releasability."
As used herein, the term "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator, which will be described later, and that is different from the resin A described above.

Examples of the ethylenically unsaturated group that the polymerizable compound has include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, a maleimide group, and the like, and an acryloyl group or a methacryloyl group is preferable.

The polymerizable compound will be described in detail below.

(Polymerizable compound A)
Polymerizable compound A is a polymerizable compound that satisfies the following requirement (X1).
Requirement (X1): 100 parts by mass of polymerizable compound A and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) 1.0 A composition consisting of parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere and heated at 150° C. for 30 minutes. The contact angle of water of the film obtained by this is 74 degrees or more.
The nitrogen atmosphere means a state in which the total pressure is 1.0 atm and the partial pressure of nitrogen is 0.98 atm or higher.
The contact angle of water is measured by the tangent method using a contact angle meter (trade name “FAMMS DM-701” manufactured by Kyowa Interface Science Co., Ltd.). More specifically, using the contact angle meter, the amount of water dropped is 1 μL under the conditions of 23° C. and 50% humidity, and the contact angle is measured 20 seconds after dropping water onto the film. do.
The contact angle of water is preferably 76 degrees or more, more preferably 80 degrees or more. Although the upper limit is not particularly limited, it may be 180 degrees or less, preferably 90 degrees or less.

The polymerizable compound A is not particularly limited as long as it satisfies the requirement (X1).
From the viewpoint of photosensitivity, the polymerizable compound A is preferably a compound having two or more ethylenically unsaturated groups in one molecule. In terms of resolution and peelability, the number of ethylenically unsaturated groups that the polymerizable compound A has in one molecule is preferably 6 or less, more preferably 3 or less, and 2 or less. More preferred.

The polymerizable compound A preferably has a hydrocarbon group in terms of better acid resistance. Although the hydrocarbon group is not particularly limited, the number of carbon atoms in the hydrocarbon group is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, from the viewpoint of better acid resistance. Although the upper limit of the number of carbon atoms is not particularly limited, 20 or less can be mentioned.
Further, the hydrocarbon group may be a hydrocarbon group having a ring structure or a hydrocarbon group having a chain structure.
The ring structure of the hydrocarbon group may be either aromatic or non-aromatic, preferably non-aromatic. Moreover, the ring structure of the above hydrocarbon group may be monocyclic or polycyclic, and is preferably polycyclic.
The ring structure of the hydrocarbon group having a ring structure includes aromatic ring structures such as benzene ring, naphthalene ring, and fluorene ring, cyclopentane ring, cyclohexane ring, norbornane ring, tetrahydrodicyclopentadiene ring, Non-aromatic ring structures such as a tricyclodecane ring and an adamantane ring are included.
The chain structure of the hydrocarbon group having a chain structure may be an alkyl chain having a branched structure or an alkyl chain having no branched structure.

Among them, the polymerizable compound A is preferably a polymerizable compound A1 represented by the following formula (A) in terms of better acid resistance and better releasability.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
From the viewpoint of ease of synthesis, Q ¹ and Q ² are preferably the same group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
The chain divalent hydrocarbon group represented by R ¹ includes an alkylene group.
The number of carbon atoms in the alkylene group is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, from the viewpoint of better acid resistance. Although the upper limit of the number of carbon atoms is not particularly limited, 20 or less can be mentioned.
The alkylene group may be linear or branched.
Linear alkylene groups include butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanylene, undecanylene, and dodecanylene groups.
The branched alkylene group includes an iso-butylene group, a tert-butylene group, a neo-pentylene group, a 2-ethylhexylene group and the like.
The alkylene group is preferably a linear alkylene group.

Specific compounds represented by the formula (A) include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol. Di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol Di(meth)acrylates are mentioned.
Among them, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , and 1,10-decanediol di(meth)acrylate are preferred.

A commercially available product may be used as the polymerizable compound A. Commercially available products of the polymerizable compound A include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,10-decanediol diacrylate, neopentyl glycol di(meth)acrylate, and the like.

The mass ratio of the content of the polymerizable compound A to the total mass of the polymerizable compounds is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of better acid resistance. . Although the upper limit is not particularly limited, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 80% by mass or less, and even more preferably 60% by mass or less from the viewpoint of resolution and peelability. 50% by mass or less is particularly preferred.
The mass ratio of the content of the polymerizable compound A to the total mass of the solid content of the photosensitive composition is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of better acid resistance. Although the upper limit is not particularly limited, it is, for example, 100% by mass or less.

(Polymerizable compound B)
Polymerizable compound B is a polymerizable compound that satisfies the following requirement (X2).
Requirement (X2): 100 parts by mass of polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) 1.0 A composition consisting of parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere for 30 minutes at 150°C. The contact angle of water on the film obtained by heating is 65 degrees or less.
The contact angle is measured by the same method as the requirement (X1).
The contact angle of water is preferably 60 degrees or less, more preferably 50 degrees or less. Although the lower limit is not particularly limited, it may be 0 degrees or more, preferably 40 degrees or more.

Polymerizable compound B is not particularly limited as long as it satisfies the above requirement (X2).
From the viewpoint of photosensitivity, the polymerizable compound B is preferably a compound having two or more ethylenically unsaturated groups in one molecule. In terms of resolution and peelability, the number of ethylenically unsaturated groups that the polymerizable compound B has in one molecule is preferably 6 or less, more preferably 3 or less, and 2 or less. More preferred.
The polymerizable compound B1, which is preferable as the polymerizable compound B, is described below.

(Polymerizable compound B1)
Polymerizable compound B is also preferably polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring; Heterocyclic rings and condensed rings thereof are included, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. In addition, the said aromatic ring may have a substituent.
Polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

Polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive composition due to a developer.
The bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). F structure and bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) can be mentioned, and bisphenol A structure is preferred from the viewpoint of resolution. That is, the polymerizable compound B preferably has a bisphenol A structure.

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

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.
2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane includes, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.) ), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) , 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane ( BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated (10) bisphenol A di Acrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated bisphenol A dimethacrylate (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.).

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

In general formula B1, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents _{C2H4 .} B represents _{C3H6 .} n1 and n3 are each independently an integer of 1-39, and n1+n3 is an integer of 2-40. n2 and n4 are each independently an integer of 0-29, and n2+n4 is an integer of 0-30. The arrangement of -(AO)- and -(B-O)- constitutional units may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group.
In one aspect, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Also, n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.

Examples of the polymerizable compound B other than the polymerizable compound B1 include polymerizable compounds having an acid group (such as a carboxy group). The acid group may form an acid anhydride group.
Examples of the polymerizable compound having an acid group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 ( manufactured by Toagosei Co., Ltd.).
As the polymerizable compound having an acid group, for example, polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 may be used.

Examples of the polymerizable compound B other than the polymerizable compound B1 include bifunctional ethylenically unsaturated compounds having no aromatic ring. Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. .
Alkylene glycol di(meth)acrylates include, for example, ethylene glycol dimethacrylate.
Polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
Examples of commercially available polyalkylene glycol di(meth)acrylates include polyethylene glycol dimethacrylate (4G, 9G, 14G, and 23G, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) M-220 (Toa) (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-240 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-270 (manufactured by Toagosei Co., Ltd.)
Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Examples of commercially available urethane di(meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). .

One type of polymerizable compound B1 may be used alone, or two or more types may be used.
In the photosensitive composition, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 0% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution. % by mass or more is more preferable, and 60% by mass or more is particularly preferable. Although the upper limit is not particularly limited, it is, for example, 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less from the viewpoint of acid resistance and peelability.

Polymerizable compound B may be used alone or in combination of two or more.
In the photosensitive composition, the mass ratio of the content of the polymerizable compound B to the total mass of the polymerizable compounds is preferably 0% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution. % by mass or more is more preferable, and 60% by mass or more is particularly preferable. Although the upper limit is not particularly limited, it is, for example, 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less from the viewpoint of acid resistance and peelability.
The mass ratio of the content of the polymerizable compound B to the total mass of the solid content of the photosensitive composition is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of better peelability. Although the upper limit is not particularly limited, it is, for example, 100% by mass or less, preferably 50% by mass or less, and more preferably 40% by mass or less.

(Other polymerizable compounds)
The photosensitive composition may contain polymerizable compounds (other polymerizable compounds) other than the polymerizable compounds specifically described above.
Polymerizable compounds other than the polymerizable compounds specifically described above are not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound are mentioned.
Other polymerizable compounds are exemplified below. Even if the compound is exemplified as another polymerizable compound, it is included in the above polymerizable compound if it corresponds to the above polymerizable compound A or polymerizable compound B.

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

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

Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified products thereof.
Here, "(tri/tetra/penta/hexa) (meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. , "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.
In one embodiment, the photosensitive composition preferably contains the above-described polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-described polymerizable compound B1 and two or more trifunctional or higher ethylenic unsaturated compounds. More preferably it contains saturated compounds. In this case, the mass ratio of the polymerizable compound B1 and the trifunctional or higher ethylenically unsaturated compound is (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compound) = 1:1. ~5:1 is preferred, 1.2:1 to 4:1 is more preferred, and 1.5:1 to 3:1 is even more preferred.
In one aspect, the photosensitive composition preferably contains the above-described polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd. etc.), ethoxylated trimethylolpropane triacrylate (SR454, SR499, and SR502, etc. manufactured by Tomoe Kogyo Co., Ltd.), alkylene oxide-modified (meth) acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., manufactured by Shin-Nakamura Chemical Co., Ltd. ATM-35E and A-9300, EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M-510 (manufactured by Toagosei Co., Ltd.).

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

A polymerizable compound may be used individually by 1 type, and may use 2 or more types simultaneously.
The content of the polymerizable compound is preferably 0 to 70% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on the total mass of the solid content of the photosensitive composition.

In the photosensitive composition, the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is preferably 0.60 to 1.50, more preferably 0.68 to 1.30, and 0.75 to 1.20 is more preferred.
When the mass ratio is 0.68 or more, a more excellent acid-resistant photosensitive composition can be obtained, and when the mass ratio is 1.30 or less, the peelability is improved. It can be a composition.

The mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A in the photosensitive composition is preferably 0.00 to 6.00, more preferably 0.50 to 4.00. 00 to 3.00 are more preferred, and 1.50 to 2.00 are particularly preferred.
When the mass ratio is 0.50 or more, a photosensitive composition with better resolution and release properties can be obtained, and when the mass ratio is 4.00 or less, better acid resistance can be obtained. can be a photosensitive composition.
Further, in terms of acid resistance, resolution and peelability, the requirements for the above mass ratio are satisfied, and the polymerizable compound A is the polymerizable compound A1, and the polymerizable compound B has a bisphenol A structure. The polymerizable compound B1 is also preferred.

[Photoinitiator]
The photosensitive composition contains a photoinitiator.
A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.

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

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

As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs [0031] to [0042] of JP-A-2011-95716 and paragraphs [0064] to [0081] of JP-A-2015-14783 may be used.

Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: Midori Chemical Co., Ltd.), benzophenone, 4,4′-bis(diethylamino)benzophenone, TAZ-111 (trade name: Midori Chemical Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (products Name: IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Chemical Industry Co., Ltd. made).

Examples of commercially available radical photopolymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01). , manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, BASF company), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4 -morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name : Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (product Name: Omnirad
127, IGM ResinsB. V. ), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1- Phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 2,2-dimethoxy- 1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV), oxime ester-based photopolymerization initiator (trade name : Lunar 6, manufactured by DKSH Japan), 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenyl imidazole dimer) (trade name: B-CIM, manufactured by Hampford), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1 -[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), 1, 2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR- PBG-326, manufactured by Changzhou 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) (trade name: TR-PBG-391, manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.).

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

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

Nonionic photocationic polymerization initiators include, for example, trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds, compounds described in paragraphs [0083] to [0088] of JP-A-2011-221494 may be used. Further, as the oxime sulfonate compound, compounds described in paragraphs [0084] to [0088] of WO 2018/179640 may be used.

The photosensitive composition preferably contains a radical photopolymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

A photoinitiator may be used individually by 1 type, and may be used 2 or more types.
The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass, based on the total mass of the solid content of the photosensitive composition. More than % by mass is more preferable. Although the upper limit is not particularly limited, it is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less, relative to the total mass of the photosensitive composition.

[Dye]
The photosensitive composition has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and , acids, bases, or radicals to change the maximum absorption wavelength (also referred to as “dye N”). Although the detailed mechanism is unknown, when the dye N is contained, the adhesion to the adjacent layer (for example, the water-soluble resin layer) is improved, and the resolution is improved.

In the present specification, the expression that the dye "changes the maximum absorption wavelength due to an acid, a base, or a radical" means that the dye in a colored state is decolored by an acid, a base, or a radical, and the dye in a decolored state is It may mean any one of a mode in which a color is developed by an acid, a base, or a radical, and a mode in which a dye in a coloring state changes to a coloring state of another hue.
Specifically, the dye N may be a compound that changes from a decolored state to develop color upon exposure, or may be a compound that changes from a colored state to decolor upon exposure. In this case, it may be a dye that changes the state of color development or decoloration due to the action of an acid, a base, or a radical generated in the photosensitive composition by exposure. It may be a dye that changes its coloring or decoloring state by changing the state of (for example, pH). Moreover, it may be a dye that changes its coloring or decoloring state by being directly stimulated by an acid, a base, or a radical without being exposed to light.

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

As an example of the coloring mechanism of the dye N, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition, and the photoradical polymerization initiator is added after exposure. A radical, acid, or base generated from a photocationic polymerization initiator or a photobase generator causes a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) to develop color. .

Dye N preferably has a maximum absorption wavelength of 550 nm or more, more preferably 550 to 700 nm, in the wavelength range of 400 to 780 nm during color development, from the viewpoint of visibility in the exposed and unexposed areas. More preferably ~650 nm.
Also, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths should be 450 nm or more.

The maximum absorption wavelength of Dye N was measured in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. and detecting the wavelength (maximum absorption wavelength) at which the light intensity becomes minimum.

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

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

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

Examples of dye N include the following dyes and leuco compounds.
Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophtalein, xylenol blue, methyl Orange, 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 (protective Tsuchiya 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.) company), 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-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino- 4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p- Diethylaminophenylimino-5-pyrazolone can be mentioned.

Specific examples of the leuco compound of the dye N include p,p′,p″-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p -toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methyl amino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7 -xyridinofluorane, 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-dimethyl aminophthalide, 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 .

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

The pigment N may be used singly or in combination of two or more.
The content of dye N is 0.1% by mass or more with respect to the total mass of the photosensitive composition, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. Preferably, 0.1 to 10% by mass is more preferable, 0.1 to 5% by mass is even more preferable, and 0.1 to 1% by mass is particularly preferable.

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

[Thermal crosslinkable compound]
When the photosensitive composition is a negative photosensitive composition, it may contain a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.
Thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained.
Since the blocked isocyanate compound reacts with the hydroxy group and the carboxy group, for example, when the resin and/or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film is lowered. , the function tends to be enhanced when a film obtained by curing a negative photosensitive composition is used as a protective film.
The blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160°C, more preferably 130 to 150°C.
The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate as measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

Blocking agents having a dissociation temperature of 100 to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds ( Compounds having a structure represented by -C(=N-OH)- in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).
Among these, the blocking agent having a dissociation temperature of 100 to 160° C. is preferably at least one selected from oxime compounds from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate and protecting it.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent tends to have a dissociation temperature within a preferred range and produces less development residue than compounds having no oxime structure. It is preferable because it is easy to

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

A commercial item can be used as a block isocyanate compound.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko KK), block-type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals).
Moreover, the compound of the following structure can also be used as a blocked isocyanate compound.

The thermally crosslinkable compounds may be used singly or in combination of two or more.
When the photosensitive composition contains a heat-crosslinkable compound, the content of the heat-crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition.

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

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

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

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

When the photosensitive composition is a colored resin layer, the photosensitive composition preferably contains a chromatic pigment other than the black pigment and the white pigment from the viewpoint of transferability.
The particle size (number average particle size) of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility. The lower limit is preferably 10 nm or more.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter also referred to as “CI”) 42595), Auramine (CI 41000), Fat Black HB (CI .26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Splash (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64 and C.I. I. Pigment Violet 23, C.I. I. Pigment Red 177 is preferred.

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

When the photosensitive composition contains a pigment other than a black pigment (for example, a white pigment and a chromatic pigment), the content of the pigment other than the black pigment is 30% by mass or less with respect to the total mass of the black pigment. Preferably, 1 to 20% by mass, and even more preferably 3 to 15% by mass.

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

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

[solvent]
The photosensitive composition may contain a solvent.
As the solvent, commonly used solvents can be used without particular limitation.
As the solvent, an organic solvent is preferred.
Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , methanol, ethanol, n-propanol, 2-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, and mixed solvents thereof.
Examples of the solvent include a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether acetate and methanol, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or methyl ethyl ketone and propylene glycol. A mixed solvent of monomethyl ether and propylene glycol monomethyl ether acetate is preferred.

You may use a solvent individually by 1 type or in 2 or more types.
When the photosensitive composition contains a solvent, the solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 8 to 40% by mass, even more preferably 10 to 30% by mass. That is, when the photosensitive composition contains a solvent, the content of the solvent is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, more preferably 70 to 95% by mass, based on the total solid content of the photosensitive composition. % by mass is more preferred.

When the photosensitive composition contains a solvent, the viscosity (25° C.) of the photosensitive composition is preferably 1 to 50 mPa s, more preferably 2 to 40 mPa s, more preferably 3 to 30 mPa s, from the viewpoint of coating properties. is more preferred.
Viscosity is measured using, for example, VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
When the photosensitive composition contains a solvent, the surface tension (25° C.) of the photosensitive composition is preferably 5 to 100 mN/m, more preferably 10 to 80 mN/m, more preferably 15 to 40 mN/m, from the viewpoint of coatability. m is more preferred.
Surface tension can be measured, for example, with an Automatic Surface Tensiometer
CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) is used for measurement.

Solvents can also be used as described in paragraphs 0054 and 0055 of US Published Application 2005/282073, the contents of which are incorporated herein.
Also, as the solvent, an organic solvent having a boiling point of 180 to 250° C. (high boiling point solvent) can be used as necessary.

[Other additives]
The photosensitive composition may contain known additives, if necessary, in addition to the above components.
Additives include, for example, radical polymerization inhibitors, antioxidants (e.g., phenidone, etc.), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles, etc.), sensitizers, surfactants, plasticizers, Heterocyclic compounds (eg triazole etc.), pyridines (eg isonicotinamide etc.) and purine bases (eg adenine etc.) can be mentioned.
Other additives include, for example, metal oxide particles, chain transfer agents, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, cross-linking agents, organic Or inorganic suspending agents and paragraphs [0165] to [0184] of JP-A-2014-085643, the contents of which are incorporated herein.
Each additive may be used individually by 1 type, and may be used 2 or more types.

The photosensitive composition may contain a radical polymerization inhibitor.
Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, 1-phenyl-3-pyrazolidone and 4-methoxyphenol are preferred. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition, it is preferred to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor.
The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and 0.01 to 1.0% by mass, based on the total mass of the polymerizable compound. 0% by mass is more preferred.

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

Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene Carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole and the like. As carboxybenzotriazoles, commercially available products such as CBT-1 (manufactured by Johoku Kagaku Kogyo Co., Ltd., trade name) can be used.

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

The photosensitive composition may contain a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1, 2 ,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

A sensitizer may be used alone or in combination of two or more.
When the photosensitive composition contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. It is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition.

The photosensitive composition may also contain a surfactant.
Surfactants include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. is mentioned.
As the surfactant, for example, surfactants described in paragraphs 0120 to 0125 of WO 2018/179640 can also be used.
As the surfactant, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.
Examples of commercially available fluorosurfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, and F-144. , F-437, F-475, F-477, F-479, F-482, F-551, 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 , RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC -104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, OMNOVA company), Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 ) manufactured by NEOS), U-120E (Unichem Co., Ltd.), and the like.
In addition, as a fluorine-based surfactant, an acrylic compound that has a molecular structure with a functional group containing a fluorine atom, and in which the portion of the functional group containing the fluorine atom is cleaved when heat is applied, and the fluorine atom volatilizes. can also be suitably used. Examples of such fluorosurfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
As the fluorosurfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
A block polymer can also be used as the fluorosurfactant.
Further, the fluorine-based surfactant has a structural unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). A fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.
Moreover, as a fluorosurfactant, a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used. Megafac RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation) and the like.

As fluorine-based surfactants, from the viewpoint of improving environmental friendliness, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used. Surfactants derived from alternative materials are preferred.
Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW -1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

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

Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Co.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF- 643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP- 109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF -4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK347, BYK348, BYK345 , BYK349, BYK370, BYK377, BYK378, and BYK323 (manufactured by BYK-Chemie).

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

[Impurities, etc.]
A photosensitive composition may contain impurities.
Impurities include, for example, metal impurities or their ions, halide ions, residual organic solvents, residual monomers, and water.

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

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

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

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

The content of water in the photosensitive composition is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.05% by mass, based on the total mass of the photosensitive composition, from the viewpoint of improving reliability and laminating properties. 5% by mass is more preferred.

Moreover, the photosensitive composition preferably satisfies the requirement (X4) in terms of acid resistance.
Requirement (X4): A 2.0 μm film formed using a photosensitive composition is irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere and heated at 150° C. for 30 minutes. The contact angle of water on the coated film is 60 degrees or more.
Examples of the method for forming the film formed using the photosensitive composition include a method for forming a film on a glass substrate or the like using a transfer film, which will be described later.
The contact angle is measured by the same method as the requirement (X1).
The contact angle of water is preferably 63 degrees or more, more preferably 66 degrees or more. Although the upper limit is not particularly limited, it may be 180 degrees or less, preferably 90 degrees or less.

<Transfer film>
The transfer film used in the method for producing a laminate having a conductor pattern of the present invention has a temporary support and a photosensitive composition layer, and the photosensitive composition layer contains the photosensitive composition described above. Solid content (specifically, an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, etc.) is included.
The transfer film may have other layers in addition to the temporary support and the photosensitive composition layer.
Other layers include, for example, an intermediate layer to be described later. Moreover, the transfer film may have other members (for example, a protective film, etc.) which will be described later.

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

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

In the photosensitive composition layer of the transfer film, when the surface of the photosensitive composition layer opposite to the temporary support has another composition layer, the total thickness of the other composition layer is the photosensitive composition It is preferably 0.1 to 30%, more preferably 0.1 to 20%, of the total thickness of the material layer.

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

Example embodiments of transfer films are described.
The transfer film 10 shown in FIG. 1 has a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.
Although the transfer film 10 shown in FIG. 1 has the intermediate layer 13 and the protective film 19, the intermediate layer 13 and the protective film 19 may be omitted.
In FIG. 1, each layer (for example, a photosensitive composition layer, an intermediate layer, etc.) other than the protective film 19 that can be placed on the temporary support 11 is also referred to as a "composition layer".

Each member and each component of the transfer film will be described in detail below.

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

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

The temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support, and the transmittance at 313 nm, 365 nm, 313 nm, 405 nm, and 436 nm is preferably 60% or more, 70% or more is more preferable, 80% or more is still more preferable, and 90% or more is most preferable. Preferred transmittance values include, for example, 82%, 91%, 97%, and the like.
From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.0% or less, and even more preferably 0.1% or less. Although the lower limit is not particularly limited, 0.01% can be mentioned.
From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter and defects contained in the temporary support is small. The number of fine particles having a diameter of 1 μm or more, foreign matter, and defects in the temporary support is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, further preferably 3/10 mm ² or less, and 0 pcs/10 mm ² is particularly preferred.

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

The temporary support may have a layer containing fine particles (lubricant layer) on one side or both sides of the temporary support from the viewpoint of handling.
The fine particles contained in the lubricant layer preferably have a diameter of 0.05 to 0.8 μm.
The thickness of the lubricant layer is preferably 0.05 to 1.0 μm.

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

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

[Photosensitive composition layer]
The transfer film has a photosensitive composition layer.
As the photosensitive composition layer, a negative photosensitive composition layer is preferred. When the photosensitive composition layer is a negative photosensitive composition layer, the formed resist pattern corresponds to a cured film.
The photosensitive composition layer is preferably formed from the above photosensitive composition. Therefore, the photosensitive composition layer preferably contains the solid content of the photosensitive composition.
Components contained in the photosensitive composition layer (specifically, the alkali-soluble resin, the polymerizable compound having an ethylenically unsaturated group, the photopolymerization initiator, etc.) are as described above.
A method for forming the photosensitive composition layer will be described later.
The layer thickness (film thickness) of the photosensitive composition is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, even more preferably 0.5 to 15 μm. , 1 to 10 μm, most preferably 1 to 8 μm. Thereby, the developability of the photosensitive composition layer can be improved, and the resolution can be improved. Specific examples of preferred film thicknesses include 1.2 μm, 2.5 μm, 3.5 μm, 5.0 μm, 6.0 μm, and 7.0 μm.

(Transmittance of photosensitive composition layer)
The visible light transmittance per 1.0 μm thick of the photosensitive composition layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.
The visible light transmittance preferably satisfies the average transmittance at a wavelength of 400 to 800 nm, the minimum transmittance at a wavelength of 400 to 800 nm, and the transmittance at a wavelength of 400 nm. Preferred transmittance values include, for example, 87%, 92%, and 98%.
The transmittance per 1.0 μm of film thickness of the cured film obtained by curing the photosensitive composition layer is preferably the same transmittance as above.

(Dissolution rate of photosensitive composition layer)
The dissolution rate of the photosensitive composition layer in a 1.0% aqueous solution of sodium carbonate is preferably 0.01 µm/sec or more, more preferably 0.10 µm/sec or more, more preferably 0.20 µm/sec, from the viewpoint of suppressing residue during development. Seconds or more are more preferable. Although the upper limit of the dissolution rate is not particularly limited, it is preferably 5.0 μm/sec or less, more preferably 4.0 μm/sec or less, and even more preferably 3.0 μm/sec or less from the viewpoint of pattern edge shape. Specific preferable numerical values include, for example, 1.8 μm/second, 1.0 μm/second, and 0.7 μm/second.
The dissolution rate per unit time of the photosensitive composition layer in a 1.0% by mass sodium carbonate aqueous solution is measured as follows.
A photosensitive composition layer formed on a glass substrate with a film thickness of 1.0 to 10 μm from which the solvent has been sufficiently removed is coated with a 1.0% by mass sodium carbonate aqueous solution at a liquid temperature of 25 ° C. Shower development is carried out with a maximum time of 2 minutes until the layer is completely melted. The dissolution rate is obtained by dividing the film thickness of the photosensitive composition layer by the time required for the photosensitive composition layer to completely dissolve. If the dissolution is not complete in 2 minutes, the dissolution rate is obtained by dividing the change in film thickness by the above time.
For the shower development, a 1/4 MINJJX030PP shower nozzle manufactured by Ikeuchi Co., Ltd. is used, and the shower spray pressure is 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1800 mL/min.

In addition, the dissolution rate of the cured film of the photosensitive composition layer (thickness within the range of 1.0 to 10 μm) in a 1.0% sodium carbonate aqueous solution is preferably 3.0 μm/second or less, and 2.0 μm/second or less. is more preferable, 1.0 μm/second or less is even more preferable, and 0.2 μm/second or less is most preferable. The cured film of the photosensitive composition layer is a film obtained by exposing the photosensitive composition layer to i-rays at an exposure amount of 300 mJ/cm ² . Specific preferable numerical values include, for example, 0.8 μm/second, 0.2 μm/second, and 0.001 μm/second.

(Swelling rate of photosensitive composition layer after exposure)
The swelling ratio of the photosensitive composition layer after exposure to a 1.0% by mass sodium carbonate aqueous solution is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less, from the viewpoint of improving pattern formability.
The swelling rate of the photosensitive composition layer after exposure to a 1.0% by mass sodium carbonate aqueous solution is measured as follows.
A photosensitive composition layer (film thickness in the range of 1.0 to 10 μm) formed on a glass substrate from which the solvent has been sufficiently removed is exposed with an ultrahigh pressure mercury lamp at 500 mj/cm ² (measured with i-line). The glass substrate is immersed in a 1.0% by mass sodium carbonate aqueous solution at 25° C., and the film thickness is measured after 30 seconds. Then, the ratio of the film thickness after immersion to the film thickness before immersion is calculated. Specific preferable numerical values include, for example, 4%, 13%, and 25%.

(Foreign matter in photosensitive composition layer)
From the viewpoint of pattern formability, the number of foreign substances having a diameter of 1.0 μm or more in the photosensitive composition layer is preferably 10/mm ² or less, more preferably 5/mm ² or less.
Note that the number of foreign matter is measured as follows.
Any five regions (1 mm × 1 mm) on the surface of the photosensitive composition layer are observed with an optical microscope from the normal direction of the surface of the photosensitive composition layer, and the diameter in each region The number of foreign matter of 1.0 μm or more is measured, and the number of foreign matter is calculated by arithmetically averaging them.
Specific preferable numerical values include, for example, 0/mm ² , 1/mm ² , 4/mm ² , and 8/mm ² .

(Haze of melt of photosensitive composition layer)
From the viewpoint of suppressing the generation of aggregates during development, the haze of a solution obtained by dissolving 1.0 cm ³ of a photosensitive resin layer in 1.0 L of a 30° C. aqueous solution of 1.0% by mass sodium carbonate is 60% or less. is preferably 30% or less, more preferably 10% or less, and most preferably 1% or less.
In addition, haze shall be measured in the following procedures.
First, a 1.0% by mass sodium carbonate aqueous solution is prepared and the liquid temperature is adjusted to 30°C. A photosensitive composition layer of 1.0 cm ³ is placed in 1.0 L of sodium carbonate aqueous solution. Stir at 30° C. for 4 hours, taking care not to introduce air bubbles. After stirring, the haze of the solution in which the photosensitive composition layer is dissolved is measured. Haze is measured using a haze meter (product name “NDH4000”, manufactured by Nippon Denshoku Industries Co., Ltd.) using a liquid measurement unit and a liquid measurement dedicated cell with an optical path length of 20 mm.
Specific preferred haze values include, for example, 0.4%, 1.0%, 9.0%, and 24%.

[Thermoplastic resin layer]
The transfer film may have a thermoplastic resin layer.
The thermoplastic resin layer is usually arranged between the temporary support and the photosensitive composition layer. By providing the transfer film with the thermoplastic resin layer, followability to the substrate is improved in the bonding process of the transfer film and the substrate, and air bubbles can be suppressed from entering between the substrate and the transfer film. As a result, it is possible to ensure adhesion with a layer (for example, a temporary support) adjacent to the thermoplastic resin layer.
The thermoplastic resin layer contains resin. The resin includes a thermoplastic resin in part or in whole. That is, in one aspect, it is also preferable that the resin of the thermoplastic resin layer is a thermoplastic resin.

(Alkali-soluble resin (thermoplastic resin))
The thermoplastic resin is preferably an alkali-soluble resin.
Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, and polyhydroxystyrene resins. , polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesion to adjacent layers.
Here, the acrylic resin is at least selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylic acid ester, and a structural unit derived from (meth)acrylic acid amide. It means a resin having one kind of constitutional unit.
As the acrylic resin, the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide is the total content of the acrylic resin. It is preferably 50% by mass or more based on the mass.
Among them, the total content of structural units derived from (meth) acrylic acid and structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, based on the total mass of the acrylic resin, and 50 to 100% by mass is more preferred.

Also, the alkali-soluble resin is preferably a polymer having an acid group.
The acid group includes a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with the carboxy group being preferred.
From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more.
Although the upper limit of the acid value of the alkali-soluble resin is not particularly limited, it is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins and used.
For example, among the polymers described in paragraph 0025 of JP-A-2011-095716, an alkali-soluble resin that is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more, described in paragraphs 0033 to 0052 of JP-A-2010-237589 A carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162. resin.
The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, more preferably 12 to 30% by mass, based on the total mass of the acrylic resin. is more preferred.
As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesion to an adjacent layer.

Alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and includes an ethylenically unsaturated group; a polycondensable group such as a hydroxy group and a carboxyl group; a polyaddition reactive group such as an epoxy group and a (blocked) isocyanate group. mentioned.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

Alkali-soluble resin may be used individually by 1 type, and may be used 2 or more types.
The content of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to adjacent layers. 40 to 80 mass % is more preferred, and 50 to 75 mass % is particularly preferred.

(pigment)
The thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development, and contains a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as "dye B"). is preferred.
Preferred embodiments of the dye B are the same as preferred embodiments of the dye N described above, except for the points described later.

Dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, more preferably a dye whose maximum absorption wavelength changes with acid, from the viewpoint of visibility and resolution of exposed and unexposed areas. .
From the viewpoint of visibility and resolution of the exposed and unexposed areas, the thermoplastic resin layer contains both a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound that generates an acid by light, which will be described later. preferably included.

The dye B may be used alone or in combination of two or more.
The content of the dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed and unexposed areas. , more preferably 0.2 to 5% by mass, particularly preferably 0.25 to 3.0% by mass.

Here, the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example.
A solution of 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone is prepared. A radical photopolymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm to bring all the dyes into a colored state. After that, the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
Next, the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that 0.1 g of the thermoplastic resin layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
3 g of the thermoplastic resin layer is the same as 3 g of the solid content of the composition.

(Compounds that generate acids, bases, or radicals by light)
The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical upon exposure to light (also simply referred to as “compound C”).
Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays such as ultraviolet rays and visible rays.
As compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used.

- Photoacid generator -
The thermoplastic resin layer may contain a photoacid generator from the viewpoint of resolution.
Examples of the photoacid generator include photocationic polymerization initiators that may be included in the negative photosensitive composition layer described above, and preferred embodiments are the same except for the points described later.

From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoint of compatibility, it is more preferable to contain an oxime sulfonate compound.
Moreover, as a photo-acid generator, the photo-acid generator which has the following structures is also preferable.

- Photoradical polymerization initiator -
The thermoplastic resin layer may contain a radical photopolymerization initiator.
Examples of the photoradical polymerization initiator include photoradical polymerization initiators that may be included in the negative photosensitive composition layer described above, and preferred embodiments are also the same.

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

Compound C may be used alone or in combination of two or more.
The content of compound C is preferably 0.1 to 10% by mass, preferably 0.5 to 5%, based on the total mass of the thermoplastic resin layer, from the viewpoint of visibility and resolution of exposed and unexposed areas. % by mass is more preferred.

(Plasticizer)
The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to adjacent layers, and developability.
The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
The plasticizer is not particularly limited as long as it is a compound that exhibits plasticity by being compatible with the alkali-soluble resin, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, such as polyalkylene glycol. Compounds are more preferred. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

Moreover, the plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.
Examples of the (meth)acrylate compound used as the plasticizer include the (meth)acrylate compounds described above as the polymerizable compound contained in the negative photosensitive composition layer.
In the transfer film, when the thermoplastic resin layer and the negative photosensitive composition layer are laminated in direct contact, both the thermoplastic resin layer and the negative photosensitive composition layer contain the same (meth)acrylate compound. is preferred. This is because the thermoplastic resin layer and the negative photosensitive composition layer each contain the same (meth)acrylate compound, thereby suppressing the diffusion of components between layers and improving the storage stability.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, from the viewpoint of adhesion between the thermoplastic resin layer and adjacent layers, the (meth)acrylate compound should not be polymerized even in the exposed areas after exposure. preferable.
Further, the (meth)acrylate compound used as a plasticizer has two or more (meth) Polyfunctional (meth)acrylate compounds having acryloyl groups are preferred.
Furthermore, as the (meth)acrylate compound used as a plasticizer, a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferable.

A plasticizer may be used individually by 1 type, and may be used 2 or more types.
The content of the plasticizer is preferably 1 to 70% by mass based on the total mass of the thermoplastic resin layer from the viewpoints of the resolution of the thermoplastic resin layer, the adhesion to adjacent layers, and the developability. 10 to 60% by mass is more preferable, and 20 to 50% by mass is even more preferable.

(sensitizer)
The thermoplastic resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and includes sensitizers that may be included in the negative photosensitive composition layer described above.

A sensitizer may be used alone or in combination of two or more.
The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and visibility of the exposed area and the non-exposed area, it is 0.01 with respect to the total mass of the thermoplastic resin layer. ~5% by mass is preferable, and 0.05 to 1% by mass is more preferable.

(Additives, etc.)
The thermoplastic resin layer may contain known additives such as surfactants, if necessary, in addition to the above components.
Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-085643, and the contents described in this publication are incorporated herein.

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

[Middle layer]
The transfer film also preferably has an intermediate layer between the temporary support and the photosensitive composition layer.
Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-072724.
As the intermediate layer, an oxygen-blocking layer is preferable from the viewpoint that the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved. More preferred is an oxygen barrier layer dispersed or dissolved in a 1% by weight aqueous solution of sodium carbonate.
Each component that can be included in the water-soluble resin layer (intermediate layer) is described below.

The water-soluble resin layer (intermediate layer) contains a resin.
It is preferable that the resin contains a water-soluble resin as part or all of it.
Examples of resins that can be used as water-soluble resins include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Examples include resins such as coalescence.
A (meth)acrylic acid/vinyl compound copolymer or the like can also be used as the water-soluble resin. As the (meth)acrylic acid/vinyl compound copolymer, a (meth)acrylic acid/allyl (meth)acrylate copolymer is preferable, and a methacrylic acid/allyl methacrylate copolymer is more preferable.
When the water-soluble resin is a (meth)acrylic acid/vinyl compound copolymer, the composition ratio (mol%) is preferably 90/10 to 20/80, and preferably 80/20 to 30/70. more preferred.

The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. Moreover, the upper limit thereof is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
The dispersity (Mw/Mn) of the water-soluble resin is preferably 1-10, more preferably 1-5.

One type of water-soluble resin may be used alone, or two or more types may be used.
Although the content of the water-soluble resin is not particularly limited, it is preferably 50% by mass or more with respect to the total mass of the water-soluble resin layer (intermediate layer) in order to further improve the oxygen barrier property and the ability to suppress interlayer mixing. , more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Although the upper limit is not particularly limited, for example, 99.9% by mass or less is preferable, and 99.8% by mass or less is more preferable.

The intermediate layer may contain other components in addition to the above water-soluble resin.
As other components, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferred, and polyhydric alcohols, phenol derivatives or amide compounds are more preferred.
In addition, other components include, for example, known surfactants.

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

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

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

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

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

The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the inter-layer mixing suppression ability is excellent without lowering the oxygen barrier properties. Furthermore, it is possible to suppress the increase in the time required for removing the water-soluble resin layer (intermediate layer) during development.

[Protective film]
The transfer film may have a protective film on the photosensitive composition layer.
As the protective film, a resin film having heat resistance and solvent resistance can be used. Examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. be done.
Also, as the protective film, a resin film made of the same material as the temporary support may be used.
Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and still more preferably a polyethylene film.

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

In the protective film, the number of fisheyes with a diameter of 80 μm or more contained in the protective film is preferably 5/m ² or less.
In addition, "fish eye" refers to foreign matter, undissolved matter, and oxidative degradation products of the material when producing a film by methods such as heat melting, kneading, extrusion, biaxial stretching, and casting. is captured in the film.

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

From the viewpoint of imparting windability, the surface of the protective film opposite to the surface in contact with the photosensitive composition layer preferably has an arithmetic mean roughness Ra of 0.01 μm or more, more preferably 0.02 μm or more, and 0 0.03 μm or more is more preferable. On the other hand, it is preferably less than 0.50 µm, more preferably 0.40 µm or less, and even more preferably 0.30 µm or less.
From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface in contact with the photosensitive composition layer of the protective film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50 µm, more preferably 0.40 µm or less, and even more preferably 0.30 µm or less.

[Manufacturing method of transfer film]
The method for producing the transfer film is not particularly limited, and includes known methods.
As a method for producing the transfer film 10, for example, a process of applying an intermediate layer forming composition to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the intermediate layer 13. and a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form a photosensitive composition layer 15, and a temporary support A method including a step of applying a photosensitive composition to the surface of the body 11 to form a coating film and then drying the coating film to form a photosensitive composition layer 15 may be mentioned.

When the transfer film 10 has a protective film 19, the protective film 19 may be pressure-bonded onto the composition layer 17 of the transfer film 10 manufactured by the manufacturing method described above.
The method for producing the transfer film 10 includes a step of providing a protective film 19 so as to be in contact with the surface of the composition layer 17 opposite to the temporary support 11 side, whereby the temporary support 11, the intermediate layer 13, the photosensitive Preferably, the transfer film 10 is manufactured with a protective composition layer 15 and a protective film 19 .
After manufacturing the transfer film 10 by the manufacturing method described above, the transfer film 10 may be wound up to produce and store a roll-shaped transfer film. The roll-shaped transfer film 10 can be provided as it is to the laminating step with a substrate in a roll-to-roll system, which will be described later.

Further, the method of manufacturing the transfer film 10 may be a method of forming the composition layer 17 on the protective film 19 .

(Composition for forming thermoplastic resin layer and method for forming thermoplastic resin layer)
When the transfer film has a thermoplastic resin layer, the method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and known methods can be used. For example, it can be formed by applying a composition for forming a thermoplastic resin layer onto a temporary support and drying it if necessary.
The composition for forming a thermoplastic resin layer preferably contains the above-described various components for forming the thermoplastic resin layer and a solvent. In addition, in the composition for forming a thermoplastic resin layer, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the thermoplastic resin layer described above. be.
The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and known solvents can be used. Examples of the solvent include those similar to the solvent contained in the photosensitive composition described later, and the preferred embodiments are also the same.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

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

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

(Method for forming photosensitive composition and photosensitive composition layer)
Coating method using a photosensitive composition containing components (e.g., resin A, a polymerizable compound, a polymerization initiator, etc.) and a solvent that constitutes the above-described photosensitive composition in terms of excellent productivity It is desirable to be formed by In the photosensitive composition, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the photosensitive composition layer described above.
Specifically, the transfer film is produced by coating a photosensitive composition on the intermediate layer to form a coating film, and drying the coating film at a predetermined temperature to form a photosensitive composition layer. A method of forming is preferred.

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

Heat drying and reduced pressure drying are preferable as a method for drying the coating film of the photosensitive composition. As used herein, "drying" means removing at least part of the solvent contained in the composition. Drying methods include, for example, natural drying, heat drying, and vacuum drying. The methods described above can be applied singly or in combination.
The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. Further, the upper limit thereof is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously.
Moreover, the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. Although the upper limit is not particularly limited, it is preferably 600 seconds or less, more preferably 300 seconds or less.

Furthermore, a transfer film can be produced by laminating a protective film to the photosensitive composition layer.
A method for laminating the protective film to the photosensitive composition layer is not particularly limited, and includes known methods.
Apparatuses for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an autocut laminator.
Preferably, the laminator is equipped with any heatable roller, such as a rubber roller, and can be applied with pressure and heat.

<Application>
The photosensitive composition and transfer film of the present invention can be applied to various uses. For example, it can be applied to electrode protective films, insulating films, planarizing films, overcoat films, hard coat films, passivation films, barrier ribs, spacers, microlenses, optical filters, antireflection films, etching resists, plating members, and the like. More specific examples include protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, color filters, overcoat films for color filters, and An etching resist etc. can be mentioned.

<Method for producing a laminate having a conductor pattern>
The photosensitive composition and the transfer film can be suitably used for producing a laminate having a conductor pattern. Among others, the photosensitive composition and the transfer film can be suitably used for producing a laminate having a conductor pattern containing silver in the conductor pattern.
More specifically, the method for producing a laminate having a conductor pattern of the present invention comprises:
A preparation step of preparing a laminate having a substrate, a conductive layer containing silver, and a photosensitive composition layer in this order;
An exposure step of pattern-exposing the photosensitive composition layer;
a developing step of developing the exposed photosensitive composition layer to form a resist pattern;
It is preferable to include an etching step of etching the conductive layer in a region where the resist pattern is not formed, with an etchant having a pH of less than 2.0.
The photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, and the polymerizable compound satisfies the following requirement (X1): a polymerizable compound A including.
Requirement (X1): 100 parts by mass of polymerizable compound A and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) 1.0 A composition consisting of parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere for 30 minutes at 150°C. The contact angle of water on the film obtained by heating is 74 degrees or more.
Since the contact angle is the same as the requirement (X1), the description is omitted.
Each step will be described below. Also, steps that may be performed in manufacturing a laminate having a conductor pattern will be described.

[Preparation process]
The preparation step is a step of preparing a laminate having a substrate, a conductive layer containing silver, and a photosensitive composition layer in this order. The photosensitive composition layer contains an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated group, and a photopolymerization initiator, and the polymerizable compound contains a polymerizable compound A that satisfies the above requirement (X1). . That is, the photosensitive composition layer is preferably formed using the above photosensitive composition.
The preparation step is preferably a method of forming a conductive layer containing silver on a substrate and then forming a photosensitive composition layer on the conductive layer containing silver. The photosensitive composition layer may be formed on the conductive layer containing silver using the photosensitive composition, or may be formed using the transfer film.
When the photosensitive composition layer is formed from the above photosensitive composition, the photosensitive composition layer can be formed by applying the photosensitive composition on the electroconductive layer containing silver according to the production method of the transfer film. preferable.
When a transfer film is used to form a photosensitive composition layer on a silver-containing conductive layer, it is preferable to form the photosensitive composition layer by a lamination step, which will be described later.
The laminate prepared in the preparation step may be one in which a conductive layer containing silver and a photosensitive composition layer are formed on one side of the substrate in this order from the substrate side. and the photosensitive composition layer may be formed in this order from the substrate side.

(substrate)
The substrate is not particularly limited, but examples thereof include resin substrates, glass substrates, ceramic substrates, and semiconductor substrates, and substrates described in paragraph [0140] of WO2018/155193 are preferable.
As a material for the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable.
The thickness of the resin substrate is preferably 5-200 μm, more preferably 10-100 μm.

(Conductive layer)
The conductive layer comprises silver, and the conductive layer is disposed on the surface of the substrate.
The conductive layer containing silver includes a conductive layer formed of a silver conductive material such as silver mesh and silver nanowires, and a metal layer (conductive layer) made of silver or a silver alloy.
Also, one conductive layer may be arranged on the substrate, or two or more layers may be arranged. When two or more conductive layers are arranged, the conductive layers are preferably made of different materials.
The conductive layer other than the silver-containing conductive layer is selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine line formation. is preferably at least one layer.
Preferred embodiments of the conductive layer are described, for example, in paragraph [0141] of WO2018/155193, the content of which is incorporated herein.

As the substrate on which the conductive layer is arranged, a substrate having at least one of a transparent electrode and lead wiring is preferable. The substrate as described above can be suitably used as a touch panel substrate.
A transparent electrode can function suitably as an electrode for touch panels. The transparent electrode preferably includes metal oxide films such as ITO (indium tin oxide) and IZO (indium zinc oxide), metal meshes, and fine metal wires such as metal nanowires. As the transparent electrode, a conductive layer containing silver is preferably used, and a transparent electrode formed of silver mesh or silver nanowires is also preferable.

A metal is preferable as the material of the routing wiring.
Examples of metals for the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metal elements. Silver, copper, molybdenum, aluminum, or titanium is preferable as the material of the routing wiring, and silver or copper is particularly preferable.

(Photosensitive composition layer)
The method of forming a photosensitive composition layer on a conductive layer containing silver is not particularly limited, but a method by applying a photosensitive composition onto a conductive layer containing silver (coating step), and a photosensitive composition of a transfer film. and lamination (lamination step) of a conductive layer containing silver and a conductive composition layer.

-Coating process-
The application step is a step of applying a photosensitive composition onto the conductive layer containing silver to form a photosensitive composition layer.
The coating step is formed by a coating method using a photosensitive composition containing components (for example, resin A, a polymerizable compound, a polymerization initiator, etc.) constituting the photosensitive composition described above and a solvent. preferably In the photosensitive composition, the preferred range of the content of each component with respect to the total solid content of the composition is the same as the preferred range of the content of each component with respect to the total mass of the photosensitive composition layer described above.

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

Heat drying and reduced pressure drying are preferable as a method for drying the coating film of the photosensitive composition. As used herein, "drying" means removing at least part of the solvent contained in the composition. Drying methods include, for example, natural drying, heat drying, and vacuum drying. The methods described above can be applied singly or in combination.
The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. Further, the upper limit thereof is preferably 130° C. or lower, more preferably 120° C. or lower. Drying can also be performed by changing the temperature continuously.
Moreover, the drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and even more preferably 60 seconds or longer. Although the upper limit is not particularly limited, it is preferably 600 seconds or less, more preferably 300 seconds or less.

-Lamination process-
In the lamination step, the surface of the transfer film having the temporary support and the photosensitive composition layer on the side opposite to the temporary support side is in contact with the conductive layer of the substrate having the conductive layer on the surface. It is a step of laminating. By carrying out the lamination step, a substrate with a photosensitive composition layer having a substrate, a conductive layer, a photosensitive composition layer and a temporary support in this order is obtained.
In addition, when a transfer film is the structure which has a protective film, after peeling off a protective film, the bonding process is implemented.

In the lamination, the photosensitive composition layer side of the transfer film (the surface opposite to the temporary support side) is preferably brought into contact with the metal layer on the substrate and pressure-bonded.
The method of pressure bonding is not particularly limited, and known transfer methods and lamination methods can be used. Among others, it is preferable that the surface of the photosensitive composition layer is placed on a substrate having a conductive portion, and pressure and heat are applied using rolls or the like.
A known laminator such as a vacuum laminator and an autocut laminator can be used for bonding.
Although the lamination temperature is not particularly limited, it is preferably 70 to 130° C., for example.

[Exposure process]
The exposure step is a step of patternwise exposing the photosensitive composition layer.
A resist pattern that protects at least part of the conductive layer is formed on the conductive layer on the substrate by performing the exposure process and the development process described later.
"Pattern exposure" is a form of exposure in a pattern, and means an exposure form in which an exposed portion and an unexposed portion are present.
The positional relationship between the exposed portion (exposed area) and the unexposed portion (unexposed area) in the pattern exposure can be appropriately adjusted. The exposure may be performed from the side of the photosensitive composition opposite to the substrate, or from the side of the photosensitive composition layer.

Exposure methods in the exposure step include, for example, mask exposure, direct imaging exposure, and projection exposure.
When the composition layer is formed by the lamination step, the exposure step may be performed after peeling the temporary support, or may be performed without peeling. The peeling method of the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP-A-2010-072589 can be used.

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

The light source for pattern exposure can be appropriately selected and used as long as it can irradiate at least light in a wavelength range capable of curing the photosensitive composition layer (for example, 365 nm or 405 nm). Among others, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. Note that the dominant wavelength is the wavelength with the highest intensity.

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

Preferred embodiments of the light source, exposure dose and exposure method used for exposure are described in, for example, paragraphs [0146] to [0147] of WO 2018/155193, the contents of which are incorporated herein. .

[Development process]
The development step is a step of developing the exposed photosensitive composition layer to form a resist pattern.
In addition, when the photosensitive composition layer is formed using the transfer film mentioned above, the process of peeling a temporary support is implemented before implementing a developing process. The step of peeling off the temporary support may be performed before the exposure step or between the exposure step and the development step.
Development of the photosensitive composition layer can be performed using a developer.
As a developer, an alkaline aqueous solution is preferred. Alkaline compounds that can be contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

The liquid temperature of the developer during development is preferably 10 to 50.degree. C., more preferably 15 to 40.degree. C., even more preferably 20 to 35.degree.
The pH of the developer during development is preferably 9 or higher, more preferably 10 or higher, and even more preferably 11 or higher. The upper limit is preferably 14 or less, more preferably less than 13.

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

Examples of the development method include methods such as puddle development, shower development, spin development, and dip development.

Examples of the developer suitably used in the present specification include the developer described in paragraph [0194] of International Publication No. 2015/093271. Examples include the development method described in paragraph [0195] of 2015/093271.

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

Although the position and size of the resist pattern formed on the metal layer-coated substrate are not particularly limited, it preferably includes a fine line shape.
Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is often 1.0 μm or more.

[Etching process]
The etching step is a step of etching the conductive layer in the region where the resist pattern is not formed with an etchant having a pH of less than 2.0.
By performing the etching step, the conductive layer is removed at the openings of the resist pattern, and the conductive layer has the same pattern shape as the resist pattern. Thus, the etching step yields a laminate having a conductor pattern.
As the etching method, known methods can be applied, for example, the method described in paragraphs [0209] to [0210] of JP-A-2017-120435, paragraphs [0048] to JP-A-2010-152155. [0054] and the like, and a wet etching method in which the substrate is immersed in an etchant.
In addition, pH of the said etching liquid is less than 2.0.
Examples of etching solutions having a pH of less than 2.0 include ferric nitrate aqueous solution, mixed acid of ferric nitrate and sulfuric acid, mixed acid of phosphoric acid, nitric acid, acetic acid and water, and mixed acid of chromic acid, sulfuric acid and water. be done.
The etchant preferably does not dissolve the resist pattern. Since the resist pattern has acid resistance, even if the pH of the etchant is less than 2.0, the silver-containing conductive layer covered with the resist pattern is not easily denatured or etched by the etchant.
The developer used in the development step may also serve as the etchant used in the etching process. In this case, the development process and the etching process may be performed simultaneously.

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

[Peeling process]
The method for producing a laminate having a conductor pattern of the present invention may have a peeling step.
The stripping step is a step of stripping the resist pattern remaining after the etching step.
A method for removing the remaining resist pattern is not particularly limited, but a method of removing by chemical treatment is mentioned, and a method of removing using a remover is preferable.
Moreover, you may remove by well-known methods, such as a spray method, a shower method, and a paddle method, using a remover.

Examples of stripping solutions include stripping solutions obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Organic alkali components include primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium salt compounds. Tetramethylammonium hydroxide or an alkanolamine compound is preferable as the alkaline organic compound.
It is also preferable that the stripping solution does not dissolve the metal layer.

As a method for removing the resist pattern, the substrate having the remaining resist pattern is immersed for 1 to 30 minutes in an agitated stripping solution having a liquid temperature of preferably 30 to 80° C., more preferably 50 to 80° C. is mentioned.

The pH of the stripping solution during the stripping treatment is preferably 11 or higher, more preferably 12 or higher, and even more preferably 13 or higher. The upper limit is preferably 14 or less, more preferably 13.8 or less.
It is preferable that the liquid temperature of the stripping solution during the stripping process is higher than the liquid temperature of the developer during the development process. Specifically, the value obtained by subtracting the liquid temperature of the developer from the liquid temperature of the stripper (liquid temperature of the stripper - liquid temperature of the developer) is preferably 10°C or higher, and more preferably 20°C or higher. preferable. The upper limit is preferably 100°C or lower, more preferably 80°C or lower.
It is preferable that the pH of the stripping solution for the stripping treatment is higher than the pH of the developer for the development treatment. Specifically, the value obtained by subtracting the pH of the developer from the pH of the stripper (pH of the stripper - pH of the developer) is preferably 1 or more, more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.

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

[Other processes]
A method for manufacturing a laminate having a conductor pattern may include arbitrary steps (other steps) other than the steps described above.
For example, the step of reducing the visible light reflectance described in paragraph [0172] of WO2019/022089, a new metal layer on the insulating film described in paragraph [0172] of WO2019/022089 Examples include a forming step and the like, but are not limited to these steps.

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

(Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film)
It is also preferable that the method for manufacturing a laminate having a conductor pattern includes the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film.
Through the above steps, a second electrode pattern insulated from the first electrode pattern can be formed.
The process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used. Alternatively, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive layer on the insulating film is not particularly limited. For example, a conductive photosensitive material may be used to form a new conductive layer in a desired pattern by photolithography.

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

<Use of laminate having conductor pattern>
The method for producing a laminate having a conductor pattern is not limited in application, and for example, production of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and light control films; printed wiring boards and semiconductor packages. production of interconnect pillars and pins between semiconductor chips and packages; production of metal masks; production of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding);
Moreover, as said touch panel, a capacitive touch panel is mentioned. The method for manufacturing a laminate according to the present invention can be used for forming a conductive film and peripheral circuit wiring in a touch panel. The touch panel can be applied to display devices such as organic EL (electro-luminescence) display devices and liquid crystal display devices.

The present invention will be described in more detail based on examples below.
The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.
"Parts" and "%" are based on mass unless otherwise specified.
Further, in the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene. Also, as the acid value of the resin, a theoretical acid value derived from the ratio of constituent units of the resin was used.

<Transfer film>
A transfer film used in each example and each comparative example was produced using the components shown in Table 1 below.
A photosensitive composition having the composition shown in Table 1 was applied onto a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle. The coating amount was adjusted so that the thickness of the formed photosensitive composition layer was as shown in Table 1. The photosensitive composition on the temporary support was dried in a convection oven at 100° C. for 2 minutes to form a photosensitive composition layer. A protective film (polypropylene film, thickness: 12 μm, haze: 0.2%) was laminated on the photosensitive composition layer to prepare a transfer film. The unit of the amount (added amount) of each component described in Table 1 is parts by mass.
The details of each component in the table are as follows.

[Alkali-soluble resin (resin A)]
Polymer 1: styrene/methacrylic acid/methyl methacrylate copolymer (constituent unit mass ratio: 52/29/19, acid value: 189 mgKOH/g, contact angle: 75 degrees, corresponding to resin A1 above)
Polymer 2: styrene/methacrylic acid/methyl methacrylate copolymer (constituent unit mass ratio: 52/15/33, acid value: 99 mgKOH/g, contact angle: 78 degrees, corresponding to resin A1 above)
Polymer 3: benzyl methacrylate/methacrylic acid/acrylic acid copolymer (mass ratio of structural units: 74.5/10/15.5, acid value: 186 mgKOH/g, contact angle: 62 degrees, for the resin A1 Not applicable)
Polymer 4: benzyl methacrylate/methacrylic acid copolymer (constituent unit mass ratio: 82.7/17.3, acid value: 113 mgKOH/g, contact angle: 72 degrees, corresponding to resin A1 above)
Whether or not the resin A corresponds to the resin A1 was determined by measuring the contact angle using the method described in the requirement (X3).
A film for contact angle measurement was prepared by the following method.
Resin A was spin-coated on glass under the conditions that a film with a thickness of 2.0 μm can be formed, and dried at 100° C. for 2 minutes using a hot plate to obtain a film with a thickness of 2.0 μm. For resins that were too viscous to form a 2.0 μm film, the resin was diluted with methyl ethyl ketone to a suitable viscosity and spin-coated. When the resin does not dissolve in methyl ethyl ketone, a solvent having a boiling point of 150° C. or less in which the resin dissolves was used. The resulting film was heated in an oven at 150° C. for 30 minutes to obtain a film for contact angle measurement.

[Polymerizable compound]
・BPE500: Ethoxylated bisphenol A dimethacrylate (average number of —CH ₂ CH ₂ O— groups in one molecule is 10), manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 44 degrees, the above polymerization having a bisphenol A structure Corresponding to sexual compound B)
・BPE900: Ethoxylated bisphenol A dimethacrylate (average number of —CH ₂ CH ₂ O— groups in one molecule is 17), manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 34 degrees, the above polymerization having a bisphenol A structure Corresponding to sexual compound B)
・HD-N: 1,6-hexanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 77 degrees, corresponding to the above polymerizable compound A1)
・ A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 86 degrees, corresponding to the above polymerizable compound A1)
・ NOD-N: 1,9-nonanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 87 degrees, corresponding to the above polymerizable compound A1)
・A-HD-N: 1,6-hexanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 76 degrees, corresponding to the above polymerizable compound A1)
・ A-DOD-N: 1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 89 degrees, corresponding to the above polymerizable compound A1)
・ A-DCP: Tricyclodencan dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. (contact angle: 90 degrees, corresponding to the above polymerizable compound A)
・ TO2349: Aronix (registered trademark) TO-2349, manufactured by Toagosei Co., Ltd. (contact angle: 58 degrees, corresponding to the above polymerizable compound B)
Whether or not the polymerizable compound corresponds to the polymerizable compound A and the polymerizable compound B was determined by measuring the contact angle using the method described in the above requirements (X1) and (X2). .
A film for contact angle measurement was prepared by the following method.
To 100 parts by mass of the polymerizable compound, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) 1.0 parts by mass, and A coating composition was prepared by mixing 9 parts by mass of methyl ethyl ketone.
The above coating liquid was spin-coated on glass under conditions that formed a film of 2.0 μm after drying, and dried at room temperature for 10 minutes to obtain a film with a thickness of 2.0 μm. This film was placed in a nitrogen purge box (MUVPBQ-150×135×33 manufactured by ITEC System Co., Ltd.) and purged with nitrogen until the partial pressure of nitrogen reached 0.99 atm. After purging, exposure was performed by irradiating i-line with an exposure amount of 500 mJ/cm ² using a high-pressure mercury lamp. The exposed film was heated in an oven at 150° C. for 30 minutes to obtain a cured film for contact angle measurement.

[Photoinitiator]
BCIM: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

[Sensitizer]
・EAB-F: 4,4′-bis(diethylamino)benzophenone

[Polymerization inhibitor]
・Heavy drug 1: phenothiazine ・Heavy drug 2: 1-phenyl-3-pyrazolidone

[Additive]
・LCV: Leuco Crystal Violet, manufactured by Tokyo Chemical Industry Co., Ltd. ・Chain transfer agent A: N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・CBT-1: Carboxybenzotriazole, Johoku Chemical Co., Ltd. Manufactured F-552: Megafac (registered trademark) F-552, manufactured by DIC BYK-330: BYK-330, manufactured by BYK Chemie

[solvent]
・MEK: methyl ethyl ketone ・PGMEA: propylene glycol monomethyl ether acetate ・MeOH: methanol

<Measurement>
[Photosensitive composition water contact angle]
For the photosensitive composition of each example and each comparative example, a film of the photosensitive composition for measurement of the contact angle of water was prepared by the following method, and the contact angle of water of the film was measured.
Each photosensitive composition was applied onto the temporary support using a slit nozzle and dried in a convection oven at 100° C. for 2 minutes to form a photosensitive composition layer having a thickness of 2.0 μm. A transfer film for water contact angle measurement was prepared by laminating the above protective film onto the photosensitive composition layer.
The protective film of the transfer film for water contact angle measurement was peeled off to expose the photosensitive composition layer, and the photosensitive composition layer and the glass substrate were bonded together. The bonding was performed by lamination under the conditions of a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m/min. By the above procedure, a laminate having a glass substrate, a photosensitive composition layer, and a temporary support in this order was obtained.
The temporary support of the laminate was peeled off, and under the same conditions as in the preparation of the cured film of the polymerizable compound, i-rays were irradiated at an exposure amount of 500 mJ/cm ² in a nitrogen atmosphere, and 30 in an oven at 150 ° C. After heating for a minute, a cured film for contact angle measurement was obtained.
The contact angle of water of the cured film was measured under the same conditions as the contact angle of water of the polymerizable compound.

<Evaluation>
[Resolution]
The protective film of the transfer film was peeled off to expose the photosensitive composition layer, and the photosensitive composition layer and the substrate 1 (polyethylene terephthalate film, thickness: 40 µm) were laminated. The bonding was performed by lamination under the conditions of a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m/min. By the above procedure, a laminate having the substrate 1, the photosensitive composition layer, and the temporary support in this order was obtained.
Without peeling off the temporary support of the laminate, the temporary support and a glass mask (Duty ratio 1:1) having a line and space pattern with a line width of 3.0 to 50 μm are brought into close contact, It was exposed with a high-pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.).
The exposure amount in the above exposure was determined as follows.
Using an ultra-high pressure mercury lamp (USH-2004MB, manufactured by Ushio Inc.), exposure was performed while changing the exposure amount according to the above procedure. After that, it was left for 1 hour after exposure, and the exposure amount was such that when developing under the conditions described later, the remaining pattern width was in the range of 49.0 microns to 51.0 microns in the pattern area of 50 μm line/50 μm space. was obtained and used as the exposure amount in the above procedure.

After leaving for 1 hour after exposure, the temporary support was peeled off, and then a resist pattern was formed by development. Development was performed by shower development for 30 seconds using a 1.0% potassium carbonate aqueous solution (developer) at 30°C.
Of the resist patterns formed after development, the line width of the pattern corresponding to the mask with the narrowest line width was defined as the attained resolution. Based on the attained resolution, the resolution of the photosensitive composition layer was evaluated according to the following criteria.
If the side wall of the pattern is greatly roughened, or if the trailing edge is conspicuous and is connected to the adjacent line pattern, it is assumed that the pattern cannot be resolved. As for the evaluation of resolution, A to C are within a practically acceptable range, B is preferred, and A is particularly preferred.

(Resolution Evaluation Criteria)
A: Ultimate resolution of 10 μm or less B: Ultimate resolution of more than 10 μm and 15 μm or less C: Ultimate resolution of more than 15 μm and 20 μm or less D: Ultimate resolution of more than 20 μm and 30 μm or less E: Ultimate resolution of more than 30 μm or unresolvable not

[Acid resistance]
The protective film of the transfer film is peeled off to expose the photosensitive composition layer, and the photosensitive composition layer and substrate 2 (a substrate having a 50 nm thick silver nanowire layer (conductive layer) on the surface of a 40 μm PET film). It was laminated so that the conductive layer of . The bonding was performed by lamination under the conditions of a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m/min. By the above procedure, a laminate having substrate 2 (PET film, conductive layer), photosensitive composition layer, and temporary support in this order was obtained.
When the surface resistance value of the conductive layer in the laminate was measured with a non-destructive sheet resistance meter (EC-80P, manufactured by Napson), the surface resistance value (resistance value before treatment) was 60Ω/□. .

Exposure and development were carried out in the same procedure as for the above resolution exposure, except that the entire surface was exposed without a mask. Through the above treatment, a laminate was obtained in which a cured film (resist film) derived from the photosensitive composition layer was formed on the entire surface of the conductive layer of the substrate 2 .
A 30 wt % aqueous solution of ferric nitrate (pH: 0.6) at 40° C. was supplied to the surface of the laminate on the resist film side by a shower method for 120 seconds.
Next, the surface resistance value (post-treatment resistance value) was measured using the non-destructive sheet resistance measuring instrument, and the amount of change from the pre-treatment resistance value was determined. The amount of change in resistance value (%) was calculated by the following formula. However, when the amount of change in resistance value calculated by the following formula is a negative value, the absolute value was used as the amount of change in resistance value.
(Formula) (Amount of change in resistance value) = {(Resistance value after treatment) - (Resistance value before treatment)} x 100/(Resistance value before treatment)
Based on this amount of change, the acid resistance of the resist film formed from the photosensitive composition was evaluated according to the following criteria. As for the evaluation of acid resistance, A to C are within a practically acceptable range, B is preferred, and A is particularly preferred.

(Acid resistance evaluation criteria)
A: The amount of change in resistance value is 2% or less B: The amount of change in resistance value is more than 2% and 5% or less C: The amount of change in resistance value is more than 5% and 10% or less D: The amount of resistance value change is more than 10% and 20 % or less E: The amount of change in resistance value is over 20%, or the resistance value after treatment exceeds the upper limit of measurement

[Peelability]
A resist pattern for peelability evaluation was formed in the same procedure as for resolution evaluation, except that a glass mask (Duty ratio 1:1) having a line-and-space pattern with a line width of 50 μm was used.
The resist pattern was immersed in a 3 wt % NaOH aqueous solution at 50° C., and the time required for the resist pattern to be peeled off was measured. Based on the time required for the resist pattern to be peeled off (peeling time), the peelability of the resist pattern formed by the photosensitive composition was evaluated according to the following criteria.
As for the evaluation, A to C are within a practically acceptable range, B is preferred, and A is particularly preferred.

(Peelability evaluation criteria)
A: peeling time of 30 seconds or less B: peeling time of more than 30 seconds and 45 seconds or less C: peeling time of more than 45 seconds and 60 seconds or less D: peeling time of more than 60 seconds and 80 seconds or less E: peeling time of 80 seconds Seconds or more, or the resist pattern cannot be peeled off

<Results>
Table 1 shows the formulation of the components of the photosensitive composition of each example and each comparative example, the thickness of the photosensitive composition layer, the contact angle of water of the photosensitive composition, and the resolution, acid resistance, and The evaluation results of peelability are shown. Table 1 is divided into Table 1-1 and Table 1-2.
In addition, in Table 1, each component of the photosensitive composition is as described above.
In Table 1, the content of each component is parts by mass.
In Table 1, the expression "polymerizable compound/resin A" represents the mass ratio of the total content of polymerizable compounds to the content of resin.
In Table 1, the expression "polymerizable compound B/polymerizable compound A" represents the mass ratio of the content of polymerizable compound B to the content of polymerizable compound A.

From the results in Table 1, it was confirmed that the photosensitive composition of the present invention exhibited the desired effects.
From the comparison of Examples 11 and 13 with other examples, it was confirmed that when the polymerizable compound A was the polymerizable compound A1 represented by the above formula (A), the resolution was superior.
From the comparison of Examples 10 and 11 with other examples, it was confirmed that when the polymerizable compound contained the polymerizable compound B satisfying the above requirement (X2), it was superior to the peelability.
From the comparison of Examples 5-7 and 10-12 with other Examples, it was confirmed that when the polymerizable compound B has the bisphenol A structure, the resolution is superior.
From the comparison of Examples 6, 7, and 10 to 12 with other examples, when the mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00 , resolution, acid resistance, and peelability were confirmed to be superior.
From the comparison of Examples 8 and 9 with other examples, when the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30, acid resistance and peeling It was confirmed that any one or more of the sexes were superior.
From the comparison of Examples 1, 3, 4 and 15 to 24 with other examples, the polymerizable compound A is the polymerizable compound A1 represented by the above formula (A), and the polymerizable compound satisfies the above requirements ( X2) is satisfied and contains a polymerizable compound B having a bisphenol A structure, the mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00, and polymerization When the mass ratio of the content of the alkali-soluble resin to the content of the soluble compound is 0.68 to 1.30, one or more of resolution, acid resistance, and peelability are superior. was confirmed.
A comparison between Example 1 and Example 4 confirms that when the alkali-soluble resin is Resin A1 that satisfies the above requirement (X3), at least one of acid resistance and peelability is superior. rice field.
From a comparison between Example 1 and Example 3 and a comparison between Example 7 and Example 12, when the acid value of the alkali-soluble resin is 100 mgKOH/g or more, both acid resistance and peelability are improved. or one or more was confirmed to be superior.
From the comparison between Example 2 and other examples, it was confirmed that when the thickness of the photosensitive composition layer in the transfer film was 1 to 10 μm, the resolution was superior.

<Formation of photosensitive composition layer using photosensitive composition>
[Example 1B]
The photosensitive composition used for producing the transfer film of Example 1 shown in Table 1 was spin-coated on the substrate 1 to form a coating film. The coating amount was adjusted so that the formed photosensitive composition layer had the film thickness shown in Table 1. The coating film on the substrate 1 was dried on a hot plate at 90° C. for 2 minutes to form a photosensitive composition layer on the substrate 1 . Next, the surface of the photosensitive composition layer and the temporary support used for producing the transfer film were laminated. By the above procedure, a laminate having the substrate 1, the photosensitive composition layer, and the temporary support in this order was obtained.
The laminate was exposed and developed in the same procedure as in the evaluation of resolution, and the resolution was evaluated according to the same criteria as described above. there were.

Further, in the same manner as the resolution evaluation procedure of Example 1B, a photosensitive composition layer is formed on the substrate 2, and a laminate having the substrate 2, the photosensitive composition layer, and the temporary support in this order is obtained. Obtained. The laminate was exposed and developed in the same procedure as the acid resistance evaluation, and the acid resistance was evaluated according to the same criteria as described above.
Further, the laminate used in the evaluation of the resolution of Example 1B having the substrate 1, the photosensitive composition layer, and the temporary support in this order was subjected to the same procedure as the evaluation of the peelability. When the peelability was evaluated according to the same evaluation criteria, the evaluation of the peelability was the same as in Example 1.

[Examples 2B to 24B]
In the same manner as in Example 1B, using the photosensitive compositions used to prepare the transfer films of Examples 2 to 24 shown in Table 1, the resolution, acid resistance, and peelability were evaluated. , the same evaluation as each example.

<Change of temporary support and protective film>
[Examples 1C to 24C]
In the production of the transfer film, the temporary support was changed to a 16 μm thick biaxially stretched polyethylene terephthalate film (Lumirror 16FB40, manufactured by Toray Industries, Inc.), and the protective film was a 30 μm thick biaxially stretched polypropylene film (Alphan E-201F , Oji F-Tex Co., Ltd.) were evaluated for resolution, acid resistance, and peelability in the same manner as in Examples 1 to 24, and the evaluation was the same as in each example. .

[Examples 1D to 24D]
In the production of the transfer film, the temporary support was changed to a 38 μm thick biaxially stretched polyethylene terephthalate film (Lumirror #38-U48, manufactured by Toray Industries, Inc.), and the protective film was a 30 μm thick biaxially stretched polypropylene film (Alphan FG-201, manufactured by Oji F-Tex Co., Ltd.) were evaluated for resolution, acid resistance, and peelability in the same manner as in Examples 1 to 24. The evaluation was the same as in each example. Met.

[Examples 1E to 24E]
In the production of the transfer film, the temporary support was changed to a 16 μm thick biaxially stretched polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Industries, Inc.), and the protective film was a 30 μm thick biaxially stretched polypropylene film (Alphan FG-201 , Oji F-Tex Co., Ltd.) were evaluated for resolution, acid resistance, and peelability in the same manner as in Examples 1 to 24, and the evaluation was the same as in each example. .

[Examples 1F to 24F]
In the production of the transfer film, the temporary support was changed to a 38 μm thick biaxially stretched polyethylene terephthalate film (Cosmoshine A4160, Toyobo Co., Ltd.), and the protective film was a 30 μm thick biaxially stretched polypropylene film (Alphan FG- 201, manufactured by Oji F-Tex Co., Ltd.). rice field.

<Production of circuit wiring board>
[Example 101]
A laminate having substrate 2 (PET film, conductive layer), photosensitive composition layer, and temporary support in this order was obtained in the same manner as in the acid resistance evaluation procedure.
The laminate obtained without peeling off the temporary support is subjected to photolithography provided with the pattern shown in FIG. Using a mask, the temporary support and the photomask were brought into contact with each other for pattern exposure. A high-pressure mercury lamp with i-line (365 nm) as the main exposure wavelength was used for exposure. In FIG. 2, the pattern A is a pattern in which the solid line portion and the oblique line portion are exposed and the other portions are shielded, and the dotted line portion DL represents a virtual alignment frame.
Thereafter, the temporary support was peeled off, and development and washing were performed to obtain a resist (cured film of photosensitive composition) pattern in the shape of pattern A.
Then, a 30 wt % aqueous solution of ferric nitrate (pH: 0.6) at 40° C. was supplied for 120 seconds by a shower method. After that, it was immersed in a 3 wt % NaOH aqueous solution at 50° C. to remove the resist.
With a 30 wt% aqueous solution of ferric nitrate at 40°C, the conductive layer (silver nanowire layer) could be etched, and a circuit wiring board on which silver nanowires were formed in a shape corresponding to pattern A was obtained. .
Observation of the obtained circuit wiring board with a microscope revealed that there was no peeling or chipping, and the pattern was clean.

[Examples 102 to 124]
A circuit wiring board was produced in the same manner as in Example 101, except that the transfer films used in Example 101 were changed to the transfer films used in Examples 2 to 24, respectively. Observation of the obtained circuit wiring boards with a microscope revealed that all of the circuit wiring boards had a clean pattern without peeling or chipping.

[Example 101B]
In Example 101, the photosensitive composition layer was formed on the substrate 2 in the same manner as in Example 1B. Other than that, a circuit wiring board was produced in the same manner as in Example 101. Observation of the resulting circuit wiring board with a microscope revealed that the pattern was clean without peeling or chipping.

[Examples 101B to 124B]
A circuit wiring board was produced in the same manner as in Example 101B, except that the photosensitive composition used in Example 101B was changed to the photosensitive composition used in Examples 2 to 24, respectively. Observation of the obtained circuit wiring boards with a microscope revealed that all of the circuit wiring boards had a clean pattern without peeling or chipping.

REFERENCE SIGNS LIST 10 transfer film 11 temporary support 13 intermediate layer 15 photosensitive composition layer 17 composition layer 19 protective film SL non-image area G non-image area DL alignment frame

Claims (25)

an alkali-soluble resin;
a polymerizable compound having an ethylenically unsaturated group;
and a photopolymerization initiator,
The photosensitive composition, wherein the polymerizable compound includes a polymerizable compound A that satisfies the following requirements (X1).
Requirement (X1): 100 parts by mass of the polymerizable compound A and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 74 degrees or more. The photosensitive composition according to claim 1, wherein the polymerizable compound A is a polymerizable compound A1 represented by the following formula (A).
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group. The photosensitive composition according to claim 1 or 2, wherein the polymerizable compound contains a polymerizable compound B that satisfies the following requirement (X2).
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less. 4. The photosensitive composition according to claim 3, wherein said polymerizable compound B has a bisphenol A structure. 5. The photosensitive composition according to claim 3, wherein the mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00. The photosensitive composition according to any one of claims 1 to 5, wherein a mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30. The polymerizable compound A is a polymerizable compound A1 represented by the following formula (A),
The photosensitive composition according to claim 1, wherein the polymerizable compound satisfies the following requirement (X2) and contains a polymerizable compound B having a bisphenol A structure.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less. The polymerizable compound A is a polymerizable compound A1 represented by the following formula (A),
The polymerizable compound contains a polymerizable compound B that satisfies the following requirements (X2) and has a bisphenol A structure,
The mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00,
2. The photosensitive composition according to claim 1, wherein the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less. The photosensitive composition according to any one of claims 1 to 8, wherein the alkali-soluble resin is a resin A1 that satisfies the following requirement (X3).
Requirement (X3): After forming a 2.0 μm film made of the resin A1, the film obtained by heating at 150° C. for 30 minutes has a water contact angle of 65 degrees or more. The alkali-soluble resin contains a structural unit derived from styrene,
10. The photosensitive composition according to any one of claims 1 to 9, wherein the content of structural units derived from styrene is 20% by mass or more with respect to the total mass of the alkali-soluble resin. The photosensitive composition according to any one of claims 1 to 10, wherein the alkali-soluble resin has an acid value of 100 mgKOH/g or more. The photosensitive composition according to any one of claims 1 to 11, which satisfies the following requirement (X4).
Requirement (X4): A 2.0 μm film formed using the photosensitive composition was irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere, and heated at 150° C. for 30 minutes. The resulting film has a water contact angle of 60 degrees or more. a temporary support;
A transfer film comprising a photosensitive composition layer formed using the photosensitive composition according to any one of claims 1 to 12. 14. The transfer film according to claim 13, wherein the photosensitive composition layer has a thickness of 1 to 10 μm. A preparation step of preparing a laminate having a substrate, a conductive layer containing silver, and a photosensitive composition layer in this order;
An exposure step of pattern-exposing the photosensitive composition layer;
a developing step of developing the exposed photosensitive composition layer to form a resist pattern;
A method for manufacturing a laminate having a conductor pattern, comprising an etching step of etching the conductive layer in a region where the resist pattern is not formed, with an etchant having a pH of less than 2.0,
The photosensitive composition layer is
an alkali-soluble resin;
a polymerizable compound having an ethylenically unsaturated group;
and a photopolymerization initiator,
A method for producing a laminate having a conductor pattern, wherein the polymerizable compound contains a polymerizable compound A that satisfies the following requirement (X1).
Requirement (X1): 100 parts by mass of the polymerizable compound A and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 74 degrees or more. 16. The method for producing a laminate having a conductor pattern according to claim 15, wherein the polymerizable compound A is a polymerizable compound A1 represented by the following formula (A).
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group. 17. The method for producing a laminate having a conductor pattern according to claim 15 or 16, wherein the polymerizable compound contains a polymerizable compound B that satisfies the following requirement (X2).
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less. 18. The method for producing a laminate having a conductor pattern according to claim 17, wherein the polymerizable compound B is a polymerizable compound B1 having a bisphenol A structure. The method for producing a laminate having a conductor pattern according to claim 17 or 18, wherein the mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00. . The laminate having the conductor pattern according to any one of claims 15 to 19, wherein the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30. manufacturing method. The polymerizable compound A includes a polymerizable compound A1 represented by the following formula (A),
16. The method for producing a laminate having a conductor pattern according to claim 15, wherein the polymerizable compound satisfies the following requirement (X2) and contains a polymerizable compound B having a bisphenol A structure.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less. The polymerizable compound A includes a polymerizable compound A1 represented by the following formula (A),
The polymerizable compound is a photosensitive composition that satisfies the following requirement (X2) and contains a polymerizable compound B having a bisphenol A structure,
The mass ratio of the content of the polymerizable compound B to the content of the polymerizable compound A is 0.50 to 4.00,
16. The method for producing a laminate having a conductor pattern according to claim 15, wherein the mass ratio of the content of the alkali-soluble resin to the content of the polymerizable compound is 0.68 to 1.30.
Q ¹ -R ¹ -Q ² Formula (A)
In formula (A), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group.
In formula (A), R ¹ represents a chain divalent hydrocarbon group.
Requirement (X2): 100 parts by mass of the polymerizable compound B and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime)1. A composition consisting of 0 parts by mass and 9 parts by mass of methyl ethyl ketone was applied to form a film of 2.0 μm, and then irradiated with i-rays at an exposure dose of 500 mJ/cm ² in a nitrogen atmosphere. The contact angle of water on the film obtained by heating for minutes is 65 degrees or less. The method for producing a laminate having a conductor pattern according to any one of claims 15 to 22, wherein the alkali-soluble resin is a resin A1 that satisfies the following requirement (X3).
Requirement (X3): After forming a 2.0 μm film made of the resin A1, the film obtained by heating at 150° C. for 30 minutes has a water contact angle of 65 degrees or more. The alkali-soluble resin contains a structural unit derived from styrene,
The method for producing a laminate having a conductor pattern according to any one of claims 15 to 23, wherein the structural unit derived from styrene accounts for 20% by mass or more of the total mass of the alkali-soluble resin. The method for producing a laminate having a conductor pattern according to any one of claims 15 to 24, wherein the alkali-soluble resin has an acid value of 100 mgKOH/g or more.

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