Composition, transfer film, method for producing laminate, method for producing circuit wiring, and method for producing electronic device

Abstract

The present invention provides a composition having excellent coating properties. Another aspect of the present invention provides a transfer film, a method for manufacturing a laminate, a method for manufacturing a circuit wiring, and a method for manufacturing an electronic device related to the above composition. The composition of the present invention comprises an alkali-soluble resin, a polymerizable compound, and compound A, wherein compound A is a compound having a group represented by the following general formula (1). General formula (1): *-CF2-H, wherein * represents a bonding position.

Description

Technical Field

[0001] The present invention relates to a composition, a transfer film, a method for producing a laminate, a method for producing a circuit wiring, and a method for producing an electronic device.

[0002] In recent years, transfer films such as photosensitive transfer materials have been increasingly used in a wide variety of fields.

[0003] Photosensitive transfer materials can contribute to reducing product costs, and therefore have been proposed for use as etching resist films, wiring protection films, and the like.

[0004] At the same time, depending on the field, the properties of the polymer serving as the matrix and the coating properties when preparing the transfer film are also important.

[0005] For example, in Patent Document 1, a transfer film is produced using a photosensitive composition to which a fluorine-containing / lipophilic group-containing oligomer is added (see Patent Document 1

[0211]

[0214]

[0215] , etc.).

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2018 / 008376 Summary of the Invention

[0009] Technical issues to be solved by the invention

[0010] As a result of studies conducted by the present inventors, they found that there is room for improvement in the coating properties of the composition (photosensitive composition) disclosed in Patent Document 1.

[0011] Furthermore, the excellent coating properties of the composition mean that when the composition is applied, depression of the composition is less likely to occur, uneven coating of the composition is less likely to occur, and a homogeneous film (composition layer) is easily obtained.

[0012] Therefore, an object of the present invention is to provide a composition having excellent coating properties. Another object is to provide a transfer film, a method for producing a laminate, a method for producing a circuit wiring, and a method for producing an electronic device using the composition.

[0013] Means for solving technical problems

[0014] The present inventors conducted intensive studies to solve the above-mentioned problems and found that the above-mentioned problems can be solved by the following configuration.

[0015] [1] A composition comprising an alkali-soluble resin, a polymerizable compound, and a compound A, wherein the compound A is a compound having a group represented by the general formula (1) described below.

[0016] [2] The composition according to [1], wherein the compound A is a compound having a group represented by the general formula (2) described below.

[0017] [3] The composition according to [1] or [2], wherein the compound A is a compound having a group represented by the general formula (3) described below.

[0018] [4] The composition according to any one of [1] to [3], wherein the compound A is a polymer compound having a weight average molecular weight of 5,000 or more.

[0019] [5] The composition according to any one of [1] to [4], wherein the compound A is a polymer compound,

[0020] The polymer compound includes a structural unit derived from a monomer represented by the general formula (4A) described later.

[0021] [6] The composition according to [5], wherein the polymer compound further comprises a structural unit derived from a monomer represented by the general formula (5) described below.

[0022] [7] The composition according to any one of [1] to [3], wherein the molecular weight of the compound A is 2,000 or less.

[0023] [8] The composition according to any one of [1] to [3] and [7], wherein the compound A is a compound represented by the general formula (6A) described below.

[0024] [9] The composition according to [8], wherein Z represents a monovalent organic group containing a poly(oxyalkylene) structural portion which may have a substituent.

[0025]

[10] The composition according to any one of [1] to [9], further comprising a polymerization initiator.

[0026]

[11] The composition according to any one of [1] to [9], wherein the alkali-soluble resin is a thermoplastic resin.

[0027]

[12] The composition according to any one of [1] to

[11] , further comprising black particles.

[0028]

[13] A transfer film comprising a temporary support and one or more composition layers, wherein at least one of the composition layers is formed using the composition according to any one of [1] to

[12] .

[0029]

[14] A method for manufacturing a laminate, comprising:

[0030] a laminating step of bringing a substrate into contact with a surface of the transfer film described in

[13] on the opposite side of the temporary support, laminating the transfer film and the substrate to obtain a substrate with a transfer film;

[0031] an exposure step of performing pattern exposure on the composition layer; and

[0032] a developing step of developing the exposed composition layer to form a resin pattern;

[0033] A peeling step of peeling the temporary support from the substrate with the transfer film is further included between the laminating step and the exposure step or between the exposure step and the development step.

[0034]

[15] A method for manufacturing a circuit wiring, comprising:

[0035] a laminating step of bringing the surface of the transfer film described in

[13] opposite to the temporary support into contact with a substrate having a conductive layer, laminating the transfer film and the substrate having the conductive layer to obtain a substrate with a transfer film;

[0036] An exposure step of performing pattern exposure on the composition layer;

[0037] a developing step of developing the exposed composition layer to form a resin pattern; and

[0038] an etching step of etching the conductive layer in a region where the resin pattern is not provided;

[0039] A peeling step of peeling the temporary support from the substrate with the transfer film is further included between the laminating step and the exposure step or between the exposure step and the development step.

[0040]

[16] A method for producing an electronic device, comprising the method for producing a laminate according to

[14] , wherein the electronic device includes the resin pattern as a cured film.

[0041] Effects of the Invention

[0042] According to the present invention, a composition having excellent coating properties can be provided, and a transfer film, a method for producing a laminate, a method for producing a circuit wiring, and a method for producing an electronic device using the composition can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a schematic diagram showing an example of the structure of a transfer film. DETAILED DESCRIPTION

[0044] Hereinafter, the present invention will be described in detail.

[0045] The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0046] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values described before and after "to" as the lower limit and the upper limit.

[0047] Furthermore, in this specification, the bonding direction of the divalent group (for example, -CO-O-) is not particularly limited.

[0048] In this specification, (meth)acrylate refers to acrylate and methacrylate, (meth)acrylic acid refers to acrylic acid and methacrylic acid, and (meth)acryloyl refers to methacryloyl or acryloyl.

[0049] Regarding the notation of groups (atomic groups) in this specification, the notation noting whether or not substituted includes groups without substitution and also includes groups with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups). Furthermore, "organic group" in this specification refers to a group containing at least one carbon atom.

[0050] Furthermore, in this specification, when a compound is referred to as "may have a substituent", the type, position, or number of substituents is not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Furthermore, the compound may be unsubstituted.

[0051] Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, and the substituent can be selected from the following substituent group T, for example.

[0052] (Substituent T)

[0053] Examples of the substituent T include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy, ethoxy and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and methylsulfoyl; alkylthio groups such as methylthio and tert-butylthio; arylthio groups such as phenylthio and p-tolylthio; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamido groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups; and combinations thereof.

[0054] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC).

[0055] Regarding GPC, measurement was performed under the following conditions.

[0056] [Eluent] Tetrahydrofuran (THF)

[0057] [Device name] EcoSEC HLC-8320GPC (manufactured by TOSOH CORPORATION)

[0058] [Column] TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by TOSOH CORPORATION)

[0059] [Column temperature] 40℃

[0060] [Flow rate] 0.35ml / min

[0061] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).

[0062] In this specification, room temperature is 25°C unless otherwise specified.

[0063] In this specification, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22°C is 0.1 g or more.

[0064] In this specification, "water-soluble" means that the solubility in 100 g of water with a pH of 7.0 at a liquid temperature of 22°C is 0.1 g or more.

[0065] In this specification, the layer thickness (film thickness) of each layer possessed by a transfer film, etc. is measured as follows: a cross section perpendicular to the main surface of the layer (film) is observed using a scanning electron microscope (SEM), the thickness of each layer at more than 10 points is measured based on the obtained observation image, and the average value is calculated.

[0066] [Composition]

[0067] The composition of the present invention contains an alkali-soluble resin, a polymerizable compound, and compound A. Compound A is a compound having a group represented by the general formula (1) described below.

[0068] Although the mechanism by which the problems of the present invention are solved by such a structure is not yet clear, the present inventors speculate as follows.

[0069] Compound A contains a fluoroalkyl group (a group represented by the general formula (1)) containing a hydrogen atom at its terminal portion in its structure. This compound A has good compatibility with the resin and the like in the composition and good solubility in an organic solvent (which may be a water-soluble solvent) added as needed. Therefore, it is believed that aggregation of compound A in the composition is less likely to occur, uneven coating of the composition is less likely to occur, and coating properties are improved.

[0070] Furthermore, it is believed that when compound A further contains a poly(oxyalkylene) structural moiety, compound A is more easily transferred to the coating film surface. It is speculated that the presence of compound A in the composition further reduces the surface tension of the coating film, further improves the wettability of the composition to the substrate during application, and further improves the surface shape of the coating film surface, thereby further improving coating properties.

[0071] Furthermore, it is speculated that when Compound A is a polymer compound having a poly(oxyalkylene) structural moiety and a weight average molecular weight of 5,000 to 11,500, the rate of transfer of Compound A to the coating surface is further accelerated, and coating properties are further improved.

[0072] [Compound A]

[0073] The composition of the present invention comprises compound A.

[0074] Compound A is a compound having a group represented by the following general formula (1).

[0075] General formula (1): *-CF2-H

[0076] Where * represents the bonding position.

[0077] Compound A may be a polymer compound or a low molecular compound. In addition, when Compound A is a polymer compound, Compound A as a polymer compound is sometimes referred to as "polymer compound A". In addition, when Compound A is a low molecular compound, Compound A as a low molecular compound is sometimes referred to as "low molecular compound A". From the viewpoint of achieving a more excellent effect of the present invention, Compound A is preferably a polymer compound A.

[0078] The lower limit of the weight average molecular weight of polymer compound A is preferably 1,000 or more, more preferably 1,500 or more, more preferably more than 2,000, and particularly preferably 5,000 or more. The upper limit is preferably 100,000 or less, more preferably 80,000 or less, further preferably 60,000 or less, further preferably 40,000 or less, particularly preferably 20,000 or less, and most preferably 11,500 or less.

[0079] The number average molecular weight (Mn) of the polymer compound A is preferably 500 to 40,000, more preferably 600 to 20,000, and even more preferably 600 to 10,000.

[0080] The dispersion degree (Mw / Mn) of the polymer compound A is preferably 1.00 to 12.00, more preferably 1.00 to 11.00, and even more preferably 1.00 to 10.00.

[0081] The polymer compound A preferably contains a structural unit having a group represented by the general formula (1).

[0082] The molecular weight of the low molecular compound A is preferably 100 or more, more preferably 500 or more. The upper limit of the molecular weight of the low molecular compound A is preferably 5,000 or less, more preferably 3,000 or less, and further preferably 2,000 or less.

[0083] The number of groups represented by the general formula (1) in the low molecular weight compound A is not particularly limited as long as it is 1 or more, but is preferably 1 to 3, for example.

[0084] Specific aspects of the polymer compound A and the low molecular compound A will be described later.

[0085] Furthermore, from the viewpoint of achieving a more excellent effect of the present invention, compound A is preferably a compound having a group represented by the general formula (2) described later (hereinafter also referred to as "compound Aa"), and more preferably a compound having a group represented by the general formula (3) described later (hereinafter also referred to as "compound Ab").

[0086] In addition, compound Aa is a compound in which the connection form of the group represented by general formula (1) in compound A is further limited. That is, -CF2-H present at the terminal portion of the group represented by general formula (2) in compound Aa is a compound in which the connection form of the group represented by general formula (1) in compound A and the connection form of the group represented by general formula (2) in compound Aa are further limited. That is, -CF2-H present at the terminal portion of the group represented by general formula (3) in compound Ab is a compound in which the connection form of the group represented by general formula (1) is further limited, and -CF2-CF2-H present at the terminal portion of the group represented by general formula (3) in compound Ab is a compound in which the connection form of the group represented by general formula (2) is further limited.

[0087] General formula (2): *-CF2-CF2-H

[0088] Where * represents the bonding position.

[0089] General formula (3): *-(CH2) m-(CF2-CF2) n -H

[0090] In the formula, m and n each independently represent an integer of 1 to 6.

[0091] m is preferably 1 to 4, more preferably 1 or 2.

[0092] As n, 1 to 4 are preferable, and 2 or 3 is more preferable.

[0093] *Indicates bonding position.

[0094] Hereinafter, the polymer compound A and the low molecular compound A will be described separately.

[0095] <Polymer Compound A>

[0096] As described above, the polymer compound A refers to an embodiment in which the compound A is a polymer compound. Preferred embodiments of the weight average molecular weight and dispersity of the polymer compound A are as described above.

[0097] The polymer compound A preferably contains a structural unit having a group represented by any one of the general formulas (1) to (3) described above, more preferably contains a structural unit derived from a monomer represented by the general formula (4) described below, and even more preferably contains a structural unit derived from a monomer represented by the general formula (4A) described below. Furthermore, the structural unit derived from the monomer represented by the general formula (4) described below corresponds to the structural unit having a group represented by the general formula (1) or (2), and the structural unit derived from the monomer represented by the general formula (4A) described below corresponds to the structural unit having a group represented by the general formula (3) described above.

[0098] [Chemical Formula 1]

[0099]

[0100] In the general formula (4), R 1 represents a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or -N(R 2 )-. R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 1 Represents a divalent linking group. T It represents a group represented by the above-mentioned general formula (1) or (2).

[0101] As R 2 The alkyl group having 1 to 4 carbon atoms represented by may be linear, branched, or cyclic.

[0102] As R 1 , preferably a hydrogen atom.

[0103] As R 2, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

[0104] As X, an oxygen atom is preferred.

[0105] As L 1 The divalent linking group represented by is not particularly limited, and examples thereof include -O-, -CO-, -S-, -SO2-, and -NR X -(R X is a hydrogen atom or a substituent), an alkylene group, an alkenylene group, an alkynylene group, an aromatic ring group, an alicyclic group, and a group composed of these. X The substituent represented by is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T. An alkyl group having 1 or 2 carbon atoms is preferred.

[0106] The above-mentioned alkylene, alkenylene, alkynylene, aromatic ring group, and alicyclic group may further have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in Substituent Group T. Among these substituents, a halogen atom is preferred, and a fluorine atom is more preferred.

[0107] The alkylene group, the alkenylene group, and the alkynylene group may be linear or branched.

[0108] The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 11, and particularly preferably 1 to 10.

[0109] Furthermore, the number of carbon atoms in the alkenylene group and the alkynylene group is preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 11, and particularly preferably 2 to 10.

[0110] The aromatic ring group may be any of an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

[0111] The aromatic ring constituting the aromatic ring group may be monocyclic or polycyclic. Furthermore, the number of aromatic rings constituting the aromatic ring group is not particularly limited, and is, for example, 5 to 15. Furthermore, the number of heteroatoms contained in the aromatic heterocyclic group is not particularly limited, and is preferably 1 to 3, for example. The type of heteroatom is not particularly limited, and examples thereof include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0112] Examples of the aromatic ring constituting the aromatic ring group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; and aromatic heterocyclic rings such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.

[0113] The alicyclic group may be any of an aliphatic hydrocarbon ring group and an aliphatic heterocyclic group.

[0114] The alicyclic ring constituting the alicyclic group may be monocyclic or polycyclic. Furthermore, the number of alicyclic rings constituting the alicyclic group is not particularly limited, and is, for example, 5 to 15. Furthermore, the number of heteroatoms contained in the aliphatic heterocyclic group is not particularly limited, and is, for example, preferably 1 to 3. The type of heteroatom is not particularly limited, and examples thereof include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0115] Examples of the alicyclic ring constituting the alicyclic group include cycloalkane rings and cyclohexene rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring and exo-tetrahydrodicyclopentadiene ring.

[0116] As L 1 The divalent linking group represented by A -Fluorine-substituted alkylene group-* B , can be * A -Fluorine-substituted alkenylene-* B or can be * A -Fluorine-substituted alkynylene group-* B , more preferably can be * A -Fluorine-substituted alkylene group-* B .in addition,* A Indicates the connection position with X in formula (4), * B Represents the same as R in formula (4) T connection location.

[0117] [Chemical Formula 2]

[0118]

[0119] In formula (4A), R 1 and X are respectively related to R in formula (4) 1 and X have the same meanings and preferred embodiments are also the same.

[0120] m and n each independently represent an integer of 1 to 6. m is preferably 1 to 4, more preferably 1 or 2. n is preferably 1 to 4, more preferably 2 or 3.

[0121] In the polymer compound A, the lower limit of the content of the structural unit having a group represented by any of the general formulae (1) to (3) is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total mass of the polymer compound A. The upper limit is preferably 100% by mass or less, more preferably 90% by mass, and even more preferably 80% by mass.

[0122] As the structural unit having a group represented by any of the general formulae (1) to (3), one type may be used alone, or two or more types may be used in combination.

[0123] The structural unit having a group represented by any of the general formulae (1) to (3) can be synthesized by a known method.

[0124] The polymer compound A may have other structural units (hereinafter also referred to as "other structural units") in addition to the structural unit having a group represented by any one of the general formulae (1) to (3).

[0125] The other structural units are not particularly limited, but from the viewpoint of further improving the effects of the present invention, it is preferred that a structural unit having a poly(oxyalkylene) structure be included.

[0126] As the poly(oxyalkylene) structure, a structure represented by the following formula (PAL) is preferred.

[0127] [Chemical Formula 3]

[0128]

[0129] In the formula (PAL), nAL represents an integer of 2 or greater, more preferably 2-100, further preferably 4-20, particularly preferably 4-15, and most preferably 4-12.

[0130] AL represents an alkylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group represented by AL is preferably 1 to 10, more preferably 1 to 6, further preferably 2 to 4, and particularly preferably 2 or 3.

[0131] The nAL ALs may be the same or different.

[0132] The alkylene group represented by AL may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.

[0133] Among them, AL is preferably -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2- or -CH(CH2CH3)CH2-, and more preferably -CH(CH3)CH2- or -CH2CH2CH2-.

[0134] *Indicates bonding position.

[0135] The structural unit having a poly(oxyalkylene) structure preferably has a poly(oxyalkylene) structure in a side chain, and more preferably is a structural unit derived from a monomer represented by the general formula (5) described later.

[0136] [Chemical Formula 4]

[0137]

[0138] Where R 3 represents a hydrogen atom or a methyl group. Y represents an oxygen atom, a sulfur atom or -N(R 5 )-. AL represents an alkylene group which may have a substituent. nAL represents an integer greater than 2. R 4 represents a hydrogen atom or a substituent. 5 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0139] AL and nAL in formula (5) have the same meanings as AL and nAL in formula (PAL), and preferred embodiments are also the same.

[0140] As R 4 The substituent represented by is not particularly limited, and the substituents exemplified in the substituent group T may be mentioned. An alkyl group having 1 to 6 carbon atoms is preferred.

[0141] As R 5 The alkyl group having 1 to 4 carbon atoms represented by may be linear, branched, or cyclic.

[0142] As R 3 and R 4 , preferably a hydrogen atom.

[0143] As R 5 , preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

[0144] As Y, an oxygen atom is preferred.

[0145] When the polymer compound A contains a structural unit having a poly(oxyalkylene) structure, the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more, relative to the total mass of the polymer compound A. The upper limit thereof is preferably 95% by mass or less, and more preferably 90% by mass or less.

[0146] The structural unit having a poly(oxyalkylene) structure may be used alone or in combination of two or more.

[0147] As other structural units that the polymer compound A may contain, in addition to the above-mentioned structural units, for example, a structural unit derived from a (meth)acrylate and a structural unit derived from (meth)acrylic acid are also preferred.

[0148] Examples of the (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 18 carbon atoms. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearic (meth)acrylate.

[0149] When the polymer compound A contains a structural unit selected from a structural unit derived from a (meth)acrylate and a structural unit derived from (meth)acrylic acid, the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to the total mass of the polymer compound A. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0150] When the polymer compound A is a copolymer, the polymer compound A also preferably has a block structure, a graft structure, a branched structure, and / or a star structure.

[0151] Various monomers constituting the polymer compound A and the polymer compound A can be produced by known methods.

[0152] <Low molecular compound A>

[0153] As described above, the low molecular compound A refers to an embodiment in which the compound A is a low molecular compound. Preferred embodiments of the molecular weight of the low molecular compound A are as described above.

[0154] As the low molecular weight compound A, a compound having a group represented by any of the general formulas (1) to (3) described above is preferred, a compound represented by the later-described (6) is more preferred, a compound represented by the later-described general formula (6A) is further preferred, and a compound represented by the later-described general formula (6B) is particularly preferred. Furthermore, the compound represented by the later-described general formula (6) corresponds to a compound having a group represented by the above-described general formula (1) or (2), and the compound represented by the later-described general formula (6A) or (6B) corresponds to a compound having a group represented by the above-described general formula (3).

[0155] [Chemical Formula 5]

[0156] ZL 2 -R T (6)

[0157] In the general formula (6), Z represents a monovalent organic group. 2 represents a single bond or a divalent linking group. T It represents a group represented by the above-mentioned general formula (1) or (2).

[0158] The monovalent organic group represented by Z is not particularly limited, and may contain, for example, a heteroatom (for example, a heteroatom may contain -O-, -CO-, -S-, -SO2-, and -NR X -(R X is a hydrogen atom or a substituent)), an alkyl group, an alkenyl group, and an alkynyl group. X The substituent represented by is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T.

[0159] The above-mentioned alkyl, alkenyl, and alkynyl groups may further have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in Substituent Group T.

[0160] The alkyl group, alkenyl group, and alkynyl group may be linear, branched, or cyclic.

[0161] Furthermore, the number of carbon atoms in the alkyl group is not particularly limited, and is, for example, 1 to 40, preferably 1 to 30, and more preferably 1 to 20.

[0162] Furthermore, the number of carbon atoms in the alkenyl group and the alkynyl group is not particularly limited, and is, for example, 2 to 40, preferably 2 to 30, and more preferably 2 to 20.

[0163] Among them, a monovalent organic group having a poly(oxyalkylene) structure is preferred as Z. As the poly(oxyalkylene) structure, a structure represented by the above-mentioned formula (PAL) is preferred.

[0164] In addition, Z and L in formula (6) 2 The atom at the attachment position of is preferably a carbon atom.

[0165] As L 2 The divalent linking group represented by L in the above general formula (4) can be cited as an example. 1 The divalent linking groups represented are the same linking groups.

[0166] As L 2 The divalent linking group represented by A -L 21 -Fluorine-substituted alkylene group-* B , can be * A -L 21 -Fluorine-substituted alkenylene-* B or can be * A -L 21 -Fluorine-substituted alkynylene group-* B , more preferably can be * A -L 21 -Fluorine-substituted alkylene group-* B .

[0167] L 21 Indicates -O-, -CO-, -S-, -SO2-, -NR X -(R X is a hydrogen atom or a substituent) or a group composed of these. X The substituent represented by is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T, and an alkyl group having 1 or 2 carbon atoms is preferred. 21 Among them, -O-, -S- or -NR X -, more preferably -O-.

[0168] * A Indicates the connection position with Z in formula (6), * B Represents the same as R in formula (6) T connection location.

[0169] [Chemical Formula 6]

[0170]

[0171] In the formula, Z represents a monovalent organic group. 3 represents an oxygen atom, a sulfur atom or -N(R 6 )-. m and n each independently represent an integer of 1 to 6. R 6 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0172] Examples of the monovalent organic group represented by Z in formula (6A) include the same ones as the monovalent organic group represented by Z in formula (6), and preferred embodiments are also the same.

[0173] As R 6 The alkyl group having 1 to 4 carbon atoms represented by may be linear, branched, or cyclic.

[0174] As L 3 , preferably an oxygen atom.

[0175] m is preferably 1 to 4, more preferably 1 or 2.

[0176] As n, 1 to 4 are preferable, and 2 or 3 is more preferable.

[0177] [Chemical Formula 7]

[0178]

[0179] AL and nAL in formula (6B) have the same meanings as AL and nAL in formula (PAL), and preferred embodiments are also the same.

[0180] L in formula (6B) 3, m, and n are each the same as L in formula (6A) 3 , m and n have the same meanings and the preferred embodiments are also the same.

[0181] In formula (6B), R 7 represents a hydrogen atom or a substituent.

[0182] As R 7 The substituent represented by is not particularly limited, and the substituents exemplified in the substituent group T may be mentioned. An alkyl group having 1 to 6 carbon atoms is preferred.

[0183] As R 7 , preferably a hydrogen atom.

[0184] The low molecular compound A can be produced by a known method.

[0185] Specific examples of Compound A are shown below, but Compound A in the present invention is not limited thereto.

[0186] [Chemical Formula 8]

[0187]

[0188] [Chemical Formula 9]

[0189]

[0190] [Chemical Formula 10]

[0191]

[0192] [Chemical Formula 11]

[0193]

[0194] The content of compound A is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, and even more preferably 0.02 to 1% by mass relative to the total solid content of the composition (negative photosensitive resin composition, thermoplastic resin composition and / or colored resin composition described below).

[0195] In this specification, the "solid content" of a composition refers to the components that form a composition layer (e.g., a negative photosensitive resin layer) formed using the composition. If the composition contains a solvent (e.g., an organic solvent, water, etc.), the solid content refers to all components excluding the solvent. Furthermore, liquid components are also considered solid components if they form a composition layer.

[0196] 〔Alkali-soluble resin〕

[0197] The composition of the present invention comprises an alkali-soluble resin.

[0198] The alkali-soluble resin is a component different from the polymer compound A.

[0199] The nature and / or characteristics of the alkali-soluble resin are not limited and can be appropriately selected depending on the application of the composition.

[0200] The details of the alkali-soluble resin contained in the composition of the present invention will be described later according to each form of the composition.

[0201] 〔Polymerizable compounds〕

[0202] The composition of the present invention contains a polymerizable compound.

[0203] The properties and / or characteristics of the polymerizable compound are not limited and can be appropriately selected depending on the application of the composition.

[0204] The details of the polymerizable compound contained in the composition of the present invention will be described later according to each aspect of the composition.

[0205] [Other ingredients]

[0206] The composition of the present invention may contain an alkali-soluble resin, a polymerizable compound, and other components besides compound A.

[0207] Examples of other components include polymerization initiators, dyes, heat-crosslinkable compounds, solvents, plasticizers, sensitizers, and compounds that generate acids, bases, or radicals by light.

[0208] The details of other components contained in the composition of the present invention will be described later according to each form of the composition.

[0209] [Composition method]

[0210] The form of the composition of the present invention is not particularly limited.

[0211] For example, the composition of the present invention may be a negative photosensitive resin composition for forming a negative photosensitive resin layer, a thermoplastic resin composition for forming a thermoplastic resin layer, or a colored resin composition for forming a colored resin layer.

[0212] Hereinafter, components that may be contained in each composition in each embodiment will be described.

[0213] In addition, components described as components of a composition of one embodiment are not only permitted to be included in the composition of that embodiment, but can also be used as components of a composition of another embodiment. For example, the components described below as components of a negative photosensitive resin layer composition can be used as components of a composition other than a negative photosensitive resin composition.

[0214] [Negative photosensitive resin composition]

[0215] In a display device (such as an organic electroluminescent (EL) display device and a liquid crystal display device) equipped with a touch panel, such as an electrostatic capacitive input device, a conductive layer pattern including an electrode pattern of a sensor corresponding to a visual recognition portion, a peripheral wiring portion, and wiring for extracting the wiring portion is provided inside the touch panel.

[0216] Generally, a method is widely used to form a patterned layer by providing a layer (photosensitive layer) of a negative photosensitive resin composition on a substrate using a transfer film or the like, exposing the photosensitive layer through a mask having a desired pattern, and then developing the layer.

[0217] Here, first, when the composition is a negative photosensitive resin composition, components that can be contained as components other than compound A will be described.

[0218] When the composition is a negative photosensitive resin composition, it is preferred that the negative photosensitive resin composition contains compound A, an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

[0219] Such a composition (eg, a negative photosensitive resin composition) preferably contains, based on the total solids content of the composition, 10 to 90% by mass of an alkali-soluble resin, 5 to 70% by mass of a polymerizable compound, and 0.01 to 20% by mass of a polymerization initiator. Each component will be described below in order.

[0220] <Polymer P (resin)>

[0221] When the composition is a negative photosensitive resin composition, the alkali-soluble resin contained in the composition is particularly referred to as a polymer P.

[0222] From the viewpoint of achieving better resolution by suppressing swelling of the negative photosensitive resin layer by the developer, the acid value of the polymer P is preferably 220 mgKOH / g or less, more preferably less than 200 mgKOH / g, and even more preferably less than 190 mgKOH / g.

[0223] The lower limit of the acid value of the polymer P is not particularly limited, but is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more from the viewpoint of better developability.

[0224] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and in this specification, the unit is expressed as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

[0225] The acid value of the polymer P may be adjusted according to the type of structural unit constituting the polymer P and the content of the structural unit containing an acid group.

[0226] The weight average molecular weight of polymer P is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferred from the perspective of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and further preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, it is preferred from the perspective of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge melting property and wafer cutting property when it is a negative photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. Edge melting property refers to the ease with which the negative photosensitive resin layer (i.e., the layer containing the negative photosensitive resin composition) protrudes from the end surface of the roll when the negative photosensitive resin laminate is wound into a roll. Wafer cutting property refers to the ease with which the wafer flies off when the unexposed film is cut with a cutter. If the wafer adheres to the upper surface of a negative-type photosensitive resin laminate, it may be transferred to the mask during the subsequent exposure process, causing defective products. The dispersion degree of the polymer P is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0227] In the negative photosensitive resin composition, from the viewpoint of suppressing the thickening of the line width and the degradation of the resolution when the focus position is offset during exposure, the polymer P preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. In addition, as such an aromatic hydrocarbon group, for example, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group can be mentioned. Relative to the total mass of the polymer P, the content of the structural unit based on the monomer having an aromatic hydrocarbon group in the polymer P is preferably 20% by mass or more, more preferably 30% by mass or more. As an upper limit, there is no particular limitation, but it is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, when comprising a plurality of polymers P, it is preferred that the average value of the content of the structural unit based on the monomer having an aromatic hydrocarbon group is within the above range.

[0228] Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among these, monomers having an aralkyl group or styrene are preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer P is styrene, the content of the structural unit based on styrene relative to the total mass of the polymer P is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, further preferably 30 to 60% by mass, and particularly preferably 30 to 55% by mass.

[0229] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding the benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferred.

[0230] Examples of the monomer having a phenylalkyl group include phenethyl (meth)acrylate and the like.

[0231] Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and benzyl alcohol. Among these, benzyl (meth)acrylate is preferred. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer P is benzyl (meth)acrylate, the content of the structural unit based on benzyl (meth)acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, further preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, relative to the total mass of the polymer P.

[0232] The polymer P containing a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one of the first monomers described below and / or at least one of the second monomers described below.

[0233] The polymer P containing no structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and more preferably by copolymerizing at least one of the first monomers and at least one of the second monomers described below.

[0234] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.

[0235] The content of the structural unit based on the first monomer in the polymer P is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% by mass, relative to the total mass of the polymer P.

[0236] From the perspective of exhibiting good developability and controlling edge melting properties, the above content is preferably 5% by mass or more. From the perspective of high resolution and edge shape of the resist pattern, and further from the perspective of chemical resistance of the resist pattern, the above content is preferably 50% by mass or less.

[0237] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include (meth)acrylates such as 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, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred.

[0238] The content of the structural unit based on the second monomer in the polymer P is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 17 to 45% by mass, relative to the total mass of the polymer P.

[0239] When the polymer P contains structural units based on a monomer having an aralkyl group and / or structural units based on a monomer having styrene, it is preferred from the viewpoint of suppressing thickening of line width and degradation of resolution due to focus position shift during exposure. For example, copolymers containing structural units based on methacrylic acid, structural units based on benzyl methacrylate, and structural units based on styrene, and copolymers containing structural units based on methacrylic acid, structural units based on methyl methacrylate, structural units based on benzyl methacrylate, and structural units based on styrene are preferred.

[0240] In one embodiment, the polymer P preferably comprises 25 to 55% by mass of structural units based on a monomer having an aromatic hydrocarbon group, 20 to 35% by mass of structural units based on the first monomer, and 15 to 45% by mass of structural units based on the second monomer. Furthermore, in another embodiment, the polymer preferably comprises 70 to 90% by mass of structural units based on a monomer having an aromatic hydrocarbon group and 10 to 25% by mass of structural units based on the first monomer.

[0241] The polymer P may have a branched structure and / or an alicyclic structure in the side chain. Furthermore, the side chain may have a linear structure. By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer P. The group having an alicyclic structure may be monocyclic or polycyclic.

[0242] Specific examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate, t-amyl (meth)acrylate, sec-isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate. Among these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or t-butyl methacrylate is preferred, and isopropyl methacrylate or t-butyl methacrylate is more preferred.

[0243] Specific examples of the monomer containing a group having an alicyclic structure in a side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include (bicyclo〔2.2.1]heptyl-2-(meth)acrylate), 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5-yl (meth)acrylate, octahydro-4,7-menthyl-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo〔3.1.1〕heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo〔4.1.0〕heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these (meth)acrylates, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0244] The polymer P may be used alone or in combination of two or more.

[0245] When two or more polymers P are used, it is preferred to use a mixture of two polymers P containing structural units based on a monomer having an aromatic hydrocarbon group, or to use a mixture of a polymer P containing structural units based on a monomer having an aromatic hydrocarbon group and a polymer P not containing structural units based on a monomer having an aromatic hydrocarbon group. In the latter case, the proportion of the polymer P containing structural units based on a monomer having an aromatic hydrocarbon group used relative to the total mass of the polymer P is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

[0246] The synthesis of polymer P is preferably carried out by adding an appropriate amount of a free radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution of the above-mentioned monomers or monomers diluted with a solvent such as acetone, methyl ethyl ketone, and isopropyl alcohol, followed by heating and stirring. Synthesis is sometimes performed while a portion of the mixture is dropwise added to the reaction solution. Sometimes, further solvent is added after the reaction is completed to adjust the desired concentration. Synthesis methods include bulk polymerization, suspension polymerization, or emulsion polymerization, in addition to solution polymerization.

[0247] The glass transition temperature Tg of polymer P is preferably 30 to 135°C. By using a polymer P having a Tg of 135°C or lower, it is possible to suppress the thickening of the line width and the degradation of the resolution when the focus position shifts during exposure. From this viewpoint, the Tg of polymer P is more preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, from the viewpoint of improving edge melting resistance, it is preferred to use a polymer P having a Tg of 30°C or higher. From this viewpoint, the Tg of polymer P is more preferably 40°C or higher, further preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

[0248] The negative photosensitive resin composition may contain other resins in addition to the above.

[0249] Examples of other resins include acrylic resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0250] As the polymer P, the alkali-soluble resin described in the description of the thermoplastic resin composition to be described later can be used.

[0251] The content of polymer P is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 20 to 70% by mass, particularly preferably 20 to 60% by mass, further preferably 30 to 60% by mass, and most preferably 40 to 60% by mass, relative to the total solids content of the composition. From the perspective of controlling the development time, the content of polymer P is preferably 90% by mass or less. On the other hand, from the perspective of improving edge melting resistance, the content of polymer P is preferably 10% by mass or more.

[0252] <Polymerizable Compound>

[0253] The negative photosensitive resin composition contains a polymerizable compound having a polymerizable group.

[0254] In this specification, the "polymerizable compound" refers to a compound different from the compound A and the polymer P described above.

[0255] The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction. Examples thereof include groups having ethylenically unsaturated groups such as vinyl groups, acryloyl groups, methacryloyl groups, styryl groups, and maleimide groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups.

[0256] As the polymerizable group, a group having an ethylenically unsaturated group is preferred, and an acryloyl group or a methacryloyl group is more preferred.

[0257] As the polymerizable compound, from the viewpoint of better photosensitivity of the negative photosensitive resin layer, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compounds) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compounds) is more preferred.

[0258] Furthermore, from the viewpoint of achieving better resolution and releasability, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0259] From the viewpoint of achieving a better balance between the photosensitivity, resolution, and releasability of the negative photosensitive resin layer, it is preferred that the negative photosensitive resin layer contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferred that the negative photosensitive resin layer contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.

[0260] From the perspective of excellent releasability, the content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or greater, more preferably greater than 40% by mass, and even more preferably 55% by mass or greater, relative to the total solids content of the composition. The upper limit is not particularly limited and may be 100% by mass. In other words, all polymerizable compounds may be bifunctional ethylenically unsaturated compounds.

[0261] Furthermore, as the ethylenically unsaturated compound, a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group is preferred.

[0262] (Polymerizable compound B1)

[0263] The negative photosensitive resin composition also preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.

[0264] From the perspective of achieving superior resolution, the mass ratio of the polymerizable compound B1 content relative to the total mass of the polymerizable compound in the negative photosensitive resin composition is preferably 40% or more, more preferably 50% or more, further preferably 55% or more, and particularly preferably 60% or more. The upper limit is not particularly limited, but from the perspective of releasability, it is, for example, 100% or less, preferably 99% or less, more preferably 95% or less, further preferably 90% or less, and particularly preferably 85% or less.

[0265] Examples of the aromatic ring possessed by the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring, aromatic heterocyclic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring, and condensed rings thereof. Aromatic hydrocarbon rings are preferred, and a benzene ring is more preferred. The aromatic rings may have substituents.

[0266] The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0267] From the viewpoint of improving resolution by suppressing swelling of the photosensitive resin layer due to a developer, the polymerizable compound B1 preferably has a bisphenol structure.

[0268] Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol A structure is preferred.

[0269] 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.

[0270] The two polymerizable groups at both ends of the bisphenol structure may be bonded directly or through one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, with ethyleneoxy being more preferred. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, and more preferably 6 to 14, per molecule.

[0271] The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in the publication are incorporated into the present specification.

[0272] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane is more preferred.

[0273] Examples of 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydodeethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methacryloyloxypentadecethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.). Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0274] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0275] [Chemical Formula 12]

[0276]

[0277] In the general formula B1, R1 and R2 each independently represent a hydrogen atom or a methyl group. A represents C2H4. B represents C3H6. n1 and n3 each independently represent an integer from 1 to 39, and n1+n3 represents an integer from 2 to 40. n2 and n4 each independently represent an integer from 0 to 29, and n2+n4 represents an integer from 0 to 30. The constituent units of -(AO)- and -(BO)- may be arranged randomly or in blocks. In the case of blocks, both -(A-0)- and -(B-0)- may be on the biphenyl side.

[0278] In one embodiment, n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12. Furthermore, n2+n4 is preferably 0 to 10, more preferably 0 to 4, even more preferably 0 to 2, and particularly preferably 0.

[0279] The polymerizable compound B1 may be used alone or in combination of two or more.

[0280] From the perspective of achieving better resolution, the content of polymerizable compound B1 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total solids content of the composition. The upper limit is not particularly limited, but from the perspective of transferability and edge melting (a phenomenon in which the photosensitive resin oozes out from the edges of the transfer film), it is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0281] The negative photosensitive resin composition may contain a polymerizable compound other than the above-mentioned polymerizable compound B1.

[0282] The polymerizable compounds other than polymerizable compound B1 are not particularly limited and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), bifunctional ethylenically unsaturated compounds without an aromatic ring, and trifunctional or higher ethylenically unsaturated compounds.

[0283] Examples of the monofunctional ethylenically unsaturated compound 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.

[0284] Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, polyurethane di(meth)acrylate, and trimethylolpropane diacrylate.

[0285] Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

[0286] Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

[0287] Examples of polyurethane di(meth)acrylates include propylene oxide-modified polyurethane di(meth)acrylates and ethylene oxide- and propylene oxide-modified polyurethane di(meth)acrylates. Examples of commercially available products include 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO., LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0288] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentatriol (tri / tetra / penta / hexa) (meth)acrylate, pentatriol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, and alkylene oxide-modified products thereof.

[0289] Here, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0290] In one embodiment, the negative photosensitive resin composition also preferably contains the aforementioned polymerizable compound B1 and a trifunctional or higher-functional ethylenically unsaturated compound, and more preferably contains the aforementioned polymerizable compound B1 and two or more trifunctional or higher-functional ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher-functional ethylenically unsaturated compound is preferably (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher-functional ethylenically unsaturated compound) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

[0291] Furthermore, in one embodiment, the negative photosensitive resin composition preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.

[0292] Examples of the alkylene oxide-modified trifunctional or higher ethylenically unsaturated compound include caprolactone-modified (meth)acrylate compounds (such as KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd. and ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. and EBECRYL (registered trademark) 135 manufactured by Dai-Cell-Allnex Ltd.), ethoxylated glycerol triacrylate (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and ARONIX (registered trademark) TO-2349 (Toagosei CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.) and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.).

[0293] Furthermore, as the polymerizable compound, a polymerizable compound having an acid group (such as a carboxyl group) can be used. The acid group can form an acid anhydride group. Examples of polymerizable compounds 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.).

[0294] As the polymerizable compound having an acid group, for example, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

[0295] The polymerizable compound may be used alone or in combination of two or more.

[0296] The content of the polymerizable compound is preferably 10 to 70 mass %, more preferably 15 to 70 mass %, further preferably 20 to 70 mass %, particularly preferably 20 to 60 mass %, and most preferably 20 to 50 mass % relative to the total solid content of the composition.

[0297] The molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0298] <Polymerization Initiator>

[0299] The negative photosensitive resin composition also preferably contains a polymerization initiator.

[0300] The polymerization initiator can be selected according to the form of the polymerization reaction, and examples thereof include thermal polymerization initiators and photopolymerization initiators.

[0301] The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0302] The negative photosensitive resin composition preferably contains a photopolymerization initiator.

[0303] The photopolymerization initiator is a compound that receives actinic radiation such as ultraviolet rays, visible rays, and x-rays to initiate polymerization of a polymerizable compound. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0304] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0305] Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

[0306] Furthermore, from the perspectives of photosensitivity, visibility of the exposed and non-exposed areas, and resolution, the photosensitive resin layer preferably contains at least one selected from 2,4,5-triarylimidazole dimers and derivatives thereof as a photoradical polymerization initiator. Furthermore, the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different.

[0307] Examples of the derivatives of 2,4,5-triaryl imidazole dimers include 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.

[0308] As the photoradical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-095716 and paragraphs 0064 to 0081 of JP-A-2015-014783 can be used.

[0309] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, methoxyphenyl (p,p'-dimethoxybenzyl ester), TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, and OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0310] Examples of commercially available photoradical polymerization 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-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), and 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 BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1-one (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-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), an oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Management Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Research Inc.), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Institute of Technology) Chemical Industry Co., Ltd.manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd. Rials CO., LTD.).

[0311] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid upon exposure to actinic radiation. Preferred photocationic polymerization initiators are compounds that generate an acid upon exposure to actinic radiation having a wavelength of 300 nm or longer, preferably 300 to 450 nm, but their chemical structure is not particularly limited. Furthermore, photocationic polymerization initiators that are not directly sensitive to actinic radiation having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer if they generate an acid upon exposure to actinic radiation having a wavelength of 300 nm or longer.

[0312] As the photocationic polymerization initiator, one that generates an acid with a pKa of 4 or less is preferred, one that generates an acid with a pKa of 3 or less is more preferred, and one that generates an acid with a pKa of 2 or less is particularly preferred. The lower limit of the pKa is not particularly limited, but is preferably -10.0 or greater, for example.

[0313] Examples of the photocationic polymerization initiator include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

[0314] Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

[0315] As the ionic photocationic polymerization initiator, those described in paragraphs 0114 to 0133 of JP-A-2014-085643 can be used.

[0316] Examples of nonionic photocationic polymerization initiators include trichloromethyl-symmetrical triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Trichloromethyl-symmetrical triazines, diazomethane compounds, and imide sulfonate compounds may be those described in paragraphs 0083 to 0088 of JP-A-2011-221494. Oxime sulfonate compounds may be those described in paragraphs 0084 to 0088 of WO-2018 / 179640.

[0317] Examples of the photocationic polymerization initiator (photoacid generator) include the photoacid generators described in the description of the photosensitive resin composition and the photoacid generators described in the description of the thermoplastic resin composition.

[0318] The negative photosensitive resin composition preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from 2,4,5-triarylimidazole dimers and derivatives thereof.

[0319] The polymerization initiator may be used alone or in combination of two or more.

[0320] The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total solids content of the composition. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total solids content of the composition.

[0321] <Pigment>

[0322] From the perspective of visibility of the exposed and unexposed areas, pattern visibility after development, and resolution, it is also preferred that the negative photosensitive resin composition contain a dye (also referred to as "dye N") having a maximum absorption wavelength of 450 nm or longer within the wavelength range of 400 to 780 nm during color development and whose maximum absorption wavelength is altered by acid, base, or free radicals. While the detailed mechanism of inclusion of dye N is unclear, adhesion to adjacent layers (e.g., a temporary support and an intermediate layer) is improved, resulting in better resolution.

[0323] In this specification, the "maximum absorption wavelength of a pigment is changed by an acid, an alkali or a free radical" may refer to any one of a method in which a pigment in a color-developing state is decolorized by an acid, an alkali or a free radical, a method in which a pigment in a decolorized state is colored by an acid, an alkali or a free radical, and a method in which a pigment in a color-developing state is changed to a color-developing state of another hue.

[0324] Specifically, the pigment N can be a compound that develops color by changing from a bleached state through exposure, or a compound that changes from a developed state through exposure to discolor. In this case, it can be a pigment that generates an acid, base, or free radical in the photosensitive resin layer through exposure and acts to change the state of color development or discoloration, or it can be a pigment that changes the state of color development or discoloration by changing the state (e.g., pH) in the photosensitive resin layer due to an acid, base, or free radical. Furthermore, it can also be a pigment that directly accepts an acid, base, or free radical as a stimulus to change the state of color development or discoloration without exposure.

[0325] Among them, from the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.

[0326] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the negative photosensitive resin composition preferably contains both a dye N whose maximum absorption wavelength changes due to radicals and a photoradical polymerization initiator.

[0327] Furthermore, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by acid, alkali, or radicals.

[0328] As an example of the color development mechanism of the pigment N, the following method can be cited: a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive resin layer, and after exposure, the radical-reactive pigment, the acid-reactive pigment or the base-reactive pigment (for example, a colorless pigment) develops color due to the radicals, acid or base generated by the photoradical polymerization initiator, the photocationic polymerization initiator or the photobase generator.

[0329] Regarding the dye N, from the viewpoint of visibility of the exposed and non-exposed areas, the maximum absorption wavelength in the wavelength range of 400 to 780 nm during color development is preferably 550 nm or longer, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm.

[0330] Furthermore, the pigment N may have only one maximum absorption wavelength within the wavelength range of 400 to 780 nm during color development, or may have two or more. If the pigment N has two or more maximum absorption wavelengths within the wavelength range of 400 to 780 nm during color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or longer.

[0331] The maximum absorption wavelength of Dye N is obtained by measuring the transmission spectrum of a solution containing Dye N (liquid temperature 25°C) in the range of 400 to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an atmospheric atmosphere, and detecting the wavelength at which the light intensity reaches a minimum (maximum absorption wavelength).

[0332] Examples of dyes that develop or fade color by exposure include colorless compounds.

[0333] Examples of the dye that is discolored by exposure include colorless compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

[0334] As the dye N, a colorless compound is preferred from the viewpoint of visibility of the exposed portion and the non-exposed portion.

[0335] Examples of colorless compounds include colorless compounds having a triarylmethane skeleton (triarylmethane-based pigments), colorless compounds having a spiropyran skeleton (spiropyran-based pigments), colorless compounds having a fluoran parent skeleton (fluoran parent-based pigments), colorless compounds having a diarylmethane skeleton (diarylmethane-based pigments), colorless compounds having a rhodamine lactam skeleton (rhodamine lactam-based pigments), colorless compounds having an indolylphthalide lactone skeleton (indolylphthalide lactone-based pigments), and colorless compounds having a colorless auramine skeleton (colorless auramine-based pigments).

[0336] Among them, triarylmethane-based dyes or fluoran-based dyes are preferred, and colorless compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferred.

[0337] From the perspective of visibility of the exposed and non-exposed areas, the colorless compound preferably has a lactone ring, a sultine ring, or a sultone ring. Therefore, the lactone ring, sultine ring, or sultone ring of the colorless compound can react with free radicals generated by a photoradical polymerization initiator or an acid generated by a photocationic polymerization initiator, thereby converting the colorless compound to a closed-ring state and decolorizing it, or converting the colorless compound to an open-ring state and developing color. The colorless compound preferably has a lactone ring, a sultine ring, or a sultone ring, and develops color when the lactone ring, sultine ring, or sultone ring is opened by free radicals or acids. More preferably, the compound has a lactone ring, and develops color when the lactone ring is opened by free radicals or acids.

[0338] Examples of the pigment N include the following dyes and colorless compounds.

[0339] Specific examples of the dye in the pigment N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, methylquinoline red, rose bengal, meta-amino yellow, bromocarbyl blue, xylenol blue, methyl orange, p-methyl red, Congo red, phenyl red violet 4B, α-naphthyl red, Nile Blue 2B, Nile Blue A, methyl violet, malachite green, fuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Powder #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Co., Ltd.), and more. Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Co., Ltd.), SPIRON Red BEH SPECIAL (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol violet, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyphenylamino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamido-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.

[0340] Specific examples of the colorless compound in the dye N include p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco-methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran precursor, 2-phenylamino-3-methyl-6-(N-ethyl-p-tolylamino)fluoran precursor, 3,6-dimethoxyfluoran precursor, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran precursor, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-phenylamino Fluoran precursor, 3-(N,N-diethylamino)-6-methyl-7-phenylaminofluoran precursor, 3-(N,N-diethylamino)-6-methyl-7-thiocyanofluoran precursor, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran precursor, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran precursor, 3-(N,N-diethylamino)-7-(4-chlorophenylamino)fluoran precursor, 3-(N,N-diethylamino)-7-chlorofluoran precursor, 3-(N,N-diethylamino)-7-chlorofluoran precursor, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran precursor. N-diethylamino)-7-benzylaminofluoran precursor, 3-(N,N-diethylamino)-7,8-benzofluoran precursor, 3-(N,N-dibutylamino)-6-methyl-7-phenylaminofluoran precursor, 3-(N,N-dibutylamino)-6-methyl-7-phenylaminofluoran precursor, 3-piperidinyl-6-methyl-7-phenylaminofluoran precursor, 3-pyrrolidinyl-6-methyl-7-phenylaminofluoran precursor, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide lactone, 3,3- Bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

[0341] From the viewpoint of visibility of the exposed and non-exposed areas, and pattern visibility and resolution after development, the dye N is preferably a dye whose maximum absorption wavelength changes due to radicals, and more preferably a dye that develops color due to radicals.

[0342] As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate is preferred.

[0343] The dye N may be used alone or in combination of two or more.

[0344] From the viewpoint of visibility of the exposed and non-exposed areas, and pattern visibility and resolution after development, the content of the pigment N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, further preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, relative to the total solids content of the composition.

[0345] The content of pigment N refers to the content of the pigment when all the pigment N contained in the total solid content of the composition is in a colored state. The following describes a method for quantifying the content of pigment N using a pigment that develops color due to free radicals as an example.

[0346] The preparation method was to dissolve 0.001 g and 0.01 g of the pigment in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) was added to each obtained solution and irradiated with 365 nm light to generate free radicals, so that all the pigments were set to a color-developing state. Then, under an atmospheric atmosphere, a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) was used to measure the absorbance of each solution at a liquid temperature of 25° C. to create a calibration curve.

[0347] Next, the absorbance of the solution containing the entire pigment was measured using the same method as above, except that 3 g of the solid component of the composition was dissolved in methyl ethyl ketone instead of the pigment. The pigment content in the solid component of the composition was calculated using a calibration curve based on the absorbance of the solution containing the solid component of the composition obtained.

[0348] In addition, 3 g of the solid content of the composition is the same as 3 g of the layer (negative photosensitive resin layer, etc.) formed using the composition.

[0349] <Thermal Crosslinking Compound>

[0350] From the perspective of the strength of the resulting cured film and the adhesiveness of the resulting uncured film, the negative photosensitive resin composition preferably contains a thermally crosslinkable compound. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, as described below, is not considered a polymerizable compound but rather a thermally crosslinkable compound.

[0351] Examples of the heat-crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.

[0352] The blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group. Therefore, for example, when a resin and / or a polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film decreases, and the function of the film formed by curing the negative photosensitive resin layer as a protective film tends to be enhanced.

[0353] The blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) by a blocking agent."

[0354] 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.

[0355] The dissociation temperature of the blocked isocyanate refers to "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter."

[0356] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.

[0357] Examples of the end-capping agent having a dissociation temperature of 100 to 160° C. include active methylene compounds [malonic acid diesters (such as dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate)] and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, which have a structure represented by -C(=N-OH)- in the molecule).

[0358] Among these, as the blocking agent having a dissociation temperature of 100 to 160° C., for example, at least one selected from oxime compounds is preferred from the viewpoint of storage stability.

[0359] For example, from the viewpoints of improving the brittleness of the film, enhancing the adhesion to the transfer target, and the like, the blocked isocyanate compound preferably has an isocyanurate structure.

[0360] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating and protecting hexamethylene diisocyanate.

[0361] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure having an oxime compound as a blocking agent are preferred from the viewpoints of easily setting the dissociation temperature within a preferred range and easily reducing development residues compared to compounds not having an oxime structure.

[0362] The blocked isocyanate compound may have a polymerizable group.

[0363] The polymerizable group is not particularly limited, and a known polymerizable group can be used, but a radical polymerizable group is preferred.

[0364] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0365] Among these, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0366] As the blocked isocyanate compound, a commercially available product can be used.

[0367] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and blocked DURANATE series (for example, DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

[0368] Furthermore, as the blocked isocyanate compound, compounds having the following structures can also be used.

[0369] [Chemical Formula 13]

[0370]

[0371] The heat-crosslinkable compound may be used alone or in combination of two or more.

[0372] When the negative photosensitive resin composition contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total solid content of the composition.

[0373] <Solvent>

[0374] The negative photosensitive resin composition also preferably contains a solvent.

[0375] The solvent contained in the negative photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the components other than the solvent (compound A and / or polymer P, etc.), and a known solvent can be used.

[0376] Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and mixed solvents containing two or more of these.

[0377] When producing a transfer film comprising a temporary support, a thermoplastic resin layer, an intermediate layer (water-soluble resin layer), and a negative-type photosensitive resin layer, the negative-type photosensitive resin composition preferably contains at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent comprising at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from ketone solvents and cyclic ether solvents is more preferred. A mixed solvent comprising at least one solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0378] Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

[0379] Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

[0380] As the solvent, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and the solvents described in paragraph 0014 of Japanese Patent Application Laid-Open No. 2018-177889 can be used, and these contents are incorporated into this specification.

[0381] One solvent may be used alone, or two or more solvents may be used.

[0382] The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1,200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0383] <Additives>

[0384] The negative photosensitive resin composition may contain known additives as needed in addition to the above components.

[0385] Examples of the additives include radical inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazole), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants.

[0386] Each additive may be used alone or in combination of two or more.

[0387] The negative photosensitive resin composition may contain a radical polymerization inhibitor.

[0388] Examples of free radical inhibitors include the thermal inhibitors described in paragraph 0018 of Japanese Patent Gazette No. 4502784. Among these, preferred are morphothiazine, morphooxazine, or 4-methoxyphenol. Other free radical inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosoamine. To prevent the sensitivity of the negative-type photosensitive resin layer from being compromised, nitrosophenylhydroxylamine aluminum salt is preferably used as the free radical inhibitor.

[0389] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0390] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of the carboxybenzotriazoles include commercially available products such as CBT-1 (trade name, JOHOKU CHEMICAL CO., LTD.).

[0391] When the total solid content of the composition is set to 100% by mass, the total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. From the perspective of imparting storage stability to the composition, the content is preferably set to 0.01% by mass or more. On the other hand, from the perspective of maintaining sensitivity and suppressing dye discoloration, the content is preferably set to 3% by mass or less.

[0392] The negative photosensitive resin composition may contain a sensitizer.

[0393] There are no particular limitations on the sensitizer, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

[0394] The sensitizer may be used alone or in combination of two or more.

[0395] When the negative photosensitive resin composition contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving sensitivity to light sources and improving the curing speed based on the balance between polymerization rate and chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive resin layer.

[0396] The negative photosensitive resin composition may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.

[0397] Examples of the plasticizer and heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0398] Furthermore, the negative photosensitive resin composition may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents.

[0399] Additives contained in the negative photosensitive resin composition are described in paragraphs 0165 to 0184 of JP-A-2014-085643, the contents of which are incorporated into this specification.

[0400] From the viewpoint of improving reliability and lamination properties, the water content in the negative photosensitive resin composition is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0401] <Physical Properties of the Formed Layer>

[0402] The coating method of the negative photosensitive resin composition is not particularly limited, and it can be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0403] Furthermore, a composition layer (negative photosensitive resin layer) formed using a negative photosensitive resin composition can be formed by applying the negative photosensitive resin composition on a coating object such as a cover film described later and drying the coating object.

[0404] The thickness of the negative photosensitive resin layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, further preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm. Therefore, the developability of the negative photosensitive resin layer is improved, thereby enabling higher resolution.

[0405] Furthermore, in one embodiment, the thickness is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and even more preferably 0.5 to 3 μm.

[0406] Furthermore, from the viewpoint of better adhesion, the transmittance of the negative photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

[0407] (impurities, etc.)

[0408] The negative photosensitive resin layer formed using the negative photosensitive resin composition may contain a predetermined amount of impurities.

[0409] Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily incorporated as impurities, and therefore are preferably set to the following contents.

[0410] The impurity content in the negative photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less, based on mass. The impurity content can be 1 ppb or more, or 0.1 ppm or more, based on mass.

[0411] Methods for keeping impurities within the above range include: selecting raw materials for the composition with low impurity content; preventing impurities from entering during the production of the negative photosensitive resin layer; and removing them by washing. These methods can keep the impurity content within the above range.

[0412] Impurities can be quantified by, for example, a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0413] The negative photosensitive resin layer preferably contains a low content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane. The content of these compounds relative to the total mass of the composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.

[0414] The lower limit can be set to 10 ppb or greater, and can be set to 100 ppb or greater, based on mass, relative to the total mass of the negative photosensitive resin layer. The content of these compounds can be suppressed using the same methods as for the aforementioned metal impurities. Furthermore, their quantification can be performed using known measurement methods.

[0415] From the viewpoint of improving reliability and lamination properties, the water content in the negative photosensitive resin layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass.

[0416] [Thermoplastic resin composition]

[0417] The composition of the present invention may be a thermoplastic resin composition capable of forming a thermoplastic resin layer.

[0418] The thermoplastic resin layer is preferably formed between the temporary support and the photosensitive resin layer in a transfer film including a temporary support and a photosensitive resin layer (such as a layer containing the negative photosensitive resin composition), for example.

[0419] The transfer film has a thermoplastic resin layer between the temporary support and the photosensitive resin layer, so the followability of the transfer film to the substrate in the bonding process is improved, the mixing of bubbles between the substrate and the transfer film is suppressed, and the adhesion with the adjacent layer (such as the temporary support) can be improved.

[0420] The thermoplastic resin composition of the present invention is a composition in which the alkali-soluble resin in the composition is a thermoplastic resin. In addition, the thermoplastic resin composition of the present invention may contain other thermoplastic resins in addition to the alkali-soluble resin as the thermoplastic resin.

[0421] In addition, hereinafter, an alkali-soluble resin as a thermoplastic resin may be referred to as an "alkali-soluble thermoplastic resin".

[0422] That is, the composition of the present invention may be a thermoplastic resin composition containing compound A, an alkali-soluble thermoplastic resin, and a polymerizable compound.

[0423] <Alkali-soluble thermoplastic resin>

[0424] Examples of the alkali-soluble thermoplastic resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formaldehyde, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycol.

[0425] As the alkali-soluble thermoplastic resin, acrylic resin is preferred from the viewpoint of developability and adhesion to an adjacent layer.

[0426] Here, the acrylic resin refers to a resin having at least one structural unit selected from the group consisting of a structural unit derived from (meth)acrylic acid, a structural unit derived from (meth)acrylate, and a structural unit derived from (meth)acrylamide.

[0427] The acrylic resin preferably contains a total content of 50% by mass or more of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate, and structural units derived from (meth)acrylamide relative to the total mass of the acrylic resin.

[0428] The total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylate is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, relative to the total mass of the acrylic resin.

[0429] Furthermore, the alkali-soluble thermoplastic resin is preferably a polymer having an acid group.

[0430] Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferred.

[0431] From the viewpoint of developability, the alkali-soluble thermoplastic resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and is even more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more.

[0432] The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, further preferably 200 mgKOH / g or less, and particularly preferably 150 mgKOH / g or less.

[0433] The carboxyl 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.

[0434] For example, the alkali-soluble resin containing a carboxyl group and having an acid value of 60 mgKOH / g or more in the polymer described in paragraph 0025 of JP-A-2011-095716, the carboxyl group-containing acrylic resin containing a carboxyl group and having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs 0033 to 0052 of JP-A-2010-237589, and the carboxyl group-containing acrylic resin containing a carboxyl group and having an acid value of 60 mgKOH / g or more in the binder polymer described in paragraphs 0053 to 0068 of JP-A-2016-224162 can be cited.

[0435] The copolymerization ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and further preferably 12 to 30 mass %, relative to the total mass of the acrylic resin.

[0436] As the alkali-soluble thermoplastic resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred from the viewpoint of developability and adhesion to an adjacent layer.

[0437] The alkali-soluble thermoplastic resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples thereof include ethylenically unsaturated groups; condensation-polymerizable groups such as hydroxyl and carboxyl groups; and polyaddition-reactive groups such as epoxy and (blocked) isocyanate groups.

[0438] The weight average molecular weight (Mw) of the alkali-soluble thermoplastic resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 50,000.

[0439] The alkali-soluble thermoplastic resin may be used alone or in combination of two or more.

[0440] From the viewpoint of developability and adhesion to adjacent layers, the content of the alkali-soluble thermoplastic resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, further preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass relative to the total solid content of the composition.

[0441] <Pigment>

[0442] The thermoplastic resin layer preferably contains a pigment (also referred to as "pigment B") having a maximum absorption wavelength of 450 nm or longer in the wavelength range of 400 to 780 nm during color development and whose maximum absorption wavelength is changed by acid, base, or radical.

[0443] Preferred aspects of the dye B are the same as preferred aspects of the dye N described above, except for the points described below.

[0444] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye B is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, and more preferably a dye whose maximum absorption wavelength is changed by acid.

[0445] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the thermoplastic layer preferably contains, as the dye B, both a dye whose maximum absorption wavelength is changed by acid and a compound that generates acid by light, as described later.

[0446] The pigment B may be used alone or in combination of two or more.

[0447] From the viewpoint of visibility of the exposed and non-exposed areas, the content of the pigment B is preferably 0.2% by mass or more, more preferably 0.2 to 6% by mass, further preferably 0.2 to 5% by mass, and particularly preferably 0.25 to 3.0% by mass, relative to the total solids content of the composition.

[0448] Here, the content of the pigment B refers to the content of the pigment when all the pigment B contained in the thermoplastic resin layer is in a colored state. The following describes a method for quantifying the content of the pigment B, taking a pigment that develops color by radicals as an example.

[0449] The preparation method comprises dissolving 0.001 g and 0.01 g of the pigment in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) is added to each obtained solution and irradiated with 365 nm light to generate free radicals, thereby making all the pigments into a color-developing state. Then, under an atmospheric atmosphere, a spectrophotometer (UV3100, manufactured by SHIMADZU CORPORATION) is used to measure the absorbance of each solution at a liquid temperature of 25° C. to prepare a calibration curve.

[0450] Next, the absorbance of the solution containing the entire pigment was measured using the same method as above, except that 0.1 g of the solid component of the composition was dissolved in methyl ethyl ketone instead of the pigment. The amount of pigment contained in the solid component of the composition was calculated using a calibration curve based on the absorbance of the solution containing the solid component of the composition thus obtained.

[0451] The solid content of 3 g of the composition is the same as 3 g of the layer (thermoplastic resin layer, etc.) formed using the composition.

[0452] <Compounds that generate acids, bases, or free radicals upon exposure to light>

[0453] The thermoplastic resin composition may contain a compound that generates an acid, a base, or a radical by light (also referred to simply as "compound C").

[0454] Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic radiation such as ultraviolet rays and visible rays.

[0455] Known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used as compound C. Among them, photoacid generators are preferred.

[0456] (Photoacid generator)

[0457] From the viewpoint of resolution, the thermoplastic resin composition preferably contains a photoacid generator.

[0458] Examples of the photoacid generator include the photocationic polymerization initiator that may be contained in the negative photosensitive resin composition. Preferred embodiments are also the same except for the points described below.

[0459] The photoacid generator preferably contains at least one compound selected from an onium salt compound and an oxime sulfonate compound from the viewpoints of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.

[0460] Furthermore, as the photoacid generator, a photoacid generator having the following structure is also preferable.

[0461] [Chemical Formula 14]

[0462]

[0463] (Photoradical polymerization initiator)

[0464] The thermoplastic resin composition may contain a photoradical polymerization initiator.

[0465] Examples of the photoradical polymerization initiator include the photoradical polymerization initiator that may be contained in the above-mentioned negative photosensitive resin composition, and preferred embodiments are also the same.

[0466] (Photobase Generator)

[0467] The thermoplastic resin composition may contain a photobase generator.

[0468] The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, trityl alcohol, O-carbamoylhydroxyamide, 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)-1,6-diamine, -benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(tritylborate), 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.

[0469] Compound C may be used alone or in combination of two or more.

[0470] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the content of the compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total solid content of the composition.

[0471] <Plasticizer>

[0472] The thermoplastic resin composition preferably contains a plasticizer from the viewpoints of the resolution of the composition layer (thermoplastic resin layer) to be formed, adhesion to an adjacent layer, and developability.

[0473] The plasticizer preferably has a molecular weight (weight average molecular weight when it is an oligomer or polymer having a molecular weight distribution) smaller than that of the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.

[0474] The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble thermoplastic resin and exhibits plasticizing properties. From the perspective of imparting plasticizing properties, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethylene oxide structure or a polypropylene oxide structure.

[0475] Furthermore, from the perspectives of resolution and storage stability, the plasticizer preferably comprises a (meth)acrylate compound. From the perspectives of compatibility, resolution, and adhesion to adjacent layers, it is more preferred that the alkali-soluble resin is an acrylic resin and the plasticizer comprises a (meth)acrylate compound.

[0476] As a (meth)acrylate compound which can be used as a plasticizer, the (meth)acrylate compound described as the polymerizable compound contained in the said negative photosensitive resin composition is mentioned.

[0477] In a transfer film, when a thermoplastic resin layer and a negative photosensitive resin layer are laminated in direct contact, it is preferred that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the negative photosensitive resin layer contain the same (meth)acrylate compound, diffusion of components between the layers is suppressed, thereby improving storage stability.

[0478] When the thermoplastic resin composition contains a (meth)acrylate compound as a plasticizer, it is preferred that the (meth)acrylate compound is not polymerized even in the exposed portion after exposure from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer.

[0479] Furthermore, as the (meth)acrylate compound that can be used as a plasticizer, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

[0480] Furthermore, as the (meth)acrylate compound that can be used as the plasticizer, a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group is also preferred.

[0481] The plasticizer may be used alone or in combination of two or more.

[0482] From the viewpoint of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass relative to the total solid content of the composition.

[0483] <Sensitizer>

[0484] The thermoplastic resin composition may contain a sensitizer.

[0485] The sensitizer is not particularly limited, and examples thereof include the sensitizers that can be contained in the above-mentioned negative photosensitive resin layer.

[0486] The sensitizer may be used alone or in combination of two or more.

[0487] The content of the sensitizer can be appropriately selected depending on the purpose, but is preferably 0.01 to 5 mass %, more preferably 0.05 to 1 mass % based on the total solid content of the composition from the viewpoint of improving sensitivity to the light source and visibility of the exposed and non-exposed areas.

[0488] <Solvent>

[0489] The thermoplastic resin composition may contain a solvent.

[0490] The solvent is not particularly limited, and examples thereof include the solvents that can be contained in the above-mentioned negative photosensitive resin layer.

[0491] The thermoplastic resin composition also preferably contains at least one solvent selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates.

[0492] The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0493] <Additives, etc.>

[0494] The thermoplastic resin composition may contain known additives as needed in addition to the above-mentioned components.

[0495] The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-085643, and the contents described in this publication are incorporated into this specification.

[0496] <Physical Properties of the Formed Layer>

[0497] The thickness of the layer formed using the thermoplastic resin composition (thermoplastic resin layer) is not particularly limited, but is preferably 1 μm or greater, more preferably 2 μm or greater, from the perspective of adhesion to adjacent layers. The upper limit is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less, from the perspective of developability and resolution.

[0498] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method that can form a layer containing the above-mentioned components.

[0499] There can be mentioned a method of forming the thermoplastic resin composition by applying the thermoplastic resin composition on the surface of a temporary support or the like and drying the coating film of the thermoplastic resin composition.

[0500] Furthermore, after forming a photosensitive resin layer and an intermediate layer on a cover film described later, a thermoplastic resin layer may be formed on the surface of the intermediate layer.

[0501] [Colored resin composition]

[0502] The composition of the present invention can also be used as a colored resin composition.

[0503] In recent years, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached to a liquid crystal display window of an electronic device to protect the liquid crystal display window. Such a light-shielding layer can be formed using a coloring composition.

[0504] The colored resin composition is a composition containing a pigment.

[0505] That is, the composition of the present invention may be a colored resin composition containing a pigment in addition to compound A, an alkali-soluble resin, and a polymerizable compound. The composition of the present invention as a colored resin composition also preferably contains a polymerization initiator in addition to compound A, an alkali-soluble resin, a polymerizable compound, and a pigment.

[0506] <Pigment>

[0507] The pigment contained in the colored resin composition can be appropriately selected according to the desired hue and can be selected from black pigments, white pigments, and color pigments other than black and white. In particular, when forming a black pattern, a black pigment is preferably selected as the pigment.

[0508] As black pigment, as long as in the scope of not damaging effect of the present invention, then can suitably select known black pigment (organic pigment or inorganic pigment etc.).Wherein, with regard to the viewpoint of optical density, as black pigment, for example, can preferably enumerate carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide and black lead etc., especially preferred carbon black.As carbon black, with regard to the viewpoint of surface resistance, preferably at least a portion of surface is resin-coated carbon black.

[0509] The black pigment (preferably carbon black) is preferably used in the form of a pigment dispersion.

[0510] The dispersion can be prepared by adding a mixture obtained by pre-mixing a black pigment and a pigment dispersant to an organic solvent (or carrier) and dispersing it using a disperser. The pigment dispersant can be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used. In addition, the carrier refers to the part of the medium in which the pigment is dispersed in the case of a pigment dispersion, and 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.

[0511] As dispersion machine, there is no particular limitation, for example, known dispersion machines such as kneader, roller mill, attritor, super mill, dissolver, homomixer and sand mixer can be enumerated. And then, friction force can be utilized to carry out fine grinding by mechanical grinding. About dispersion machine and fine grinding, can refer to the record of " Encyclopedia of Pigment " (written by Asakura Bangzao, first edition, Asakura Publishing Co., Ltd., 2000, 438 pages, 310 pages).

[0512] The particle size of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm in terms of number average particle size, from the viewpoint of dispersion stability.

[0513] Here, the particle size refers to the diameter of a circle obtained by calculating the area of the pigment particles from a photograph of the pigment particles taken with an electron microscope and taking into account a circle with the same area as the area of the pigment particles. The number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes thus calculated.

[0514] As pigments other than black pigments, white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Laid-Open No. 2005-007765 can be used. Specifically, inorganic pigments among white pigments are 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, and even more preferably titanium oxide. As inorganic pigments, rutile or anatase titanium oxide is more preferably, and rutile titanium oxide is particularly preferred.

[0515] Furthermore, the surface of titanium oxide can be treated with silica, alumina, titania, zirconia, or an organic substance, or with two or more of these treatments. This can suppress the catalytic activity of titanium oxide and improve its heat resistance and matte properties.

[0516] From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of an alumina treatment and a zirconia treatment, and particularly preferably both an alumina treatment and a zirconia treatment.

[0517] Furthermore, from the perspective of transferability, the colored resin composition preferably also contains a color pigment in addition to the black pigment and the white pigment. When containing a color pigment, it is desirable that the color pigment be well dispersed in the colored resin layer. From this perspective, the particle size is preferably 0.1 μm or less, and more preferably 0.08 μm or less.

[0518] As color pigments, for example, Victoria Pure Blue BO (Color Index: Color Index (hereinafter referred to as CI) 42595), Auramine (CI41000), Fat Black HB (CI26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Magenta FBB (CI Pigment Red 146), Master Yeast Red ESB (CI Pigment Violet 19), Permanent Gemstone FBH (CI Pigment Red 11), Gouache B Supra (CI Pigment Red 81), Monash Blue (CI Pigment Blue 15), Monolight Black B (CI Pigment Black 1) and Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64 and CI Pigment Violet 23, etc. Among them, CI Pigment Red 177 is preferred.

[0519] The content of the pigment is preferably greater than 3% by mass and less than 40% by mass, more preferably greater than 3% by mass and less than 35% by mass, further preferably greater than 5% by mass and less than 35% by mass, and particularly preferably greater than 10% by mass and less than 35% by mass, relative to the total solid content of the composition.

[0520] When pigments other than the black pigment (white pigment and color pigment) are contained, the content is preferably 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass relative to the black pigment.

[0521] A pigment may be added to each of the above compositions to prepare a colored resin composition.

[0522] For example, as described above, the negative photosensitive resin composition may contain a pigment (or pigment dispersion) as a colored resin composition. That is, the negative photosensitive resin composition may be a colored resin composition.

[0523] Likewise, each of the above-mentioned composition layers may be a colored resin layer to which a pigment is added.

[0524] For example, as described above, the negative photosensitive resin layer may be a colored resin layer containing a pigment. In other words, the negative photosensitive resin layer may be a colored resin layer.

[0525] <Physical Properties of the Formed Layer>

[0526] The method for coating the composition using the colored resin composition and / or the method for forming the composition layer are not particularly limited, and can be performed in the same manner as in the method using the negative photosensitive resin composition, for example.

[0527] The thickness (film thickness) of the composition layer (colored resin layer) formed using the colored resin composition is usually 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, further preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm.

[0528] [Transfer film]

[0529] The invention also relates to a transfer film.

[0530] The transfer film of the present invention comprises a temporary support and one or more composition layers (eg, 1 to 5 layers). In the transfer film, at least one of the composition layers is formed using the composition of the present invention (composition layer).

[0531] In the transfer film, the temporary support and the one or more composition layers may be directly laminated without or with other layers interposed therebetween. Furthermore, the other layer may be laminated on the surface of the one or more composition layers opposite to the surface facing the temporary support. Other layers may also be present between the one or more composition layers.

[0532] The composition layer is a layer containing a resin, and may be a layer (composition layer) formed using the composition of the present invention, or may be a layer (composition layer) formed using a composition other than the present invention that does not conform to the composition of the present invention (such as the "composition not containing an alkali-soluble resin, a polymerizable compound, and compound A" described later).

[0533] Hereinafter, a layer formed using the composition of the present invention (composition layer) is also referred to as a "composition layer of the present invention."

[0534] Furthermore, a layer (composition layer) formed using a composition other than the present invention (such as the "composition not containing an alkali-soluble resin, a polymerizable compound, and compound A" described later) that does not conform to the present invention is also referred to as a "composition layer other than the present invention."

[0535] In the transfer film, at least one of the one or more (e.g., 1 to 5) composition layers may be the composition of the present invention. Half or more of the layers may be the composition of the present invention, or all the layers may be the composition of the present invention.

[0536] The composition layer of the present invention is, for example, a layer comprising only the solid content of the composition of the present invention. More specifically, the composition layer of the present invention is, for example, a layer (negative photosensitive resin layer, thermoplastic resin layer, and / or colored resin layer) comprising only the solid content of the negative photosensitive resin composition, thermoplastic resin composition, and / or colored resin composition.

[0537] The term "containing only solid components" herein means containing substantially only solid components, and the solid content is preferably 95 to 100% by mass, more preferably 99 to 100% by mass, and even more preferably 99.5 to 100% by mass relative to the total mass of the composition layer.

[0538] Composition layers other than those of the present invention are, for example, composition layers formed using a "composition that does not contain an alkali-soluble resin, a polymerizable compound, and Compound A" in the negative photosensitive resin composition, thermoplastic resin composition, and / or colored resin composition. Such composition layers preferably consist solely of the solid content of the "composition that does not contain an alkali-soluble resin, a polymerizable compound, and Compound A." Examples of the "composition that does not contain an alkali-soluble resin, a polymerizable compound, and Compound A" include compositions obtained by simply removing Compound A from the composition of the present invention and compositions in which Compound A in the composition of the present invention is replaced with a surfactant that is incompatible with Compound A.

[0539] Hereinafter, the negative photosensitive resin composition of the present invention and a composition that does not contain an alkali-soluble resin, a polymerizable compound, and Compound A will be distinguished and referred to as the negative photosensitive resin composition of the present invention and a negative photosensitive resin composition other than the negative photosensitive resin composition of the present invention, respectively. The same applies to other types of compositions.

[0540] Furthermore, a layer formed using the negative photosensitive resin composition of the present invention and a layer formed using a negative photosensitive resin composition other than the present invention are distinguished and are also referred to as the negative photosensitive resin layer of the present invention and the negative photosensitive resin composition other than the present invention, respectively. The same applies to other types of composition layers.

[0541] The transfer film of the present invention also preferably includes at least one negative photosensitive resin layer (the negative photosensitive resin layer of the present invention or a negative photosensitive resin layer other than the negative photosensitive resin layer of the present invention). The negative photosensitive resin layer may be a colored resin layer.

[0542] That is, it is preferred that at least one of the composition layers (one or more composition layers) of the transfer film of the present invention is a negative photosensitive resin layer (the negative photosensitive resin layer of the present invention or a negative photosensitive resin layer other than the present invention).

[0543] Temporary support

[0544] The transfer film of the present invention has a temporary support.

[0545] The temporary support is a peelable support that supports the composition layer or a laminate including the composition layer.

[0546] The temporary support preferably has light transparency in order to enable exposure via the temporary support during pattern exposure of the composition layer. In this specification, “light transparency” means that the transmittance of light of the wavelength used in pattern exposure is 50% or higher.

[0547] The temporary support preferably has a transmittance of light of a wavelength (more preferably a wavelength of 365 nm) used for pattern exposure of 60% or more, more preferably 70% or more, from the viewpoint of improving exposure sensitivity.

[0548] The transmittance of the layer of the transfer film is the ratio of the intensity of the outgoing light emitted through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using an MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0549] Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper. From the viewpoint of strength, flexibility, and light transmittance, a resin film is preferred.

[0550] Examples of the resin film include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, PET films are preferred, and biaxially stretched PET films are more preferred.

[0551] There is no particular limitation on the thickness (layer thickness) of the temporary support. It can be selected based on the material from the perspectives of the strength of the support, the flexibility required for bonding to the circuit wiring forming substrate, and the light transmittance required for the first exposure process.

[0552] The thickness of the temporary support is preferably 5 to 100 μm, more preferably 10 to 50 μm, further preferably 10 to 20 μm, and particularly preferably 10 to 16 μm from the viewpoint of ease of handling and versatility.

[0553] Furthermore, it is preferred that the film used as a temporary support body does not have deformation such as wrinkles, scratches, or defects.

[0554] From the perspective of pattern formation when pattern exposure is performed via a temporary support and the transparency of the temporary support, it is preferred that the number of particles, foreign matter, defects, and precipitates contained in the temporary support is small. The number of particles, foreign matter, and defects with a diameter of 1 μm or more is preferably 50 / 10 mm. 2 Less than 10 / 10mm, more preferably 10 / 10mm 2 Below, more preferably 3 / 10mm 2 Below, particularly preferably 0 / 10mm 2 .

[0555] Preferred forms of temporary support bodies are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Publication No. 2014-085643, paragraphs 0019 to 0026 of Japanese Patent Publication No. 2016-027363, paragraphs 0041 to 0057 of WO2012 / 081680A1, paragraphs 0029 to 0040 of WO2018 / 179370A1, and paragraphs 0012 to 0032 of Japanese Patent Publication No. 2019-101405, and the contents of these publications are incorporated into this specification.

[0556] [Covering film]

[0557] The transfer film preferably has a cover film in contact with the surface of the composition layer (the one or more composition layers) that does not face the temporary support.

[0558] Hereinafter, in this specification, the surface of the composition layer facing the temporary support is also referred to as the "first surface", and the surface opposite to the first surface is also referred to as the "second surface".

[0559] Examples of the material constituting the cover film include resin films and paper. From the viewpoint of strength and flexibility, resin films are preferred.

[0560] Examples of the resin film include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, polyethylene films, polypropylene films, and polyethylene terephthalate films are preferred.

[0561] The thickness (layer thickness) of the cover film is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 50 μm.

[0562] Furthermore, from the perspective of achieving even better resolution, the arithmetic mean roughness Ra value of the surface of the cover film in contact with the composition layer (hereinafter referred to as the "cover film surface") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less. This is believed to be because the Ra value of the cover film surface within the above range improves the uniformity of the thickness of the formed resin pattern.

[0563] The lower limit of the Ra value of the coating surface is not particularly limited, but is preferably 0.001 μm or more.

[0564] The Ra value of the cover film surface can be measured by the following method.

[0565] The surface of the cover film was measured using a three-dimensional optical profiler (New View 7300, manufactured by Zygo Corporation) under the following conditions to obtain the surface profile of the optical film.

[0566] The measurement / analysis software used was the Microscope Application in MetroPro version 8.3.2. Next, the Surface Map screen was displayed using the analysis software, and histogram data was obtained from the Surface Map screen. The arithmetic mean roughness was calculated from the obtained histogram data to obtain the Ra value of the film surface.

[0567] When the cover film and the transfer film are bonded together, the cover film may be peeled off from the transfer film, and the Ra value of the surface on the peeled side may be measured.

[0568] [Method for manufacturing transfer film]

[0569] The method for producing the transfer film of the present invention is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.

[0570] Below, reference Figure 1 , the method for producing the transfer film of the present invention will be described. However, the transfer film of the present invention is not limited to the one having Figure 1 The structure shown in .

[0571] Figure 1 This is a schematic diagram showing an example of the structure of the transfer film of the present invention. Figure 1 The transfer film 100 shown in FIG. 1 has a structure in which a temporary support 10 , a thermoplastic resin layer 12 , an intermediate layer 14 , a negative photosensitive resin layer 16 , and a cover film 18 are stacked in this order.

[0572] Furthermore, since the transfer film includes the intermediate layer 14 , mixing of components during coating of multiple layers and during storage after coating can be suppressed.

[0573] The intermediate layer may be an oxygen barrier layer having an oxygen barrier function, as described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-072724. An oxygen barrier layer is preferred because it improves sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity.

[0574] The oxygen barrier layer that can be used as the intermediate layer can be appropriately selected from known layers described in the aforementioned publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersible or soluble in water or an alkaline aqueous solution (a 1 mass % aqueous solution of sodium carbonate at 22°C) is preferred.

[0575] The intermediate layer and the resin composition capable of forming the intermediate layer will be described in detail later.

[0576] As a method for producing the above-mentioned transfer film 100, for example, there can be mentioned a method including the following steps: a step of forming a thermoplastic resin layer 12 by coating the thermoplastic resin composition of the present invention on the surface of a temporary support 10 and then drying the coating film of the thermoplastic resin composition of the present invention; a step of forming an intermediate layer 14 by coating an intermediate layer-forming resin composition on the surface of the thermoplastic resin layer 12 and then drying the coating film of the intermediate layer-forming resin composition; and a step of forming a negative photosensitive resin layer 16 by coating the negative photosensitive resin composition of the present invention on the surface of the intermediate layer 14 and then drying the coating film of the negative photosensitive resin composition of the present invention.

[0577] The transfer film 100 is produced by pressure-bonding the cover film 18 onto the negative photosensitive resin layer 16 of the laminate produced by the above-described production method.

[0578] The method for producing the transfer film of the present invention preferably includes providing the cover film 18 in contact with the second surface of the photosensitive resin layer 16 to produce the transfer film 100 including the temporary support 10, the thermoplastic resin layer 12, the intermediate layer 14, the photosensitive resin layer 16, and the cover film 18.

[0579] After the transfer film 100 is manufactured by the above-described manufacturing method, the transfer film 100 is wound up, so that a roll-shaped transfer film can be produced and stored. The roll-shaped transfer film can be provided as is in the roll-to-roll lamination step with the substrate described later.

[0580] In the above-mentioned production method, the composition of the present invention is used as both the thermoplastic resin composition and the negative photosensitive resin composition. However, it is sufficient that at least one of these is the composition of the present invention, and one may be a composition other than the present invention (a thermoplastic resin composition other than the present invention and / or a negative photosensitive resin composition other than the present invention).

[0581] Similarly, in the transfer film 100 , at least one of the thermoplastic resin layer 12 and the negative photosensitive resin layer 16 may be a composition layer of the present invention, and the other may be a composition layer other than the present invention.

[0582] <Middle Layer>

[0583] The intermediate layer contains a resin, and the resin is preferably a water-soluble resin.

[0584] Examples of resins that can be used as the water-soluble resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

[0585] In addition, when a water-soluble resin layer containing a water-soluble resin is used as an intermediate layer, from the viewpoint of suppressing mixing of components between the multiple layers, the water-soluble resin is preferably a resin different from the resin contained in the adjacent layer (for example, the polymer P contained in the negative photosensitive resin layer and / or the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer).

[0586] From the viewpoint of oxygen barrier properties and suppression of mixing of components during multi-layer coating and storage after coating, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinyl pyrrolidone.

[0587] The intermediate layer can be formed using a water-soluble resin composition containing a water-soluble resin.

[0588] The water-soluble resin may be used alone or in combination of two or more.

[0589] The content of the water-soluble resin is not particularly limited, but from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating, it is preferably 50% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, further preferably 80% by mass or more and less than 100% by mass, and particularly preferably 90% by mass or more and less than 100% by mass, relative to the total solid content of the water-soluble resin composition.

[0590] Furthermore, in order to improve coating properties, the water-soluble resin composition preferably contains a solvent in addition to the water-soluble resin. The solvent contained in the water-soluble resin composition is not particularly limited as long as it can dissolve or disperse the water-soluble resin. However, it is preferably at least one selected from water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

[0591] Preferred examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol. Of the alcohols having 1 to 3 carbon atoms, methanol or ethanol is more preferred.

[0592] 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, relative to 100 parts by mass of the total solid content of the composition.

[0593] The method for coating the composition using the water-soluble resin composition and / or the method for forming the composition layer are not particularly limited, and can be performed in the same manner as in the method using the negative photosensitive resin composition, for example.

[0594] The method for forming the intermediate layer (water-soluble resin layer containing a water-soluble resin) is not particularly limited. For example, a method of forming the water-soluble resin layer by applying a water-soluble resin composition on the surface of a thermoplastic resin layer or a photosensitive resin layer and drying the coating of the water-soluble resin composition can be cited.

[0595] The thickness of the water-soluble resin layer is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. This is because, when the thickness of the water-soluble resin layer is within this range, mixing of components during coating of multiple layers and storage after coating can be suppressed without reducing oxygen barrier properties, and an increase in the time required to remove the water-soluble resin layer during development can be suppressed.

[0596] An example of the form of the transfer film is shown below.

[0597] In each of the following structures, one or more layers (such as a cover film) may be removed as needed, or another layer may be added between arbitrary layers.

[0598] (1) “Temporary support / thermoplastic resin layer / intermediate layer (water-soluble resin layer) / negative photosensitive resin layer / cover film”

[0599] (2) “Temporary support / negative photosensitive resin layer / refractive index adjusting layer / cover film”

[0600] (3) "Temporary support / negative photosensitive resin layer / cover film"

[0601] In the composition layers (layers excluding the temporary support and the cover film) constituting the transfer film of each of the above structures, at least one of the thermoplastic resin layer and the negative photosensitive resin layer is the composition layer of the present invention.

[0602] In each of the above structures, the negative photosensitive resin layer is preferably a colored resin layer.

[0603] In the above structure, the refractive index adjusting layer may be a known refractive index adjusting layer, for example, the second resin layer disclosed in paragraphs

[0200] to

[0214] of JP-A-2020-091322.

[0604] [Method for Manufacturing Laminated Body and Method for Manufacturing Circuit Wiring]

[0605] The present invention also relates to a method for manufacturing a laminate.

[0606] The method for producing the laminate is not particularly limited as long as it is a method for producing the laminate using the above-mentioned transfer film.

[0607] The method for manufacturing a laminate preferably includes: a laminating step (hereinafter also referred to as the "laminating step"), in which a substrate (preferably a conductive substrate) is brought into contact with a surface (surface of the composition layer) on the opposite side of the temporary support body of the transfer film, and the transfer film and the substrate (preferably a conductive substrate) are laminated to obtain a substrate with a transfer film; an exposure step (hereinafter also referred to as the "exposure step"), in which a pattern is exposed to the composition layer; and a developing step (hereinafter also referred to as the "developing step"), in which the exposed composition layer is developed to form a resin pattern, and a peeling step (hereinafter also referred to as the "peeling step") of peeling the temporary support body from the substrate with the transfer film is included between the laminating step and the exposure step or between the exposure step and the development step.

[0608] The composition layer subjected to pattern exposure may include a single layer or two or more layers, and at least one layer constituting the composition layer is the composition layer of the present invention.

[0609] Furthermore, the pattern-exposed composition layer preferably includes at least one negative photosensitive resin layer (the negative photosensitive resin layer of the present invention or a negative photosensitive resin layer other than the negative photosensitive resin layer of the present invention). The negative photosensitive resin layer may be a colored resin layer.

[0610] The method for producing the circuit wiring is not particularly limited as long as it is a method for producing the circuit wiring using the above-mentioned transfer film.

[0611] As a method for manufacturing circuit wiring, a method preferably includes the following step (hereinafter also referred to as "etching step"): in a laminate in which a substrate, a conductive layer (a conductive layer possessed by the substrate) and a resin pattern manufactured using the above-mentioned transfer film are stacked in sequence, the conductive layer located in an area where no resin pattern is provided is etched.

[0612] That is, the method for manufacturing circuit wiring preferably includes: a laminating process (hereinafter also referred to as the "laminating process"), in which a substrate having a conductive layer is brought into contact with a surface (composition layer) on the opposite side of a temporary support body of the transfer film, and the transfer film and the substrate having a conductive layer are laminated to obtain a substrate with a transfer film; an exposure process (hereinafter also referred to as the "exposure process"), in which a pattern is exposed to the composition layer; a developing process (hereinafter also referred to as the "developing process"), in which the exposed composition layer is developed to form a resin pattern; and a process for etching the conductive layer in an area where a resin pattern is not provided (hereinafter also referred to as the "etching process"), further comprising a peeling process (hereinafter also referred to as the "peeling process") of peeling the temporary support body from the substrate with the transfer film between the laminating process and the exposure process or between the exposure process and the developing process.

[0613] Preferred aspects of the composition layer subjected to pattern exposure are also the same as those described above.

[0614] The following describes the various steps involved in the method for manufacturing a laminate and the method for manufacturing circuit wiring. However, except for cases where special mention is made, the description of the various steps involved in the method for manufacturing a laminate also applies to the various steps involved in the method for manufacturing circuit wiring.

[0615] 〔Lamination process〕

[0616] The method for producing a laminate preferably includes a lamination step.

[0617] During the lamination process, the substrate (or the conductive layer if a conductive layer is provided on the substrate surface) is preferably brought into contact with the surface of the transfer film opposite to the temporary support, and the transfer film and substrate are pressure-bonded. This configuration improves the adhesion of the composition layer to the substrate, making it suitable for use as an etching resist when etching the conductive layer using a resin pattern formed with a pattern after exposure and development.

[0618] In addition, when the transfer film includes a cover film, the cover film may be removed from the surface of the transfer film before lamination.

[0619] There are no particular limitations on the method for pressure-bonding the substrate and the transfer film, and a known transfer method and lamination method can be used.

[0620] The transfer film and the substrate are preferably laminated together by stacking the substrate on the side of the transfer film opposite to the temporary support and applying pressure and heat using rollers or other methods. For lamination, a known laminator such as a laminator, a vacuum laminator, or an automatic cutting laminator that can further improve productivity can be used.

[0621] The method for producing a laminate and the method for producing a circuit wiring including the lamination step are preferably performed by a roll-to-roll method.

[0622] The roll-to-roll method refers to the following method, which includes: using a substrate that can be wound and unwound as a substrate, and before any process included in the manufacturing method of a laminate or the manufacturing method of circuit wiring, a process of unwinding the substrate or a structure including the substrate (also referred to as an "unwinding process"); and after any process, a process of winding the substrate or the structure including the substrate (also referred to as a "winding process"), and performing at least any one process (preferably all processes or all processes except the heating process) while conveying the substrate or the structure including the substrate.

[0623] The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a production method employing a roll-to-roll system.

[0624] <Substrate>

[0625] As the substrate for forming a resin pattern using the transfer film of the present invention, any known substrate may be used, but a substrate having a conductive layer is preferred, and a substrate having a conductive layer on its surface is more preferred.

[0626] The substrate may have any layer other than the conductive layer as needed.

[0627] Examples of the base material constituting the substrate include glass, silicon, and films.

[0628] The base material constituting the substrate is preferably a transparent base material. In this specification, "transparent" means that the transmittance of light with a wavelength of 400 to 700 nm is 80% or more.

[0629] Furthermore, the refractive index of the base material constituting the substrate is preferably 1.50 to 1.52.

[0630] Examples of the transparent glass substrate include tempered glass such as Gorilla Glass from Corning Incorporated. Furthermore, materials described in Japanese Patent Application Laid-Open Nos. 2010-086684, 2010-152809, and 2010-257492 can be used as the transparent glass substrate.

[0631] When a film substrate is used as the substrate, it is preferred to use a film substrate with low optical distortion and / or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0632] When the substrate is produced by a roll-to-roll method, a film substrate is preferably used as the substrate. Furthermore, when the circuit wiring for a touch panel is produced by a roll-to-roll method, the substrate is preferably a sheet-like resin composition.

[0633] Examples of the conductive layer included in the substrate include conductive layers used for general circuit wiring and touch panel wiring.

[0634] From the viewpoint of conductivity and thin line formability, the conductive layer is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and still more preferably a copper layer or a silver layer.

[0635] The substrate may have a single conductive layer or may have two or more conductive layers. In the case of having two or more conductive layers, the conductive layers are preferably made of different materials.

[0636] Examples of the material for the conductive layer include metals and conductive metal oxides.

[0637] Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

[0638] Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .

[0639] In this specification, “conductive” means a volume resistivity of less than 1×10 6 Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ωcm.

[0640] When a resin pattern is produced using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

[0641] As the conductive layer, an electrode pattern of a sensor corresponding to a visual recognition portion or wiring of a peripheral extraction portion used in a capacitive touch panel is preferable.

[0642] [Exposure process]

[0643] The method for producing a laminate preferably includes a step of pattern-exposing the composition layer after the laminating step (exposure step).

[0644] The detailed configuration and specific dimensions of the pattern used in the pattern exposure are not particularly limited. At least a portion of the pattern (preferably the electrode pattern and / or lead-out wiring portion of the touch panel) preferably includes fine wires having a width of 20 μm or less. This improves the display quality of a display device (e.g., a touch panel) having an input device including circuit wiring manufactured using the circuit wiring manufacturing method and reduces the area occupied by the lead-out wiring. More preferably, the pattern includes fine wires having a width of 10 μm or less.

[0645] The light source used for exposure can be appropriately selected as long as it emits light of a wavelength capable of exposing the photosensitive resin layer (e.g., 365 nm or 405 nm). Specific examples include ultrahigh-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

[0646] The exposure dose is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 100 mJ / cm 2 .

[0647] [Peeling process]

[0648] The peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the laminating step and the exposure step or between the exposure step and the development step described later.

[0649] The peeling method is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs

[0161] and

[0162] of Japanese Patent Application Laid-Open No. 2010-072589 can be used.

[0650] Therefore, in the exposure process, pattern exposure can be carried out after peeling off the temporary support from the composition layer, or pattern exposure can be carried out via the temporary support before peeling off the temporary support, and then the temporary support is peeled off. About the mask, when peeling off the temporary support before exposure, it can be exposed by contacting with the composition layer, or it can be exposed close to exposure without contact. When the temporary support is not peeled off and exposed, the mask can be exposed by contacting with the temporary support, or it can be exposed close to exposure without contact. In order to prevent the mask contamination caused by the contact of the composition layer with the mask and to avoid the influence on exposure caused by the foreign matter attached to the mask, it is preferred not to peel off the temporary support and carry out pattern exposure. In addition, about exposure mode, in the case of contact exposure, it is possible to appropriately select to use contact exposure mode, in the case of non-contact exposure mode, it is possible to appropriately select to use proximity exposure mode, lens system and reflector system projection exposure mode and the direct exposure mode using exposure laser etc. In the case of lens system and reflector system projection exposure, it is possible to use an exposure machine with suitable lens numerical aperture (NA) according to required resolution, depth of focus. In the case of direct exposure, the drawing can be performed directly on the photosensitive layer, or the photosensitive layer can be exposed by reduced projection through a lens. Furthermore, exposure can be performed not only in the atmosphere but also under reduced pressure or vacuum. Furthermore, exposure can be performed with a liquid such as water interposed between the light source and the photosensitive layer.

[0651] [Development process]

[0652] The method for producing a laminate preferably includes, after the exposure step, a step of developing the exposed composition layer to form a resin pattern (development step).

[0653] When the composition layer includes a negative photosensitive resin layer (the negative photosensitive resin layer of the present invention or a negative photosensitive resin layer other than the present invention), the composition layer can be cured according to the exposed pattern to form a cured film (patterned cured film), and only the non-exposed portion of the composition layer can be removed using a developer (alkaline developer, etc.).

[0654] When the transfer film has a negative photosensitive resin layer and a composition layer different from these, the above-mentioned different composition layer can remove only the same part as the part removed in the negative photosensitive resin layer, or can remove all of the part including the part other than the part removed in the negative photosensitive resin layer.

[0655] For example, if the transfer film includes a negative-type photosensitive resin layer and a thermoplastic resin layer and / or a water-soluble resin layer, during the development step, only the thermoplastic resin layer and / or the water-soluble resin layer in the non-exposed area can be removed together with the negative-type photosensitive resin layer in the non-exposed area. Furthermore, during the development step, the thermoplastic resin layer and / or the water-soluble resin layer in both the exposed and non-exposed areas can be removed while dissolved or dispersed in the developer.

[0656] The resin pattern obtained after development may be partially or entirely composed of the composition layer of the present invention or a layer formed by a curing reaction of the composition of the present invention. For example, if the composition layer of the transfer film includes a negative-type photosensitive resin layer of the present invention, the resin pattern may be partially or entirely composed of a material formed by a curing reaction of the negative-type photosensitive resin layer of the present invention.

[0657] Furthermore, the resin pattern obtained after development may not include a layer of the composition of the present invention or a layer formed by a change such as a curing reaction of the composition of the present invention. In other words, the resin pattern obtained after development may only include a layer of a composition other than the present invention and / or a layer formed by a change such as a curing reaction of the composition other than the present invention.

[0658] The development of the exposed composition layer in the development step can be performed using an alkaline developer.

[0659] As the alkali developer, for example, a known developer such as one described in Japanese Patent Application Laid-Open No. 5-072724 can be used.

[0660] As the alkaline developer, an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L (liter) is preferred. The alkaline developer may contain a water-soluble organic solvent and / or a surfactant. As the alkaline developer, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 is also preferred. The content of the organic solvent in the alkaline developer is preferably 0% by mass or more and less than 90% by mass relative to the total mass of the developer.

[0661] The developing method is not particularly limited and may be any of spin immersion developing, shower developing, shower and spin developing, and immersion developing. Spray developing is a developing process in which a developer is sprayed onto the exposed photosensitive resin layer to remove unexposed areas.

[0662] After the development step, it is preferred to remove development residues by spraying a cleaning agent with a shower and wiping with a brush.

[0663] The liquid temperature of the developer is not particularly limited, but is preferably 20 to 40°C.

[0664] Etching process

[0665] The manufacturing method of circuit wiring preferably includes the following process (etching process): in a stacked body in which a substrate, a conductive layer (a conductive layer possessed by the substrate) and a resin pattern (more preferably a resin pattern manufactured by a manufacturing method including the above-mentioned bonding process, the above-mentioned exposure process and the above-mentioned development process) are stacked in sequence, the conductive layer located in an area where the resin pattern is not configured is etched.

[0666] In the etching step, the conductive layer is etched using the resin pattern formed by the photosensitive resin layer as an etching resist.

[0667] As the etching method, a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, wet etching by immersion in an etching solution, and dry etching methods such as plasma etching can be cited.

[0668] The etching solution used in wet etching may be an acidic or alkaline etching solution appropriately selected according to the etching target.

[0669] Examples of the acidic etching solution include aqueous solutions containing only an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and mixed aqueous solutions containing an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components.

[0670] Examples of alkaline etching solutions include aqueous solutions of alkaline components alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), and mixed aqueous solutions of alkaline components and salts (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.

[0671] 〔Removal process〕

[0672] In the method for producing a circuit wiring, it is preferable to perform a step of removing the remaining resin pattern (removal step).

[0673] The removal step is not particularly limited and can be performed as needed, but is preferably performed after the etching step.

[0674] The method for removing the remaining resin pattern is not particularly limited, but a method of removing by chemical treatment is exemplified, and a method of removing using a removing liquid is preferred.

[0675] Examples of a method for removing the photosensitive resin layer include a method of immersing the substrate having the remaining resin pattern in a stirring removing liquid having a liquid temperature of preferably 30 to 80° C., more preferably 50 to 80° C., for 1 to 30 minutes.

[0676] Examples of the removal liquid include those obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkaline component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0677] Furthermore, the removal can be performed by a known method such as a spraying method, a shower method, or a spin immersion method using a removal liquid.

[0678] 〔Other processes〕

[0679] The method for producing a circuit wiring may include any steps (other steps) other than the above-mentioned steps. For example, the following steps may be mentioned, but the method is not limited to these steps.

[0680] Furthermore, examples of the exposure step, the development step, and other steps applicable to the method for producing the circuit wiring include the steps described in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696.

[0681] <Cover Film Peeling Step>

[0682] When the transfer film includes a cover film, the method for producing the laminate preferably includes a step of peeling the cover film from the transfer film. The method for peeling the cover film is not limited, and a known method can be applied.

[0683] <Step of Reducing Visible Light Reflectance>

[0684] The method for producing a circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of a part or all of the plurality of conductive layers included in the substrate.

[0685] As a treatment for reducing visible light reflectance, oxidation treatment can be mentioned. When the substrate has a conductive layer containing copper, oxidation treatment of the copper to form copper oxide can blacken the conductive layer, thereby reducing the visible light reflectance of the conductive layer.

[0686] The treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Application Laid-Open No. 2013-206315, and the contents of these publications are incorporated herein by reference.

[0687] <Step of Forming an Insulating Film, Step of Forming a New Conductive Layer on the Surface of the Insulating Film>

[0688] The method for producing a circuit wiring preferably also includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.

[0689] Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.

[0690] The step 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 can be formed by photolithography using a photosensitive material having insulating properties.

[0691] The process of forming a new conductive layer on the insulating film is not particularly limited. For example, a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

[0692] The method for manufacturing circuit wiring also preferably uses a substrate having multiple conductive layers on both surfaces of the substrate, and forms circuits sequentially or simultaneously on the conductive layers formed on both surfaces of the substrate. This structure enables the formation of touch panel circuit wiring having a first conductive pattern formed on one surface of the substrate and a second conductive pattern formed on the other surface. Furthermore, it is also preferred to form touch panel circuit wiring with this structure from both surfaces of the substrate using a roll-to-roll process.

[0693] [Purpose of circuit wiring]

[0694] The circuit wiring produced by the circuit wiring production method can be applied to various devices. Devices equipped with the circuit wiring produced by the above-described production method include, for example, input devices, preferably touch panels, and more preferably capacitive touch panels. Furthermore, the input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[0695] [Method for manufacturing electronic device]

[0696] The invention also relates to a method for manufacturing the electronic device.

[0697] As the method for producing the electronic device, a method for producing an electronic device using the transfer film is preferred.

[0698] Among them, the method for manufacturing an electronic device preferably includes the method for manufacturing the above-mentioned laminate.

[0699] Examples of the electronic device include input devices, preferably touch panels, and the input device can be applied to display devices such as organic electroluminescent display devices and liquid crystal display devices.

[0700] As a method for manufacturing a touch panel, a method including the following steps is also preferred: in a laminate in which a substrate, a conductive layer (a conductive layer possessed by the substrate) and a resin pattern manufactured using the above-mentioned transfer film are sequentially stacked, the conductive layer located in an area where no resin pattern is provided is etched, thereby forming wiring for a touch panel. A method using a resin pattern manufactured by a manufacturing method including the above-mentioned lamination step, the above-mentioned exposure step and the above-mentioned development step is more preferred.

[0701] Specific aspects of each step in the touch panel manufacturing method including the step of forming touch panel wiring and the order of performing each step are as described in the above-mentioned "Method for Manufacturing Circuit Wiring", and the preferred aspects are also the same.

[0702] Furthermore, the method for manufacturing a touch panel including the step of forming touch panel wiring may include any steps (other steps) other than the above-mentioned steps.

[0703] As a method for forming a touch panel wiring, reference can also be made to International Publication No. 2016 / 190405. Figure 1 The method described in .

[0704] The touch panel manufacturing method can manufacture a touch panel having at least touch panel wiring. The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.

[0705] Examples of detection methods in touch panels include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the capacitance method is preferred.

[0706] Examples of touch panels include so-called in-cell types (e.g., as described in FIG. 5, FIG. 6, FIG. 7, and FIG. 8 of Japanese Unexamined Patent Publication No. 2012-517051), so-called out-cell types (e.g., as described in FIG. 19 of Japanese Unexamined Patent Publication No. 2013-168125, and FIG. 2012-89102). Figure 1 5 ), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, as described in FIG. 2 of Japanese Patent Publication No. 2013-54727 ), various plug-in types (the so-called GG, G1 / G2, GFF, GF2, GF1 and G1F, etc.) and other structures (for example, as described in FIG. 6 of Japanese Patent Publication No. 2013-164871 ).

[0707] As an example of a touch panel, the touch panel described in paragraph 0229 of Japanese Patent Application Laid-Open No. 2017-120345 can be cited.

[0708] Example

[0709] Below, based on embodiment, the present invention is described in further detail.The materials, usage, ratio, processing content and processing step etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention.Therefore, the scope of the present invention should not be interpreted in a limited manner by the examples shown below.

[0710] In the following examples, "parts" and "%" mean "parts by mass" and "mass %", respectively, unless otherwise specified.

[0711] Hereinafter, first, a synthesis example of compound A and preparation of various compositions will be described, and then evaluation results of each composition will be shown.

[0712] [Synthesis of Compound A]

[0713] [Synthesis Examples 1 to 4: Synthesis of Polymer Compound A]

[0714] <Synthesis example 1>

[0715] In a 300 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 25.0 g of cyclohexanone (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added, and the temperature was raised to 80° C. Subsequently, a mixed solution containing 10.40 g (36.6 mmol) of 1H,1H,5H-octafluoropentyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 60.5 g (111.8 mmol) of polyethylene glycol monoacrylate (BLEMMER AF-400, n≈10, manufactured by NOF Corporation), 25.0 g of cyclohexanone, and 0.342 g of initiator "V-601" (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise at a constant rate so that the addition was completed within 180 minutes. After the dropwise addition was completed, stirring was continued for another hour, and then a solution containing 0.342 g of "V-601" and 1.00 g of cyclohexanone was further added. Immediately after the addition, the temperature was raised to 93°C, and stirring was continued for another 2 hours, yielding 121.5 g of a cyclohexanone solution of polymer A-1 shown in the following section. The weight-average molecular weight (Mw) of this polymer was 11,000 (calculated in terms of polystyrene using gel permeation chromatography (EcoSECH LC-8320 GPC (manufactured by TOSOH CORPORATION) using THF as the eluent, a flow rate of 0.35 ml / min, and a temperature of 40°C. The columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by TOSOH CORPORATION)).

[0716] <Synthesis Example 2 to Synthesis Example 4>

[0717] Polymers A-5, A-6, and A-9 were synthesized by the same method as in Synthesis Example 1 except that the monomers and composition ratios used were changed.

[0718] The structures of polymers A-1, A-5, A-6, and A-9 are shown below. The numerical values of the structural units added to the polymers represent the content (mass %) relative to the total mass of the polymer.

[0719] [Chemical Formula 15]

[0720]

[0721] The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of each polymer are shown in Table 1 below.

[0722] [Table 1]

[0723] Types of polymers Mw Mn Mw / Mn A-1 11000 5000 2.2 A-5 12000 6030 1.99 A-6 18000 7400 2.43 A-9 9000 3900 2.29

[0724] [Synthesis Example 5: Synthesis of Low Molecular Weight Compound A]

[0725] The low molecular weight compound B-1 shown below was synthesized by a known method with reference to the literature ("Lisong et al., Oil Chemistry, 1980, Vol. 29(1), p23" and "Lisong et al., Pharmacy, 1976, Vol. 25(5), p287").

[0726] [Chemical Formula 16]

[0727]

[0728] [Examples 1 to 8, Comparative Example 1 (Tests in which the composition is a negative-type photosensitive resin composition)]

[0729] 〔Manufacturing of resin〕

[0730] In the following synthesis examples, the following abbreviations represent the following compounds, respectively.

[0731] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0732] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0733] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0734] BzMA: benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0735] AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0736] PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[0737] MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0738] V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0739] <Synthesis of Resin P-1>

[0740] PGMEA (116.5 parts) was placed in a three-necked flask and heated to 90°C under a nitrogen atmosphere. A solution containing St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts) was added dropwise over 2 hours to the solution in the flask maintained at 90°C ± 2°C. After the addition, the solution in the flask was stirred at 90°C ± 2°C for 2 hours, yielding Resin P-1 (solids concentration: 30.0% by mass).

[0741] <Synthesis of Resins P-2 and P-3>

[0742] Solutions containing resin P-2 and resin P-3 were obtained by the same method as for resin P-1, with the monomer types and compositions varied as shown in Table 2. The solids concentration of the solutions containing resin P-2 and resin P-3 was set to 30% by mass.

[0743] Table 2 below shows the composition (mass %) and weight average molecular weight of each resin.

[0744] In addition, resins P-1 to P-3 all qualify as alkali-soluble resins.

[0745] In Table 2, “St” refers to a structural unit derived from styrene, “BzMA” refers to a structural unit derived from benzyl methacrylate, “MAA” refers to a structural unit derived from methacrylic acid, and “MMA” refers to a structural unit derived from methyl methacrylate.

[0746] [Table 2]

[0747] P-1 P-2 P-3 St 52 32 BZD 81 MAA 29 19 28 MMA 19 40 Weight average molecular weight (Mw) 60000 40000 40000

[0748] [Preparation of Photosensitive Resin Compositions 1 to 9]

[0749] These components were stirred and mixed according to the formulations described in Table 3 shown later, thereby preparing photosensitive resin compositions 1 to 9.

[0750] Hereinafter, the preparation of each of the photosensitive resin compositions 1 to 9 will be shown.

[0751] In the table, the numerical values about each component in each photosensitive resin composition represent the addition amount (parts by mass) of each component.

[0752] The resin was added to each photosensitive resin composition in the form of a solution containing the resin. The numerical values indicating the amount of resin added in the table are the mass of the added "solution containing the resin".

[0753] Hereinafter, components added to the composition in the form of being contained in a mixed solution are assumed to be the same unless otherwise specified.

[0754] In the table, the column "Average film thickness of photosensitive resin layer (μm)" shows the average film thickness of the photosensitive resin layer formed when the test was performed using each photosensitive resin composition. The details of the test will be described later.

[0755] [Table 3]

[0756]

[0757] In Table 3, the details of each component are as follows.

[0758] BPE-500: 2,2-bis(4-((meth)acryloyloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0759] BPE-200: 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0760] M-270: Polypropylene glycol diacrylate (n≈12), manufactured by TOAGOSEI CO., LTD.

[0761] A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0762] SR-454: Ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema

[0763] SR-502: Ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema

[0764] A-9300-CL1: Caprolactone-modified (meth)acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0765] B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, Hampford

[0766] SB-PI 701: 4,4'-bis(diethylamino)benzophenone, manufactured by SANYO TRADING CO., LTD.

[0767] Co., Ltd. Manufacturing

[0768] Brilliant Green: Made by Tokyo Chemical Industry Co., Ltd.

[0769] N-phenylglycine: manufactured by Tokyo Chemical Industry Co., Ltd.

[0770] CBT-1: Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.

[0771] TDP-G: Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0772] Irganox 245: Hindered phenol antioxidant, manufactured by BASF

[0773] N-Nitrosophenylhydroxylamine aluminum salt: manufactured by FUJIFILM Wako Pure Chemical Corporation

[0774] Phenidone: manufactured by Tokyo Chemical Industry Co., Ltd.

[0775] F552: MEGAFACE F552, manufactured by DIC CORPORATION, a fluorine-based surfactant that does not conform to Compound A

[0776] A-1, A-5, A-6, A-9, B-1: polymers (A-1), (A-5), (A-6), (A-9), (B-1) respectively produced by the above method (all corresponding to compound A)

[0777] 〔test〕

[0778] <Example 1>

[0779] The prepared photosensitive resin composition 1 was applied to a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) using a slit nozzle at a width of 1.0 m so that the average thickness of the obtained photosensitive resin layer would be a predetermined thickness.

[0780] Then, the above-mentioned polyethylene terephthalate film (temporary support) was passed through a 3-meter drying zone with a temperature of 80°C and an air intake and exhaust volume adjusted to set the wind speed on the film surface to 3 m / sec for 60 seconds, thereby obtaining a photosensitive resin layer (negative photosensitive resin layer) on the temporary support.

[0781] <Examples 2 to 8 and Comparative Example 1>

[0782] Except having changed the photosensitive resin composition used as described in Table 3, the same method as that of the photosensitive resin composition 1 was carried out to prepare and evaluate the respective photosensitive resin layers.

[0783] [Example 9, Example 10, Comparative Example 2 (Tests in which the composition is a thermoplastic resin composition)]

[0784] [Synthesis of Resin P-4]

[0785] A solution containing resin P-4 was obtained by the same method as for resin P-1, with the types and compositions of the monomers used being changed as shown in Table 4. The solid content concentration of the solution containing resin P-4 was set to 30% by mass.

[0786] In addition, resin P-4 corresponds to an alkali-soluble resin.

[0787] The composition (mass %) of resin P-4 is shown in Table 4. In Table 4, "BzMA" refers to a structural unit derived from benzyl methacrylate, "MAA" refers to a structural unit derived from methacrylic acid, and "AA" refers to a structural unit derived from acrylic acid.

[0788] [Table 4]

[0789] P-4 BZD 75 MAA 10 AA 15 Weight average molecular weight (Mw) 30,000

[0790] [Preparation of Thermoplastic Resin Compositions 1 to 3]

[0791] Thermoplastic resin compositions 1 to 3 were prepared by mixing the formulations and blending amounts (parts by mass) shown in Table 5 below.

[0792] In the table, the column "Average film thickness of thermoplastic resin layer (μm)" shows the average film thickness of the thermoplastic resin layer formed when the test was conducted using each thermoplastic resin composition. The details of the test will be described later.

[0793] [Table 5]

[0794]

[0795] In Table 5, the abbreviations represent the following compounds, respectively.

[0796] P-4: A resin containing 75% by mass of benzyl methacrylate-based structural units, 10% by mass of methyl methacrylate-based structural units, and 15% by mass of acrylic acid-based structural units, respectively, relative to the total mass of the resin, and having a weight-average molecular weight of 30,000. P-4 qualifies as an alkali-soluble thermoplastic resin. P-4 was added to the thermoplastic resin composition in the form of a solution containing P-4 (solids concentration 30.0% by mass, solvent: PGMEA).

[0797] Acrybase FF187: a solution containing an alkali-soluble thermoplastic resin, solid content concentration: 40% by mass, solvent: PGMEA, manufactured by Fujikura Akasei Co., Ltd.

[0798] BB-1: A compound having the structure shown below (a pigment that develops color when exposed to acid)

[0799] [Chemical Formula 17]

[0800]

[0801] C-1: A compound having the structure shown below (a photoacid generator, a compound described in paragraph 0227 of JP-A-2013-047765, synthesized according to the method described in paragraph 0227.)

[0802] [Chemical Formula 18]

[0803]

[0804] A-1: Polymer (A-1) produced by the above method

[0805] 〔test〕

[0806] <Example 9>

[0807] The prepared thermoplastic resin composition 1 was applied to a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) at a width of 1.0 m using a slit nozzle so that the obtained thermoplastic resin layer had a predetermined average film thickness.

[0808] The polyethylene terephthalate film (temporary support) was then passed through a 3 m drying zone at 80°C for 60 seconds with the air intake and exhaust adjusted to set the film surface wind speed to 3 m / sec, thereby obtaining a thermoplastic resin layer 1 on the temporary support.

[0809] <Example 10 and Comparative Example 2>

[0810] Thermoplastic resin layers were prepared and evaluated in the same manner as in Thermoplastic Resin Composition 1, except that the thermoplastic resin composition used and the average film thickness of the thermoplastic resin layer to be formed were changed as described in Table 5.

[0811] [Example 11, Comparative Example 3 (Test in which the composition is both a negative photosensitive resin composition and a colored resin composition)]

[0812] [Preparation of Photosensitive Resin Compositions 10-11]

[0813] These components were stirred and mixed according to the formulations described in Table 6 below to prepare photosensitive resin compositions 10 and 11. The units of the amounts of the components are parts by mass.

[0814] In the table, the column "Average film thickness of photosensitive resin layer (μm)" shows the average film thickness of the photosensitive resin layer formed when the test was performed using each photosensitive resin composition. The details of the test will be described later.

[0815] [Table 6]

[0816]

[0817] The details of the components described in Table 6 are as follows.

[0818] -pigment-

[0819] Black pigment dispersion FDK-T-11: Aqueous solution with a solid content concentration of 27% by mass, Pigment: Carbon black, manufactured by Tokyo Printing Ink MFG Co., Ltd.

[0820] -Polymerizable compound-

[0821] A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0822] A-DCP: tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0823] 8UX-015A: Polyurethane acrylate, manufactured by TAISEI FINE CHEMICAL CO., LTD.

[0824] 75% by mass PGMEA solution of KAYARAD DPHA: 75% by mass propylene glycol monomethyl ether acetate solution of KAYARAD DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.) The composition of KAYARAD DPHA is shown below.

[0825] [Chemical Formula 19]

[0826]

[0827] -Binder (alkali-soluble resin)-

[0828] ACRIT 8KB-001: Non-crosslinking acrylic adhesive, solid content concentration: 38% by mass, solvent: PGMEA, manufactured by TAISEI FINE CHEMICAL CO., LTD., ACRIT (registered trademark) 8KB-001

[0829] -Photopolymerization initiator-

[0830] Irgacure OXE-02: manufactured by BASF, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime)

[0831] -Solvents-

[0832] 1-Methoxy-2-propyl acetate

[0833] Methyl ethyl ketone

[0834] -additive-

[0835] 1,2,4-Triazole: manufactured by Tokyo Chemical Industry Co., Ltd.

[0836] -Compound A or comparative compound-

[0837] Aa-1: polymer (A-1) produced by the above method

[0838] MEGAFACE F555A: manufactured by DIC CORPORATION, a fluorine-based surfactant that does not conform to Compound A

[0839] 〔test〕

[0840] <Example 11>

[0841] The prepared photosensitive resin composition 10 was applied to a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) using a slit nozzle at a width of 1.0 m so that the average thickness of the obtained photosensitive resin layer would be a predetermined thickness.

[0842] Then, the polyethylene terephthalate film (temporary support) was passed through a 3 m drying zone with a temperature of 80°C and an air intake and exhaust volume adjusted to set the film surface wind speed to 3 m / sec for 60 seconds, thereby obtaining a photosensitive resin layer (colored resin layer) on the temporary support.

[0843] <Comparative Example 3>

[0844] Except having changed the photosensitive resin composition used and the average film thickness of the formed photosensitive resin composition as described in Table 6, the same procedures as those for the photosensitive resin composition 10 were carried out to prepare and evaluate the coating films.

[0845] [Example 12, Example 13, Comparative Example 4 (Test in which the composition is a negative photosensitive resin composition)]

[0846] 〔Manufacturing of resin〕

[0847] <Synthesis of Resin P-5>

[0848] Propylene glycol monomethyl ether acetate (60 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and propylene glycol monomethyl ether (240 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were placed in a 2000 mL flask. The resulting liquid was heated to 90° C. while stirring at 250 rpm (round per minute; the same shall apply hereinafter).

[0849] To prepare a dropping solution (1), methacrylic acid (107.1 g, manufactured by MITSUBISHI RAYON CO., LTD., trade name: Acryester M), methyl methacrylate (5.46 g, manufactured by MITSU BTSHI GAS CHEMICAL COMPANY, INC., trade name: MMA) and cyclohexyl methacrylate (231.42 g, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., trade name: CHMA) were mixed and diluted with propylene glycol monomethyl ether acetate (60.0 g) to obtain a dropping solution (1).

[0850] To prepare a dropping solution (2), dimethyl 2,2'-azobis(2-methylpropionate) (9.637 g, manufactured by FUJIFILM Wako Pure Chemical Corporation, trade name V-601) was dissolved in propylene glycol monomethyl ether acetate (136.56 g) to obtain a dropping solution (2).

[0851] Dropwise solution (1) and dropwise solution (2) were simultaneously added dropwise to the aforementioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90°C) over 3 hours. After the dropwise addition was completed, V-601 (2.401 g) was added to the flask three times at 1-hour intervals. The mixture was then stirred at 90°C for an additional 3 hours.

[0852] The solution (reaction solution) obtained in the flask was then diluted with propylene glycol monomethyl ether acetate (178.66 g). Tetraethylammonium bromide (1.8 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) and hydroquinone monomethyl ether (0.8 g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were then added to the reaction solution. The temperature of the reaction solution was then raised to 100°C.

[0853] Next, glycidyl methacrylate (76.03 g, manufactured by NOF CORPORATION, trade name BLEMMER G) was added dropwise to the reaction solution over 1 hour. The reaction solution was allowed to react at 100°C for 6 hours to obtain 1158 g of a solution of resin P-5 (solids concentration: 36.3% by mass). The obtained resin P-5 had a weight-average molecular weight of 27,000, a number-average molecular weight of 15,000, and an acid value of 95 mgKOH / g. The amount of residual monomers, as measured by gas chromatography, was less than 0.1% by mass relative to the polymer solids.

[0854] <Synthesis of Resin P-6>

[0855] Resin P-6 was obtained by referring to the synthesis method of resin P-5.

[0856] Specifically, in the dropping liquid (1) used for the synthesis of resin P-5, the structure using methacrylic acid (107.1 g), methyl methacrylate (5.46 g), and cyclohexyl methacrylate (231.42 g) as monomers was changed to the structure using the monomers shown in Table 7 below. In addition, the amount of glycidyl methacrylate (76.03 g) added was also changed to obtain the composition of MAA-GMA shown in Table 7 below.

[0857] The solid content concentration of the obtained solution of resin P-6 was 36.3% by mass, and the weight average molecular weight of resin P-6 was 17,000.

[0858] Table 7 shows the composition (mass %) of resin P-6. In Table 7, "St" refers to a structural unit derived from styrene, "MAA" refers to a structural unit derived from methacrylic acid, and "MMA" refers to a structural unit derived from methyl methacrylate. Furthermore, "MAA-GMA" refers to a structural unit derived from methacrylic acid to which glycidyl methacrylate has been added.

[0859] [Table 7]

[0860] P-6 St 47.7 MAA-GMA 32 MAA 19 MMA 1.3 Weight average molecular weight (Mw) 17000

[0861] In addition, resins P-5 and P-6 may be any alkali-soluble resins. Resins P-5 and P-6 are added to the photosensitive resin composition in the form of solutions containing the resins.

[0862] [Synthesis of Blocked Isocyanate Compounds]

[0863] <Synthesis of Blocked Isocyanate Compound Q-1>

[0864] Under nitrogen flow, butanone oxime (manufactured by Idemitsu Kosan Co., Ltd.) (453 g) was dissolved in methyl ethyl ketone (700 g). Under ice cooling, 1,3-bis(isocyanatomethyl)cyclohexane (cis- and trans-isomer mixture, manufactured by Mitsui Chemicals, Inc., Takenate 600) (500 g) was added dropwise to the obtained solution over 1 hour, and the reaction was further carried out for 1 hour after the addition. Then, the above solution was heated to 40° C. and reacted for 1 hour. 1 Completion of the reaction was confirmed by H-NMR (Nuclear Magnetic Resonance) and HPLC (High Performance Liquid Chromatography), and a methyl ethyl ketone solution (solid content concentration: 57.7% by mass) of a blocked isocyanate compound Q-1 (see the following formula) was obtained.

[0865] In addition, the blocked isocyanate compound Q-1 is added to the photosensitive resin composition in the form of a solution containing the blocked isocyanate compound Q-1.

[0866] [Chemical Formula 20]

[0867]

[0868] <Synthesis of Blocked Isocyanate Compound Q-8>

[0869] Referring to the synthesis method of the blocked isocyanate compound Q-1, a methyl ethyl ketone solution (solid content concentration: 75.0% by mass) of the blocked isocyanate compound Q-8 (see the following formula) was obtained.

[0870] In addition, the blocked isocyanate compound Q-8 is added to the photosensitive resin composition in the form of a solution containing the blocked isocyanate compound Q-8.

[0871] [Chemical Formula 21]

[0872]

[0873] [Preparation of Photosensitive Resin Compositions 12 to 14]

[0874] These components were stirred and mixed according to the formulations described in Table 8 below to prepare photosensitive resin compositions 12 to 14. The units of the amounts of the components are parts by mass.

[0875] In the table, the column "Average film thickness of photosensitive resin layer (μm)" shows the average film thickness of the photosensitive resin layer formed when the test was performed using each photosensitive resin composition. The details of the test will be described later.

[0876] [Table 8]

[0877]

[0878] 〔test〕

[0879] <Example 12>

[0880] The photosensitive resin composition 12 was applied onto a temporary support of a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY IND USTRIES, INC.)) using a slit nozzle, adjusting the coating amount of the photosensitive resin composition so that the average film thickness of the photosensitive composition layer after drying would be a predetermined film thickness.

[0881] Next, the temporary support was passed through a 3 m drying zone with a temperature of 80°C and an air intake and exhaust volume adjusted to set the wind speed on the membrane surface to 3 m / sec for 60 seconds, thereby forming a photosensitive resin layer (negative photosensitive resin layer) on the temporary support.

[0882] <Example 13, Comparative Example 4>

[0883] Except having changed the average film thickness of the photosensitive resin composition and the formed photosensitive resin layer as described in Table 8, the same procedures as those for the photosensitive resin composition 12 were carried out to prepare and evaluate the coating films.

[0884] [Evaluation of coating properties]

[0885] As described above, the coating properties of each composition (photosensitive resin composition, etc.) when forming a composition layer (photosensitive resin layer, etc.) were evaluated in five stages, A to E, by observing the state from application to drying. The meanings of A to E are as follows. C and above represent the actual usage level.

[0886] A: After application, the product is evenly spread over the entire surface, and the coating properties are very good.

[0887] B: The coating film is slightly thick by a few mm at both ends after application, but it is leveled before drying and the coating property is good.

[0888] C: Slight unevenness was observed after application, but the coating film was leveled before drying except for a few mm at both ends, and the coating properties were fair.

[0889] D: There was no depression after application, but unevenness was observed and leveling was not performed until drying, indicating poor coating properties.

[0890] E: After application, depressions occurred on the entire surface, or application was impossible, or application properties were very poor.

[0891] Table 9 shows the evaluation results.

[0892] In the following description, the "compound used" refers to the type of Compound A or comparative compound contained in the composition.

[0893] [Table 9]

[0894] Composition Use compound Coating surface Example 1 Photosensitive resin composition 1 A-1 A Example 2 Photosensitive resin composition 2 A-5 B Example 3 Photosensitive resin composition 3 A-6 B Example 4 Photosensitive resin composition 4 A-9 C Example 5 Photosensitive resin composition 5 B-1 C Example 6 Photosensitive resin composition 6 A-1 A Example 7 Photosensitive resin composition 7 A-1 A Example 8 Photosensitive resin composition 8 A-9 C Comparative Example 1 Photosensitive resin composition 9 F552 D Example 9 Thermoplastic resin composition 1 A-1 A Example 10 Thermoplastic resin composition 2 A-1 A Comparative Example 2 Thermoplastic resin composition 3 F551A D Example 11 Photosensitive resin composition 10 A-1 A Comparative Example 3 Photosensitive resin composition 11 F555A D Example 12 Photosensitive resin composition 12 A-1 A Example 13 Photosensitive resin composition 13 A-1 A Comparative Example 4 Photosensitive resin composition 14 F551A D

[0895] From the results of the Examples, it was confirmed that the composition of the present invention can produce a film having excellent coating properties and high homogeneity.

[0896] Among them, it was confirmed that the coating properties were more excellent when the composition contained the polymer compound A having a poly(oxyalkylene) structure.

[0897] Among them, it was confirmed that the coating properties were more excellent when the composition had a poly(oxyalkylene) structure and the polymer compound A had a weight average molecular weight of 5,000 to 11,500.

[0898] [Production of transfer film and its use]

[0899] [Example 1 of Preparation and Use of Transfer Film: Example 14]

[0900] The thermoplastic resin composition 1 prepared in Example 9 was applied to a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) at a width of 1.0 m using a slit nozzle so that the average film thickness of the composition layer after drying was 2.0 μm. The film was then passed through a 3 m drying zone set at 80° C., where the air intake and exhaust volumes were adjusted to achieve a film-surface wind speed of 0.2 m / sec, for 60 seconds. This yielded a laminate A of a temporary support and a thermoplastic resin layer.

[0901] Subsequently, a water-soluble resin composition, described below, was applied to the thermoplastic resin layer of the prepared laminate A using a slit nozzle, with the coating amount adjusted so that the average film thickness of the composition layer after drying would be 1.0 μm. The laminate A was then passed through a 3 m drying zone at 100°C for 60 seconds, with the air intake and exhaust volumes adjusted to achieve a wind speed of 3 m / sec across the film surface. This yielded a laminate B having a water-soluble resin layer formed on the thermoplastic resin layer.

[0902] (Water-soluble resin composition)

[0903] These components were stirred and mixed according to the following formulation, thereby preparing a water-soluble resin composition.

[0904] Water-soluble resin ("PVA 205", manufactured by KURARAY CO., LTD.) 32.2 parts by mass

[0905] Water-soluble resin (polyvinyl pyrrolidone, manufactured by NIPPON SHOKUBAI CO., LTD.)

[0906] 14.9 parts by mass

[0907] Megaface F444 (manufactured by DIC Corporation) 0.01 parts by mass

[0908] 524.0 parts by mass of ion exchange water

[0909] Methanol (manufactured by MITSUBISHIGAS CHEMICAL COMPANY, INC.) 429.0 parts by mass

[0910] Subsequently, the photosensitive resin composition 1 prepared in Example 1 was applied to the water-soluble resin layer of the prepared laminate B using a slit nozzle, with the coating amount adjusted so that the average film thickness of the composition layer after drying would be 2.0 μm. The laminate B was then passed through a 3 m drying zone at 80°C for 60 seconds, with the air intake and exhaust volumes adjusted to a wind speed of 0.2 m / sec across the film surface. This yielded a laminate having a photosensitive resin layer formed on the water-soluble resin layer.

[0911] Finally, a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.) having a thickness of 16 μm was pressure-bonded as a cover film to prepare a transfer film (Example 14).

[0912] A PET substrate with a copper layer was prepared by providing a 200 nm thick copper layer on a 100 μm thick polyethylene terephthalate (PET) film by a sputtering method.

[0913] After the transfer film was rolled out, the above-mentioned PET substrate with a copper layer was laminated under the lamination conditions of a laminating roller temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. At this time, the cover film was peeled off and lamination was performed so that the photosensitive resin layer in the transfer film was in contact with the copper layer. After exposure to a line and space pattern (Duty ratio 1:1, line width 20 μm) under an ultra-high pressure mercury lamp without peeling off the temporary support, the temporary support was peeled off and development was performed. During development, a 1.0% sodium carbonate aqueous solution at 25°C was used, and spray development was performed for 30 seconds. When a line and space pattern was formed by the above method, good resolution was shown.

[0914] [Example 2 of Preparation and Use of Transfer Film: Example 15]

[0915] The photosensitive resin composition 12 prepared in Example 12 was applied onto a temporary support of a 16 μm-thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY IND USTRIES, INC.)) using a slit nozzle. The amount of the photosensitive resin composition applied was adjusted so that the width was 1.0 m and the thickness of the photosensitive composition layer after drying was 8.0 μm. The resulting temporary support was then passed through a 3 m drying zone at 80° C. for 60 seconds, where the air intake and exhaust volumes were adjusted to achieve a film-surface wind speed of 0.2 m / sec. This yielded a laminate C of the temporary support and the photosensitive resin layer.

[0916] Subsequently, a resin composition (refractive index adjusting layer-forming composition) described below was applied to the photosensitive resin layer of the prepared laminate C using a slit nozzle, with the coating amount adjusted so that the average film thickness of the composition layer after drying would be 80 nm. The laminate C was then passed through a 3 m drying zone at 80°C for 60 seconds, with the air intake and exhaust volumes adjusted to achieve a wind speed of 3 m / sec across the film surface. This yielded a laminate having a refractive index adjusting layer formed on the photosensitive resin layer.

[0917] Finally, a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.) having a thickness of 16 μm was pressure-bonded as a cover film to prepare a transfer film (Example 15).

[0918] (Composition for forming refractive index adjusting layer)

[0919] These components were stirred and mixed according to the following formulation to prepare a composition for forming a refractive index adjusting layer. The following composition for forming a refractive index adjusting layer was used to form a refractive index adjusting layer.

[0920] NanoUse OZS-30M (ZrO2 particles (containing tin oxide) methanol dispersion (30.5% by mass of non-volatile matter), manufactured by Nissan Chemical Industries, Ltd.) 4.34 parts by mass

[0921] Ammonia water (25% by mass) 7.84 parts by mass

[0922] 0.21 parts by mass of polymer P-7 obtained by the synthesis method described below

[0923] ARUFON UC-3920 (manufactured by OAGOSEI CO., LTD.) 0.08 parts by mass

[0924] ARONIXTO-2349 (manufactured by OAGOSEI CO., LTD.) 0.03 parts by mass

[0925] Benzotriazole BT-LX (manufactured by JOHOKU CHEMICAL CO., LTD.) 0.03 parts by mass

[0926] 0.02 parts by mass of monoisopropanolamine

[0927] Megaface F444 (manufactured by DIC Corporation) 0.01 parts by mass

[0928] 21.7 parts by mass of ion exchange water

[0929] 65.8 parts by mass of methanol

[0930] (Synthesis of Polymer P-7)

[0931] Propylene glycol monomethyl ether (270.0 g) was introduced into a three-necked flask, and the temperature was raised to 70° C. under a nitrogen stream while stirring.

[0932] On the other hand, a dropwise solution was prepared by dissolving allyl methacrylate (45.6 g, FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4 g) in propylene glycol monomethyl ether (270.0 g), further dissolving V-65 (3.94 g, FUJIFILM Wako Pure Chemical Corporation), and adding the solution dropwise to the flask over 2.5 hours. The mixture was kept stirred for 2.0 hours and reacted. Then, the temperature of the contents of the flask was returned to room temperature, and the contents of the flask were added dropwise to 2.7 L of ion exchange water in a stirred state, and reprecipitation was performed to obtain a suspension. The suspension was filtered with a suction filter (Buchner funnel) with filter paper, and the filtrate was further washed with ion exchange water to obtain a powder in a wet state. After air drying at 45°C, it was confirmed that constant weight was reached, and resin A-7 was obtained as a powder with a yield of 70%. The amount of residual monomers measured by gas chromatography was less than 0.1% by mass based on the polymer solid content.

[0933] After the protective film was removed from the resulting transfer film, it was laminated onto both sides of a polyethylene terephthalate film, Cosmo Shine A4300 (50 μm thick), manufactured by Toray Industries, Inc., which had been heat-treated at 145°C for 30 minutes. This resulted in a laminate having a layer structure of temporary support / photosensitive composition layer / refractive index adjusting layer / Cosmo Shine A4300 (50 μm thick) / refractive index adjusting layer / photosensitive composition layer / temporary support. Lamination conditions were a laminating roll temperature of 110°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min.

[0934] Then, a proximity exposure machine (manufactured by Hitachi High-Tech Corporation.) equipped with an ultra-high pressure mercury lamp was used to expose the film at an exposure dose of 100 mJ / cm2 via the temporary support. 2 After peeling off the temporary supports on both sides, the exposure dose was further 400 mJ / cm 2After double-side exposure (i-line), post-baking was performed at 145° C. for 25 minutes to cure the photosensitive composition layer to form a cured film.

[0935] Thus, a sample comprising 10 μm thick cured film / refractive index adjusting layer / Cosmo Shine A4300 (50 μm thick) / refractive index adjusting layer / 10 μm thick cured film was obtained. These films had excellent uniformity, with no surface reflection unevenness observed, and were considered good.

[0936] [Example 3 of Preparation and Use of Transfer Film: Example 16]

[0937] The photosensitive resin composition 1 prepared in Example 1 was applied to a 16 μm thick polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) at a width of 1.0 m using a slit nozzle so that the average film thickness of the composition layer after drying was 2.0 μm. The composition was then passed through a 3 m drying zone set at 80° C., where the air intake and exhaust volumes were adjusted to achieve a film-surface wind speed of 0.2 m / sec, for 60 seconds, thereby obtaining a laminate A of a temporary support and a photosensitive resin layer.

[0938] Next, a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by TORAY INDUSTRIES, INC.)) having a thickness of 16 μm was pressure-bonded as a cover film to produce a transfer film (Example 16).

[0939] A PET substrate with a copper layer was prepared by providing a 200 nm thick copper layer on a 100 μm thick polyethylene terephthalate (PET) film by a sputtering method.

[0940] After the transfer film was rolled out, the above-mentioned PET substrate with a copper layer was laminated under the lamination conditions of a laminating roller temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. At this time, the cover film was peeled off and lamination was performed so that the photosensitive resin layer in the transfer film was in contact with the copper layer. After exposure to a line and space pattern (Duty ratio 1:1, line width 20 μm) under an ultra-high pressure mercury lamp without peeling off the temporary support, the temporary support was peeled off and development was performed. During development, a 1.0% sodium carbonate aqueous solution at 25°C was used, and spray development was performed for 30 seconds. When a line and space pattern was formed by the above method, good resolution was shown.

[0941] Explanation of symbols

[0942] 10 - Temporary support, 12 - Thermoplastic resin layer, 14 - Intermediate layer, 16 - Negative photosensitive resin layer, 18 - Cover film, 100 - Transfer film.

Claims

1. A composition comprising an alkali-soluble resin, a polymerizable compound and a compound A, The compound A is a polymer compound with a weight average molecular weight of 5000 or more, The polymer compound includes a structural unit derived from a monomer represented by the following general formula (4A), Where R 1 represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or -N(R 2 )-, m and n each independently represent an integer of 1 to 6, R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, The polymer compound further comprises a structural unit derived from a monomer represented by the following general formula (5), Where R 3 represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or -N(R 5 )-, AL represents an alkylene group optionally having a substituent, nAL represents an integer greater than 2, R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 5 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The composition according to claim 1 , further comprising a polymerization initiator.

3. The composition according to claim 1, wherein The alkali-soluble resin is a thermoplastic resin. The composition according to claim 1 , further comprising black particles.

5. A transfer film comprising a temporary support and one or more composition layers, At least one of the composition layers is a layer formed using the composition according to any one of claims 1 to 4.

6. A method for manufacturing a laminate, comprising: a laminating step of bringing a substrate into contact with a surface of the transfer film according to claim 5 on the side opposite to the temporary support, laminating the transfer film and the substrate to obtain a substrate with a transfer film; an exposure step of performing pattern exposure on the composition layer; and a developing step of developing the exposed composition layer to form a resin pattern, The method for producing a laminate further includes a peeling step of peeling the temporary support from the substrate with the transfer film between the laminating step and the exposure step or between the exposure step and the development step.

7. A method for manufacturing a circuit wiring, comprising: a laminating step of bringing the surface of the transfer film according to claim 5 opposite to the temporary support into contact with a substrate having a conductive layer, laminating the transfer film and the substrate having the conductive layer to obtain a substrate with a transfer film; an exposure step of performing pattern exposure on the composition layer; a developing step of developing the exposed composition layer to form a resin pattern; and an etching step of etching the conductive layer in a region where the resin pattern is not provided, The method for producing a circuit wiring further includes a peeling step of peeling the temporary support from the substrate with the transfer film between the laminating step and the exposure step or between the exposure step and the development step. 8 . A method for producing an electronic device, comprising the method for producing a laminate according to claim 6 , wherein the electronic device includes the resin pattern as a cured film.

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