Composition, transfer film, laminate manufacturing method, circuit wiring manufacturing method, and electronic device manufacturing method

Abstract

The present invention addresses the problem of providing a composition having exceptional coating properties. The present invention also addresses the problem of providing a transfer film, a method for producing a laminate, a method for producing circuit wiring, and a method for producing an electronic device that relate to the composition.　This composition includes an acrylic soluble resin, a polymerizable compound, and a compound A, the compound A having a group represented by general formula (1).　General formula (1): *-CF2-H In the formula, * represents a bond 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 circuit wiring, and a method for producing an electronic device.

[0002] 2. Description of the Related Art Transfer films such as photosensitive transfer materials have been increasingly used in various fields in recent years. Photosensitive transfer materials can contribute to reducing product costs, and therefore their use as etching resist films, wiring protection films, and the like has been proposed. Accordingly, in accordance with each field, in addition to the properties of the polymer as a matrix, the coatability when producing a transfer film is also becoming important.

[0003] For example, in Patent Document 1, a transfer film is produced using a photosensitive composition to which a fluorine-containing group / lipophilic group-containing oligomer has been added (see Patent Document 1,

[0211] ,

[0214] ,

[0215] , etc.). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 008376 Summary of the Invention [Problem to be solved by the invention]

[0005] As a result of investigations by the present inventors, it was found that there is room for improvement in the coatability of the composition (photosensitive composition) disclosed in Patent Document 1. In addition, the excellent coatability of the composition means that when the composition is applied, repelling of the composition is unlikely to occur, and uneven application of the composition is unlikely to occur, making it easy to obtain a homogeneous film (composition layer), etc.

[0006] In view of the above, an object of the present invention is to provide a composition having excellent coatability. Another object of the present invention is to provide a method for producing a transfer film, a laminate, a circuit wiring, and an electronic device, which are related to the composition. [Means for solving the problem]

[0007] As a result of intensive research by the present inventors to solve the above problems, they have found that the above problems can be achieved by the following configuration.

[0008] [1] A composition comprising an alkali-soluble resin, a polymerizable compound, and a compound A, The composition, wherein the compound A is a compound having a group represented by general formula (1) described below. [2] The composition according to [1], wherein the compound A is a compound having a group represented by general formula (2) described below. [3] The composition according to [1] or [2], wherein the compound A is a compound having a group represented by general formula (3) described below. [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. [5] The compound A is a polymer compound, The composition according to any one of [1] to [4], wherein the polymer compound contains a structural unit derived from a monomer represented by general formula (4A) described later. [6] The composition according to [5], wherein the polymer compound further contains a structural unit derived from a monomer represented by general formula (5) described later. [7] The composition according to any one of [1] to [3], wherein the compound A has a molecular weight of 2,000 or less. [8] The composition according to any one of [1] to [3] and [7], wherein the compound A is a compound represented by general formula (6A) described later. [9] The composition according to [8], wherein Z represents a monovalent organic group containing a poly(oxyalkylene) structure moiety which may have a substituent.

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

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

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

[11] , further comprising black particles.

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

[12] .

[14] A bonding step of contacting a substrate with a surface of the transfer film according to

[13] opposite to the temporary support, and bonding the transfer film and the substrate to obtain a substrate with a transfer film; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed composition layer to form a resin pattern; The method for producing a laminate further comprises 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.

[15] A bonding step of contacting a surface of the transfer film according to

[13] opposite to the temporary support with a substrate having a conductive layer, and bonding the transfer film and the substrate having the conductive layer to obtain a substrate with a transfer film; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed composition layer to form a resin pattern; an etching step of etching the conductive layer in an area where the resin pattern is not disposed; The method for producing circuit wiring further comprises 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.

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

[14] , The electronic device includes the resin pattern as a cured film. Effect of the Invention

[0009] According to the present invention, it is possible to provide a composition having excellent coatability. It is also possible to provide a method for producing a transfer film, a laminate, a circuit wiring, and an electronic device, which are related to the composition. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram showing an example of a configuration of a transfer film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in the present specification, the bonding direction of a divalent group (for example, --CO--O--) is not particularly limited.

[0012] In this specification, (meth)acrylate refers to acrylate and methacrylate, (meth)acrylic acid refers to acrylic acid and methacrylic acid, and (meth)acryloyl group refers to methacryloyl group or acryloyl group.

[0013] In the present specification, when a group (atomic group) is described without indicating whether it is substituted or unsubstituted, it includes both a group having no substituent and a group having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, in the present specification, an "organic group" refers to a group containing at least one carbon atom.

[0014] In addition, in the present specification, when it is said that "may have a substituent", the type of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of the substituents may be, for example, one, two, three, or more. In addition, it may be unsubstituted. Examples of the substituent include monovalent nonmetallic atomic groups other than hydrogen atoms, and can be selected from the following substituent group T. (substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxalyl group. Examples of the alkyl group include acyl groups; alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups; and combinations thereof.

[0015] 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). GPC is measured under the following conditions. [Eluent] Tetrahydrofuran (THF) [Device name] EcoSEC HLC-8320GPC (Tosoh Corporation) [Column] TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (Tosoh Corporation) [Column temperature] 40℃ [Flow rate] 0.35ml / min

[0016] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).

[0017] In this specification, room temperature is 25° C. unless otherwise specified.

[0018] In this specification, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at 22°C is 0.1 g or more. In this specification, the term "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more. In this specification, the layer thickness (film thickness) of each layer in a transfer film or the like is measured by observing a cross section of the layer (film) in a direction perpendicular to the main surface thereof with a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

[0019] [Composition] 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 general formula (1) described below. The mechanism by which the problem of the present invention is solved by such a configuration is not necessarily clear, but the present inventors speculate as follows. Compound A contains in its structure a fluoroalkyl group (a group represented by general formula (1)) containing a hydrogen atom at the terminal portion. Such compound A has good compatibility with resins and the like in the composition, and good solubility in an organic solvent (which may be a water-soluble solvent) added as desired. This is believed to result in less aggregation of compound A in the composition, less uneven coating of the composition, and improved coating properties. In addition, when compound A further has a poly(oxyalkylene) structural portion, compound A is believed to be more likely to migrate to the coating film surface. It is presumed that the presence of such compound A in the composition reduces the surface tension of the coating film, improves the wettability of the composition to the substrate during coating, and improves the surface condition of the coating film, thereby improving the coatability. Furthermore, when compound A is a polymer compound having a poly(oxyalkylene) structural portion and a weight average molecular weight of 5,000 to 11,500, it is presumed that compound A migrates to the coating film surface at a faster rate, and the coating properties are further improved.

[0020] [Compound A] The composition of the present invention comprises Compound A. Compound A is a compound having a group represented by the following general formula (1). General formula (1):*-CF2-H In the formula, * represents the bonding position.

[0021] Compound A may be a polymeric compound or a low molecular weight compound. When compound A is a polymeric compound, compound A, which is a polymeric compound, may be referred to as "polymeric compound A". When compound A is a low molecular weight compound, compound A, which is a low molecular weight compound, may be referred to as "low molecular weight compound A". Compound A is preferably polymeric compound A in that the effects of the present invention are more excellent.

[0022] The lower limit of the weight-average molecular weight of the polymer compound A is preferably 1,000 or more, more preferably 1,500 or more, even 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, even more preferably 60,000 or less, even more preferably 40,000 or less, particularly preferably 20,000 or less, and most preferably 11,500 or less. The number average molecular weight (Mn) of the polymer compound A is preferably from 500 to 40,000, more preferably from 600 to 20,000, and even more preferably from 600 to 10,000. The dispersity (Mw / Mn) of the polymer compound A is preferably from 1.00 to 12.00, more preferably from 1.00 to 11.00, and even more preferably from 1.00 to 10.00. The polymer compound A preferably contains a structural unit having a group represented by general formula (1).

[0023] The molecular weight of the low molecular weight compound A is preferably 100 or more, and more preferably 500 or more. The upper limit of the molecular weight of the low molecular weight compound A is preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less. The number of groups represented by general formula (1) in the low molecular weight compound A is not particularly limited as long as it is 1 or more, but it is preferably 1 to 3, for example.

[0024] Specific embodiments of the polymer compound A and the low molecular weight compound A will be described later.

[0025] In terms of achieving better effects of the present invention, compound A is preferably a compound having a group represented by general formula (2) described below (hereinafter also referred to as "compound Aa"), and more preferably a compound having a group represented by general formula (3) described below (hereinafter also referred to as "compound Ab").

[0026] In addition, compound Aa corresponds to a compound in which the linking form of the group represented by general formula (1) in compound A is more limited. In other words, -CF2-H present at the terminal portion of the group represented by general formula (2) in compound Aa corresponds to the group represented by general formula (1) described above. In addition, compound Ab is intended to be a compound in which the linking form of the group represented by general formula (1) in compound A and the linking form of the group represented by general formula (2) in compound Aa are more limited. In other words, -CF2-H present at the terminal portion of the group represented by general formula (3) in compound Ab corresponds to the group represented by general formula (1) described above, and -CF2-CF2-H present at the terminal portion of the group represented by general formula (3) in compound Ab corresponds to the group represented by general formula (2) described above.

[0027] General formula (2):*-CF2-CF2-H In the formula, * represents the bonding position.

[0028] General formula (3):*-(CH2) m -(CF2-CF2) n -H In the formula, m and n each independently represent an integer of 1 to 6. m is preferably 1 to 4, and more preferably 1 or 2. n is preferably 1 to 4, and more preferably 2 or 3. * indicates the bond position.

[0029] Polymer compound A and low molecular weight compound A will be described below.

[0030] <High molecular compound A> As described above, the polymer compound A is an embodiment in which the compound A is a polymer compound. The preferred embodiments of the weight average molecular weight and dispersity of the polymer compound A are as described above. The polymer compound A preferably contains a structural unit having a group represented by any one of the general formulae (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. Note that the structural unit derived from a 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) described above, and the structural unit derived from a 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.

[0031] [ka]

[0032] In 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 R represents a divalent linking group. T represents a group represented by the above general formula (1) or (2).

[0033] R 2 The alkyl group having 1 to 4 carbon atoms represented by the following formula may be any of linear, branched, and cyclic.

[0034] R 1 is preferably a hydrogen atom. R 2 is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. X is preferably an oxygen atom.

[0035] L 1 The divalent linking group represented by the formula (I) is not particularly limited, and examples thereof include -O-, -CO-, -S-, -SO2-, -NR X -(R Xis 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 combining these. X The substituent represented by the formula (I) is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents, and an alkyl group having 1 or 2 carbon atoms is preferable. The alkylene group, alkenylene group, alkynylene group, 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 the substituent group T. Among them, the substituent is preferably a halogen atom, and more preferably a fluorine atom.

[0036] The alkylene group, the alkenylene group, and the alkynylene group may be linear or branched. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 11 carbon atoms, and particularly preferably 1 to 10 carbon atoms. The alkenylene group and the alkynylene group preferably have 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, further preferably 2 to 11 carbon atoms, and particularly preferably 2 to 10 carbon atoms.

[0037] The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic ring constituting the aromatic ring group may be a single ring or a polycyclic ring. The number of ring members constituting the aromatic ring group is not particularly limited, but is, for example, 5 to 15. The number of heteroatoms contained in the aromatic heterocyclic group is not particularly limited, but is, for example, preferably 1 to 3. The type of heteroatom is not particularly limited, but may, for example, be a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of the types of aromatic rings 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 heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.

[0038] The alicyclic group may be either an aliphatic hydrocarbon ring group or an aliphatic heterocyclic group. The alicyclic ring constituting the alicyclic group may be a single ring or a polycyclic ring. The number of ring members of the alicyclic ring constituting the alicyclic group is not particularly limited, but is, for example, 5 to 15. The number of heteroatoms contained in the aliphatic heterocyclic group is not particularly limited, but is, for example, preferably 1 to 3. The type of heteroatom is not particularly limited, but may, for example, be a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of the alicyclic ring constituting the alicyclic group include cycloalkane rings such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a cyclodecane ring, an adamantane ring, a norbornane ring, and an exo-tetrahydrodicyclopentadiene ring, and a cyclohexene ring.

[0039] L 1 Among them, the divalent linking group represented by the formula: A -Alkylene group optionally substituted with a fluorine atom-* B , * A -Alkenylene group optionally substituted with a fluorine atom-* B , or * A -Alkynylene group optionally substituted with a fluorine atom-* B is preferred, * A -Alkylene group optionally substituted with a fluorine atom-* B is more preferable. A represents the position of connection to X in formula (4), B is R in Eq. (4). T Represents the connection position with.

[0040] [ka]

[0041] In formula (4A), R 1 and X are each R in formula (4). 1 and X have the same meanings and preferred embodiments. m and n each independently represent an integer of 1 to 6. m is preferably an integer of 1 to 4, and more preferably 1 or 2. n is preferably an integer of 1 to 4, and more preferably 2 or 3.

[0042] The lower limit of the content of the structural unit having a group represented by any one of the general formulae (1) to (3) in the polymer compound A is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 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. As the structural unit having a group represented by any one of general formulas (1) to (3), one type may be used alone, or two or more types may be used. A structural unit having a group represented by any one of general formulas (1) to (3) can be synthesized by a known method.

[0043] The polymer compound A may have other structural units (hereinafter also referred to as "other structural units") other than the structural units having a group represented by any one of the general formulae (1) to (3). The other structural units are not particularly limited, but in terms of providing better effects for the present invention, it is preferable to include a structural unit having a poly(oxyalkylene) structure. The poly(oxyalkylene) structure is preferably a structure represented by the following formula (PAL).

[0044] [ka]

[0045] In formula (PAL), nAL represents an integer of 2 or more, more preferably 2 to 100, further preferably 4 to 20, particularly preferably 4 to 15, and most preferably 4 to 12. 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. There are nAL of these, and each AL may be the same or different. The alkylene group represented by AL may have a substituent. The substituent is not particularly limited, but examples thereof include the substituents exemplified in the group T of substituents. Of these, -AL is preferably -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2- or -CH(CH2CH3)CH2-, and more preferably -CH(CH3)CH2- or -CH2CH2CH2-. * indicates the bond position.

[0046] The structural unit having a poly(oxyalkylene) structure is preferably one having a poly(oxyalkylene) structure in a side chain, and is more preferably a structural unit derived from a monomer represented by general formula (5) described below.

[0047] [ka]

[0048] In the formula, 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 of 2 or more. R 4 represents a hydrogen atom or a substituent. 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0049] AL and nAL in formula (5) have the same meanings as AL and nAL in formula (PAL), and the preferred embodiments are also the same. R 4 The substituent represented by the formula (I) is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents, and is preferably an alkyl group having 1 to 6 carbon atoms. R 5 The alkyl group having 1 to 4 carbon atoms represented by the following formula may be any of linear, branched, and cyclic.

[0050] R 3 and R 4 is preferably a hydrogen atom. R 5 is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. Y is preferably an oxygen atom.

[0051] When the polymer compound A contains a constitutional 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, based on the total mass of the polymer compound A. The upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less. The structural unit having a poly(oxyalkylene) structure may be used alone or in combination of two or more kinds.

[0052] As other structural units that the polymer compound A may contain, in addition to the above-mentioned structural units, for example, structural units derived from (meth)acrylic acid esters and structural units derived from (meth)acrylic acid are also preferred. Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl esters in which the alkyl group has a carbon number of 1 to 18. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.

[0053] When the polymer compound A contains a structural unit selected from the group consisting of a structural unit derived from a (meth)acrylic acid ester 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, based on 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.

[0054] When the polymer compound A is a copolymer, it is also preferable that the polymer compound A has a block structure, a graft structure, a branch structure, and / or a star structure.

[0055] The various monomers constituting the polymer compound A and the polymer compound A can be produced by known methods.

[0056] <Low molecular compound A> As described above, the low molecular weight compound A is an embodiment in which the compound A is a low molecular weight compound. The preferred embodiment of the molecular weight of the low molecular weight compound A is as described above.

[0057] The low molecular weight compound A is preferably a compound having a group represented by any one of the general formulae (1) to (3) described above, more preferably a compound represented by (6) described below, even more preferably a compound represented by general formula (6A) described below, and particularly preferably a compound represented by general formula (6B) described below. The compound represented by general formula (6) described below corresponds to the compound having a group represented by general formula (1) or (2) described above, and the compound represented by general formula (6A) or (6B) described below corresponds to the compound having a group represented by general formula (3) described above.

[0058] [ka]

[0059] In the general formula (6), Z represents a monovalent organic group. 2 R represents a single bond or a divalent linking group. T represents a group represented by the above general formula (1) or (2).

[0060] The monovalent organic group represented by Z is not particularly limited, but may contain, for example, a heteroatom (heteroatoms include, for example, -O-, -CO-, -S-, -SO2-, and -NR X -(R Xis a hydrogen atom or a substituent), an alkyl group, an alkenyl group, and an alkynyl group. X The substituent represented by the formula (I) is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents. The alkyl group, alkenyl group, and alkynyl group may further have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified in the substituent group T. The alkyl group, alkenyl group, and alkynyl group may be any of linear, branched, and cyclic. The number of carbon atoms in the alkyl group is not particularly limited, but is, for example, 1 to 40, preferably 1 to 30, and more preferably 1 to 20. The number of carbon atoms in the alkenyl group and the alkynyl group is not particularly limited, but is, for example, 2 to 40, preferably 2 to 30, and more preferably 2 to 20.

[0061] Among them, Z is preferably a monovalent organic group having a poly(oxyalkylene) structure. The poly(oxyalkylene) structure is preferably the structure represented by the above formula (PAL). In addition, L in the formula (6) of Z 2 The atom at the linking position to is preferably a carbon atom.

[0062] L 2 Examples of the divalent linking group represented by the formula (4) include L 1 Examples of the divalent linking group include those similar to those represented by the following formula: L 2 Among them, the divalent linking group represented by the formula: A -L 21 -Alkylene group optionally substituted with a fluorine atom-* B , * A -L 21 -Alkenylene group optionally substituted with a fluorine atom-* B , or * A -L 21 -Alkynylene group optionally substituted with a fluorine atom-* Bis preferred, * A -L 21 -Alkylene group optionally substituted with a fluorine atom-* B is more preferred. L 21 -O-, -CO-, -S-, -SO2-, -NR X -(R X represents a hydrogen atom or a substituent, or a group formed by combining these. X The substituent represented by the formula (I) is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents, and an alkyl group having 1 or 2 carbon atoms is preferable. 21 Among them, -O-, -S-, or -NR X It is preferably -, and more preferably -O-. * A represents the position of connection with Z in formula (6), B is R in Eq. (6). T Represents the connection position with.

[0063] [ka]

[0064] In the formula, Z represents a monovalent organic group. 3 is an oxygen atom, a sulfur atom, or -N(R 6 m and n each independently represent an integer of 1 to 6. 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0065] Examples of the monovalent organic group represented by Z in formula (6A) include the same as the monovalent organic group represented by Z in formula (6), and preferred embodiments are also the same. R 6 The alkyl group having 1 to 4 carbon atoms represented by the following formula may be any of linear, branched, and cyclic. L 3 is preferably an oxygen atom. m is preferably 1 to 4, and more preferably 1 or 2. n is preferably 1 to 4, and more preferably 2 or 3.

[0066] [ka]

[0067] AL and nAL in formula (6B) have the same meanings as AL and nAL in formula (PAL), and the preferred embodiments are also the same. L in formula (6B) 3 , m, and n each represent L in formula (6A). 3 , m, and n have the same meanings and preferred embodiments.

[0068] In formula (6B), R 7 represents a hydrogen atom or a substituent. R 7 The substituent represented by the formula (I) is not particularly limited, and examples thereof include the substituents exemplified in the group T of substituents, and is preferably an alkyl group having 1 to 6 carbon atoms. R 7 is preferably a hydrogen atom.

[0069] The low molecular weight compound A can be produced by a known method.

[0070] Specific examples of compound A are given below, but compound A in the present invention is not limited thereto.

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] The content of compound A is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, and even more preferably 0.02 to 1 mass%, based on the total solid content of the composition (such as the negative photosensitive resin composition, thermoplastic resin composition, and / or colored resin composition described below). In this specification, the "solid content" of a composition means components that form a composition layer (e.g., a negative photosensitive resin layer, etc.) formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), means all components excluding the solvent. In addition, liquid components are also considered to be solid contents if they form a composition layer.

[0076] [Alkali-soluble resin] The composition of the present invention contains an alkali-soluble resin. The alkali-soluble resin is a component different from the polymer compound A. There are no limitations on the properties and / or characteristics of the alkali-soluble resin, and they can be appropriately selected depending on the application of the composition. The alkali-soluble resin contained in the composition of the present invention will be described in detail below according to the type of the composition.

[0077] [Polymerizable compound] The composition of the present invention contains a polymerizable compound. There are no limitations on the properties and / or characteristics of the polymerizable compound, and they can be appropriately selected depending on the application of the composition. The details of the polymerizable compound contained in the composition of the present invention will be described later according to each form of the composition.

[0078] [Other ingredients] The composition of the present invention may contain other components in addition to the alkali-soluble resin, the polymerizable compound, and compound A. Examples of other components include a polymerization initiator, a dye, a thermally crosslinkable compound, a solvent, a plasticizer, a sensitizer, and a compound that generates an acid, a base, or a radical when exposed to light. Details of other components contained in the composition of the present invention will be described later according to the respective forms of the composition.

[0079] [Embodiments of the composition] The embodiment of the composition of the present invention is not particularly limited. For example, the composition of the present invention may be a negative type photosensitive resin composition used for forming a negative type photosensitive resin layer, a thermoplastic resin composition used for forming a thermoplastic resin layer, or a colored resin composition used for forming a colored resin layer. Hereinafter, components that may be contained in each composition in each embodiment will be described. In addition, a component described as a component of a composition of a certain embodiment is not intended to be included only when the composition is in that embodiment, and may also be used as a component of a composition of another embodiment. For example, a component described below as a component of a negative-type photosensitive resin layer composition may be used as a component of a composition other than a negative-type photosensitive resin composition.

[0080] [Negative Photosensitive Resin Composition] In display devices (such as organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance-type input device, an electrode pattern corresponding to the sensor of the visible area, and conductive layer patterns such as wiring of the peripheral wiring portion and the extraction wiring portion are provided inside the touch panel. In general, a method for forming a patterned layer is widely adopted in which a layer of a negative photosensitive resin composition (photosensitive layer) is provided on a substrate using a transfer film or the like, and the photosensitive layer is exposed to light through a mask having a desired pattern, and then developed. Here, first, components that can be contained as components other than compound A when the composition is a negative photosensitive resin composition will be described.

[0081] When the composition is a negative photosensitive resin composition, the negative photosensitive resin composition preferably contains compound A, an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Such a composition (such as a negative photosensitive resin composition) preferably contains, based on the total solid content by mass 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 turn.

[0082] <Polymer P (resin)> When the composition is a negative-type photosensitive resin composition, the alkali-soluble resin contained in the composition is also referred to as polymer P in particular. 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, from the viewpoint of suppressing swelling of the negative photosensitive resin layer by the developer and thereby achieving superior resolution. The lower limit of the acid value of the polymer P is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and particularly preferably 170 mgKOH / g or more.

[0083] The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and is expressed in units of mgKOH / g in this specification. The acid value can be calculated, for example, from the average content of acid groups in a compound. The acid value of the polymer P may be adjusted by changing the type of structural unit constituting the polymer P and the content of the structural unit containing an acid group.

[0084] The weight average molecular weight of the polymer P is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and even more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, it is preferable from the viewpoint of controlling the properties of the development aggregate and the properties of the unexposed film such as edge fuse property and cut chip property when it is made into a negative photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree of easiness of protrusion of the negative photosensitive resin layer (i.e., the layer made of the negative photosensitive resin composition) from the end face of the roll when it is wound into a roll as a negative photosensitive resin laminate. The cut chip property refers to the degree of ease of chipping when an unexposed film is cut with a cutter. If the chip adheres to the upper surface of the negative photosensitive resin laminate, it will be transferred to a mask in a subsequent exposure step, causing defective products. The dispersity of the polymer P is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0085] In the negative photosensitive resin composition, from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, the polymer P preferably contains a structural unit based on a monomer having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the structural unit based on a monomer having an aromatic hydrocarbon group in the polymer P is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the polymer P. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of polymer P are included, it is preferable that the average content of the structural unit based on a monomer having an aromatic hydrocarbon group falls within the above range.

[0086] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Among them, a monomer having an aralkyl group or styrene is 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 is preferably 20 to 70 mass%, more preferably 25 to 65 mass%, further preferably 30 to 60 mass%, and particularly preferably 30 to 55 mass%, based on the total mass of the polymer P.

[0087] Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred.

[0088] An example of the monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

[0089] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. Of 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, based on the total mass of the polymer P.

[0090] 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 type of a first monomer described below and / or at least one type of a second monomer described below.

[0091] The polymer P that does not contain a structural unit based on a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described later, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described later.

[0092] 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 preferable. The content of the constitutional units based on the first monomer in the polymer P is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and further preferably from 15 to 30 mass %, based on the total mass of the polymer P. A content of 5% by mass or more is preferable from the viewpoints of exhibiting good developability, controlling edge fusing property, etc. A content of 50% by mass or less is preferable from the viewpoints of high resolution and foot shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

[0093] The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the 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 them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferred, and methyl (meth)acrylate is more preferred. The content of the constitutional units based on the second monomer in the polymer P is preferably from 5 to 60 mass %, more preferably from 15 to 50 mass %, and even more preferably from 17 to 45 mass %, based on the total mass of the polymer P.

[0094] When the polymer P contains a constituent unit based on a monomer having an aralkyl group and / or a constituent unit based on a monomer of styrene, it is preferable from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure. For example, a copolymer containing a constituent unit based on methacrylic acid, a constituent unit based on benzyl methacrylate, and a constituent unit based on styrene, a copolymer containing a constituent unit based on methacrylic acid, a constituent unit based on methyl methacrylate, a constituent unit based on benzyl methacrylate, and a constituent unit based on styrene, etc. are preferable. In one embodiment, the polymer P is preferably a polymer containing 25 to 55 mass% of structural units based on a monomer having an aromatic hydrocarbon group, 20 to 35 mass% of structural units based on a first monomer, and 15 to 45 mass% of structural units based on a second monomer. In another embodiment, the polymer P is preferably a polymer containing 70 to 90 mass% of structural units based on a monomer having an aromatic hydrocarbon group, and 10 to 25 mass% of structural units based on the first monomer.

[0095] The polymer P may have a branched structure and / or an alicyclic structure in the side chain. The polymer P may also have a linear structure in the side chain. 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. Specific examples of monomers containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate, etc. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, or t-butyl methacrylate is preferred, and i-propyl methacrylate or t-butyl methacrylate is more preferred. Specific examples of monomers containing a group having an alicyclic structure in the 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-2-(meth)acrylate, 2-methyl-2-(meth)acrylate, 2-ethyl-2-(meth)acrylate, 2-hydroxy ... Examples of the acrylate include 1-adamantyl (meth)acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-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)acrylic acid esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate is more preferred.

[0096] The polymer P may be used alone or in combination of two or more. When two or more kinds are used, it is preferable to mix two kinds of polymers P containing structural units based on a monomer having an aromatic hydrocarbon group, or to mix a polymer P containing structural units based on a monomer having an aromatic hydrocarbon group with 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 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, based on the total mass of the polymer P.

[0097] The synthesis of the polymer P is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting the above-mentioned one or more monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. In some cases, the solvent is further added after the reaction is completed to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0098] The glass transition temperature Tg of the polymer P is preferably 30 to 135°C. By using a polymer P having a Tg of 135°C or less, it is possible to suppress line width thickening and deterioration of resolution when the focal position is shifted during exposure. From this viewpoint, the Tg of the polymer P is more preferably 130°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. In addition, it is preferable to use a polymer P having a Tg of 30°C or more from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg of the polymer P is more preferably 40°C or more, further preferably 50°C or more, particularly preferably 60°C or more, and most preferably 70°C or more.

[0099] The negative photosensitive resin composition may contain other resins in addition to those mentioned above. Other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0100] As the polymer P, an alkali-soluble resin, which will be described later in the description of the thermoplastic resin composition, may be used.

[0101] The content of the polymer P is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 20 to 70% by mass, particularly preferably 20 to 60% by mass, even more particularly preferably 30 to 60% by mass, and most preferably 40 to 60% by mass, based on the total solid content of the composition. It is preferable to set the content of the polymer P to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the content of the polymer P to 10% by mass or more from the viewpoint of improving edge fuse resistance.

[0102] <Polymerizable compound> The negative photosensitive resin composition contains a polymerizable compound having a polymerizable group. In this specification, the term "polymerizable compound" refers to a compound different from the compound A and the polymer P described above.

[0103] The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group, such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationic polymerizable group, such as an epoxy group and an oxetane group. The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

[0104] As the polymerizable compound, a compound having one or more ethylenically unsaturated groups (ethylenically unsaturated compound) is preferred, and a compound having two or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) is more preferred, in that the photosensitivity of the negative photosensitive resin layer is superior. From the viewpoint of obtaining superior resolution and peelability, the number of ethylenically unsaturated groups that the ethylenically unsaturated compound has in one molecule is preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less.

[0105] In order to obtain a better balance between the photosensitivity, resolution, and peelability of the negative photosensitive resin layer, it is preferable to contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, and it is more preferable to contain a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule. The content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and even more preferably 55% by mass or more, relative to the total solid content of the composition, from the viewpoint of excellent peelability. The upper limit is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds. Moreover, the ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group as a polymerizable group.

[0106] (Polymerizable compound B1) The negative photosensitive resin composition 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.

[0107] In the negative photosensitive resin composition, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% or more, more preferably 50% or more, even more preferably 55% or more, and particularly preferably 60% or more from the viewpoint of better resolution. The upper limit is not particularly limited, but is, for example, 100% or less, preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, and particularly preferably 85% or less from the viewpoint of peelability.

[0108] The aromatic ring of the polymerizable compound B1 may be, for example, an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, and an anthracene ring, an aromatic heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring, or a condensed ring thereof, and is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring.The aromatic ring may have a substituent. The polymerizable compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

[0109] The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive resin layer due to a developer. 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), with the bisphenol A structure being preferred.

[0110] An example of the polymerizable compound B1 having a bisphenol structure is a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. Both ends of the bisphenol structure may be directly bonded to the two polymerizable groups, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, more preferably ethyleneoxy. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP2016-224162A, the contents of which are incorporated herein by reference.

[0111] As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable. Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of suitable ethoxylated bisphenol A diacrylates include 2,2-bis(4-(methacryloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0112] As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferred.

[0113] [ka]

[0114] 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 of 1 to 39, and n1+n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 represents an integer of 0 to 30. The arrangement of the structural units -(AO)- and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. In one embodiment, n1+n2+n3+n4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n2+n4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

[0115] The polymerizable compound B1 may be used alone or in combination of two or more kinds. The content of the polymerizable compound B1 is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content of the composition from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (phenomenon in which photosensitive resin oozes out from the edge of the transfer film).

[0116] The negative photosensitive resin composition may contain a polymerizable compound other than the above-mentioned polymerizable compound B1. The polymerizable compound other than the polymerizable compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound without an aromatic ring, and a trifunctional or higher ethylenically unsaturated compound can be mentioned.

[0117] Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

[0118] Examples of difunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate. Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. Examples of urethane di(meth)acrylate include propylene oxide modified urethane di(meth)acrylate, and ethylene oxide and propylene oxide modified urethane di(meth)acrylate. 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.).

[0119] Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified versions of these. Here, "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate. In one embodiment, the negative photosensitive resin composition preferably contains the above-mentioned polymerizable compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass of the polymerizable compound B1):(total mass of the trifunctional or higher ethylenically unsaturated compounds)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1. In one embodiment, the negative photosensitive resin composition preferably contains the above-mentioned polymerizable compound B1 and two or more kinds of trifunctional ethylenically unsaturated compounds.

[0120] Examples of alkylene oxide modified trifunctional or higher ethylenically unsaturated compounds include caprolactone modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX M-510 (manufactured by Toagosei Co., Ltd.).

[0121] In addition, a polymerizable compound having an acid group (such as a carboxy group) may be used as the polymerizable compound. The acid group may form an acid anhydride group. Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), ARONIX (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and ARONIX (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.). As the polymerizable compound having an acid group, for example, the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

[0122] The polymerizable compounds may be used alone or in combination of two or more. 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%, based on the total solid content of the composition.

[0123] The molecular weight (weight average molecular weight when the polymerizable compound has a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably from 200 to 3,000, more preferably from 280 to 2,200, and even more preferably from 300 to 2,200.

[0124] <Polymerization initiator> The negative photosensitive resin composition also preferably contains a polymerization initiator. The polymerization initiator is selected depending on the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

[0125] The negative photosensitive resin composition preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound when exposed to active light such as ultraviolet light, visible light, and X-rays. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0126] 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.

[0127] From the viewpoints of photosensitivity, visibility of exposed and non-exposed areas, and resolution, the photosensitive resin layer preferably contains at least one photoradical polymerization initiator selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole 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.

[0128] As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783 may be used.

[0129] Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Industry Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 and 369 (trade names: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0130] Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins), BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins BV), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, IGM Resins BV), BV), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins BV(trade name: Lunar 6, manufactured by DKSH Japan Co., 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 Chemical Industry Co., Ltd.), and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Chemical Industry Co., Ltd.), Examples of such oxime include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

[0131] A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid when exposed to actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferred, but the chemical structure is not limited. In addition, even if a photocationic polymerization initiator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly set, but is preferably, for example, -10.0 or more.

[0132] The photocationic polymerization initiator includes an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator. Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, as well as quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP2014-085643A may be used.

[0133] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A may be used. As oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640 may be used. Examples of the photocationic polymerization initiator (photoacid generator) include the photoacid generators described in the description of the photosensitive resin composition below, and the photoacid generators described in the description of the thermoplastic resin composition below.

[0134] The negative photosensitive resin composition preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

[0135] The polymerization initiator may be used alone or in combination of two or more kinds. The content of the polymerization initiator (preferably 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, based on the total solid 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, based on the total solid content of the composition.

[0136] <Dye> From the viewpoints of visibility of exposed and unexposed parts, pattern visibility after development, and resolution, the negative photosensitive resin composition preferably contains a dye (also referred to as "dye N") that has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm during color development and whose maximum absorption wavelength changes with an acid, a base, or a radical. When dye N is contained, the adhesion with adjacent layers (for example, a temporary support and an intermediate layer) is improved, and the resolution is more excellent, although the detailed mechanism is unknown.

[0137] In this specification, the dye "whose maximum absorption wavelength changes due to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, a dye in a decolorized state is colored by an acid, a base, or a radical, and a dye in a colored state is changed to a colored state of another hue. Specifically, the dye N may be a compound that changes from a decolorized state to a colored state by exposure to light, or may be a compound that changes from a colored state to a decolored state by exposure to light. In this case, the dye may be a dye whose colored or decolored state changes when an acid, base, or radical is generated and acts in the photosensitive resin layer by exposure to light, or a dye whose colored or decolored state changes when the state (e.g., pH) in the photosensitive resin layer changes due to an acid, base, or radical. Alternatively, the dye may be a dye whose colored or decolored state changes when it is directly stimulated by an acid, base, or radical without exposure to light.

[0138] Among these, from the viewpoints of visibility and resolution of exposed and unexposed areas, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical. From the viewpoints of visibility and resolution of exposed and unexposed areas, the negative photosensitive resin composition preferably contains, as dye N, both a dye whose maximum absorption wavelength changes due to radicals, and a photoradical polymerization initiator. From the viewpoint of visibility of exposed and unexposed areas, dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

[0139] An example of the color-developing mechanism of dye N is a mode in which a photoradical polymerization initiator, a cationic photopolymerization initiator (photoacid generator), or a photobase generator is added to a photosensitive resin layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to a radical, acid, or base generated from the photoradical polymerization initiator, the photocationic photopolymerization initiator, or the photobase generator.

[0140] From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength in the wavelength range of 400 to 780 nm upon color development of 550 nm or more, more preferably 550 to 700 nm, and even more preferably 550 to 650 nm. Furthermore, dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm when it develops color, or may have two or more maximum absorption wavelengths. When dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm when it develops color, it is sufficient that the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

[0141] 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 environment and detecting the wavelength at which the light intensity is minimal (maximum absorption wavelength).

[0142] Examples of the dye that develops or loses color upon exposure to light include leuco compounds. Examples of dyes that are decolorized by exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. As the dye N, a leuco compound is preferable from the viewpoint of visibility of exposed and non-exposed areas.

[0143] Examples of the leuco compound include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes). Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

[0144] From the viewpoint of visibility of the exposed and non-exposed parts, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, the sultine ring, or the sultone ring of the leuco compound to react with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator, thereby changing the leuco compound to a ring-closed state to cause discoloration, or changing the leuco compound to a ring-open state to cause color development. The leuco compound is preferably a compound having a lactone ring, a sultine ring, or a sultone ring, which is colored by being opened by a radical or an acid, and more preferably a compound having a lactone ring, which is colored by being opened by a radical or an acid.

[0145] Examples of the dye N include the following dyes and leuco compounds. Specific examples of dyes among the pigments N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), and Examples of the oil-soluble pigments include Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0146] Specific examples of the leuco compound among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-(N-cyclohexyl-N-methylamino)fluoran, and the like. -methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)- 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

[0147] From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals. As dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalenesulfonate is preferred.

[0148] The dye N may be used alone or in combination of two or more kinds. From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 to 10 mass %, even more preferably 0.1 to 5 mass %, and particularly preferably 0.1 to 1 mass %, based on the total solid content of the composition.

[0149] The content of dye N means the content of dye when all of dye N contained in the total solid content of the composition is in a color-developing state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. Add a photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals and make all the dyes colored. Then, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere, and create a calibration curve. Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 3 g of the solid content of the composition is dissolved in methyl ethyl ketone instead of the dye. The content of the dye contained in the solid content of the composition is calculated based on the calibration curve from the absorbance of the solution containing the solid content of the composition obtained. The 3 g solid content of the composition is the same as 3 g of a layer (such as a negative photosensitive resin layer) formed using the composition.

[0150] <Thermal crosslinkable compound> The negative photosensitive resin composition preferably contains a thermal crosslinking compound from the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film. In this specification, the thermal crosslinking compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound but as a thermal crosslinking compound. Examples of the thermally 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 adhesion of the resulting uncured film. Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and / or a polymerizable compound has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when a film obtained by curing a negative photosensitive resin layer is used as a protective film. The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

[0151] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 100 to 160°C, and more preferably from 130 to 150°C. The dissociation temperature of a blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of a blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0152] Examples of blocking agents having a dissociation temperature of 100 to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, and other compounds having a structure represented by -C(=N-OH)- in the molecule). 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 preferable from the viewpoint of storage stability.

[0153] The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by converting it into an isocyanurate. Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred from the viewpoints that the dissociation temperature can be set in a preferred range more easily than a compound not having an oxime structure, and that development residues can be reduced.

[0154] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radically polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, as well as groups having an epoxy group such as a glycidyl group. Of these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0155] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation). In addition, as the blocked isocyanate compound, a compound having the following structure can also be used.

[0156] [ka]

[0157] The thermally crosslinkable compounds may be used alone or in combination of two or more. When the negative photosensitive resin composition contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the total solid content of the composition.

[0158] <Solvent> The negative photosensitive resin composition also preferably contains a solvent. 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 any known solvent can be used. 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. When preparing a transfer film having a temporary support, a thermoplastic resin layer, an intermediate layer (a water-soluble resin layer), and a negative photosensitive resin layer, the negative photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferred, and a mixed solvent containing at least three of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is even more preferred.

[0159] Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether acetate), propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers. Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate. 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 JP-A-2018-177889 may be used, the contents of which are incorporated herein by reference.

[0160] The solvent may be used alone or in combination of two or more. The content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0161] <Additives> The negative photosensitive resin composition may contain known additives, if necessary, in addition to the above components. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds (such as triazoles), benzotriazoles, carboxybenzotriazoles, pyridines (such as isonicotinamide), purine bases (such as adenine), and surfactants. Each of the additives may be used alone or in combination of two or more.

[0162] The negative photosensitive resin composition may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Other radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the negative photosensitive resin layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

[0163] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0164] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Examples of carboxybenzotriazoles that can be used include commercially available products such as CBT-1 (Johoku Chemical Industry Co., Ltd., trade name).

[0165] The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3 mass%, and more preferably 0.05 to 1 mass%, when the total solid content of the composition is 100 mass%. A content of 0.01 mass% or more is preferable from the viewpoint of imparting storage stability to the composition. On the other hand, a content of 3 mass% or less is preferable from the viewpoints of maintaining sensitivity and suppressing decolorization of the dye.

[0166] The negative photosensitive resin composition may contain a sensitizer. The sensitizer is not particularly limited, 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.

[0167] The sensitizers may be used alone or in combination of two or more. When the negative type photosensitive resin composition contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, based on the total mass of the photosensitive resin layer.

[0168] The negative photosensitive resin composition may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs 0097-0103 and 0111-0118 of WO 2018 / 179640.

[0169] In addition, the negative photosensitive resin composition may further contain known additives such as metal oxide particles, an antioxidant, a dispersant, an acid multiplier, a development accelerator, a conductive fiber, an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic suspending agent. The additives contained in the negative photosensitive resin composition are described in paragraphs

[0165] to

[0184] of JP2014-085643A, the contents of which are incorporated herein by reference.

[0170] The water content in the negative photosensitive resin composition is preferably from 0.01 to 1.0 mass %, and more preferably from 0.05 to 0.5 mass %, from the viewpoint of improving reliability and lamination properties.

[0171] <Physical properties of the layer formed> The method for applying the negative photosensitive resin composition is not particularly limited, and may be any known method, such as slit coating, spin coating, curtain coating, and inkjet coating. In addition, a composition layer (negative photosensitive resin layer) formed using a negative photosensitive resin composition may be formed by applying the negative photosensitive resin composition onto a substrate such as a cover film described below, and drying it.

[0172] The thickness (film 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, which can improve the developability of the negative photosensitive resin layer and the resolution. In one embodiment, the thickness is preferably from 0.5 to 5 μm, more preferably from 0.5 to 4 μm, and even more preferably from 0.5 to 3 μm.

[0173] From the viewpoint of obtaining superior 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. Although there is no particular upper limit, it is preferably 99.9% or less.

[0174] (Impurities, etc.) The negative photosensitive resin layer formed using the negative photosensitive resin composition may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so it is preferable to set the content to the following.

[0175] The content of impurities in the negative photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass. The content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, by mass.

[0176] Methods for controlling the amount of impurities within the above range include selecting raw materials for the composition that contain a small amount of impurities, preventing the inclusion of impurities during the preparation of the negative photosensitive resin layer, and removing the impurities by washing. By such methods, the amount of impurities can be controlled within the above range.

[0177] The amount of impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

[0178] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the negative photosensitive resin layer is preferably small. 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, by mass. The lower limit, based on mass, can be 10 ppb or more, and can be 100 ppb or more, based on the total mass of the negative photosensitive resin layer. The content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Also, they can be quantified by known measurement methods.

[0179] The water content in the negative photosensitive resin layer is preferably from 0.01 to 1.0 mass %, and more preferably from 0.05 to 0.5 mass %, from the viewpoint of improving reliability and lamination properties.

[0180] [Thermoplastic resin composition] The composition of the present invention may be a thermoplastic resin composition capable of forming a thermoplastic resin layer. For example, in a transfer film having a temporary support and a photosensitive resin layer (such as a layer made of the above-mentioned negative type photosensitive resin composition), the thermoplastic resin layer is preferably formed between the temporary support and the photosensitive resin layer. By providing the transfer film with a thermoplastic resin layer between the temporary support and the photosensitive resin layer, the transfer film can conform to the substrate better during the bonding process, preventing air bubbles from being trapped between the substrate and the transfer film, and ensuring perfect adhesion to adjacent layers (e.g., the temporary support).

[0181] The thermoplastic resin composition as the composition of the present invention is intended to be an embodiment in which the alkali-soluble resin in the composition is a thermoplastic resin. Note that the thermoplastic resin composition as the composition of the present invention may contain a thermoplastic resin other than the alkali-soluble resin that is a thermoplastic resin. In the following description, an alkali-soluble resin that is a thermoplastic resin may also be referred to as an "alkali-soluble thermoplastic resin." 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.

[0182] <Alkali-soluble thermoplastic resin> Examples of alkali-soluble resins that are thermoplastic resins (alkali-soluble thermoplastic resins) include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols.

[0183] As the alkali-soluble thermoplastic resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin is preferred. Here, the acrylic resin means a resin having at least one type of structural unit selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. The acrylic resin preferably contains a total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylic acid ester, and constituent units derived from (meth)acrylic acid amide of 50 mass% or more relative to the total mass of the acrylic resin. In particular, the total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester is preferably 30 to 100 mass %, and more preferably 50 to 100 mass %, based on the total mass of the acrylic resin.

[0184] The alkali-soluble thermoplastic resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with the carboxy group being preferred. From the viewpoint of developability, the alkali-soluble thermoplastic resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. 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.

[0185] 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. Examples of the alkali-soluble resin include a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, and a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2016-224162. The copolymerization ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 12 to 30 mass %, based on the total mass of the acrylic resin. As the alkali-soluble thermoplastic resin, from the viewpoints of developability and adhesion to adjacent layers, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferred.

[0186] The alkali-soluble thermoplastic resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples of the reactive group include ethylenically unsaturated groups, polycondensable groups such as hydroxyl groups and carboxyl groups, and polyaddition reactive groups such as epoxy groups and (blocked) isocyanate groups.

[0187] The weight average molecular weight (Mw) of the alkali-soluble thermoplastic resin is preferably 1,000 or more, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 50,000.

[0188] The alkali-soluble thermoplastic resin may be used alone or in combination of two or more kinds. From the viewpoints of developability and adhesion to adjacent layers, the content of the alkali-soluble thermoplastic resin is preferably from 10 to 99 mass%, more preferably from 20 to 90 mass%, even more preferably from 40 to 80 mass%, and particularly preferably from 50 to 75 mass%, based on the total solid content of the composition.

[0189] <Dye> The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 to 780 nm when colored and whose maximum absorption wavelength changes due to an acid, a base, or a radical. A preferred embodiment of dye B is the same as the preferred embodiment of dye N described above, except for the points described below.

[0190] From the viewpoints of visibility of exposed and unexposed areas and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid. From the viewpoints of visibility and resolution of exposed and unexposed areas, the thermoplastic layer preferably contains both a dye, as dye B, whose maximum absorption wavelength changes in response to acid, and a compound that generates acid when exposed to light, as described below.

[0191] The dye B may be used alone or in combination of two or more kinds. From the viewpoint of visibility of exposed and non-exposed areas, the content of dye B is preferably 0.2 mass % or more, more preferably 0.2 to 6 mass %, even more preferably 0.2 to 5 mass %, and particularly preferably 0.25 to 3.0 mass %, based on the total solid content of the composition.

[0192] Here, the content of dye B means the content of dye when all of dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of dye B will be described below using a dye that develops color by radicals as an example. Prepare solutions by dissolving 0.001 g and 0.01 g of dye in 100 mL of methyl ethyl ketone. Add a photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) to each of the obtained solutions, and irradiate with 365 nm light to generate radicals and make all the dyes colored. Then, measure the absorbance of each solution at a liquid temperature of 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere, and create a calibration curve. Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 0.1 g of the solid content of the composition is dissolved in methyl ethyl ketone instead of the dye. The amount of the dye contained in the solid content of the composition is calculated based on the calibration curve from the absorbance of the solution containing the solid content of the composition obtained. The 3 g solid content of the composition is the same as 3 g of a layer (such as a thermoplastic resin layer) formed using the composition.

[0193] <Compounds that generate acids, bases, or radicals when exposed to light> The thermoplastic resin composition may contain a compound that generates an acid, a base, or a radical when exposed to light (also simply referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical upon exposure to actinic rays such as ultraviolet light and visible light. Known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used as the compound C. Among them, photoacid generators are preferred.

[0194] (Photoacid generator) From the viewpoint of resolution, the thermoplastic resin composition preferably contains a photoacid generator. Examples of the photoacid generator include the cationic photopolymerization initiators that may be contained in the negative photosensitive resin composition described above, and preferred aspects are the same as those described below.

[0195] From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and from the viewpoints of sensitivity, resolution and adhesion, it is more preferable that the photoacid generator contains an oxime sulfonate compound. As the photoacid generator, a photoacid generator having the following structure is also preferred.

[0196] [ka]

[0197] (Photoradical polymerization initiator) The thermoplastic resin composition may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include the photoradical polymerization initiators that may be contained in the negative photosensitive resin composition described above, and preferred embodiments are also the same.

[0198] (Photobase Generator) The thermoplastic resin composition may contain a photobase generator. The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- Examples of suitable dimethylamino compounds include 1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

[0199] The compound C may be used alone or in combination of two or more. The content of compound C is preferably from 0.1 to 10 mass %, more preferably from 0.5 to 5 mass %, based on the total solid content of the composition, from the viewpoints of visibility and resolution of exposed and non-exposed areas.

[0200] <Plasticizer> The thermoplastic resin composition preferably contains a plasticizer from the viewpoints of the resolution, adhesion to adjacent layers, and developability of the composition layer (thermoplastic resin layer) to be formed. The plasticizer preferably has a smaller molecular weight (weight average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) than the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000. The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble thermoplastic resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

[0201] From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as a plasticizer include the (meth)acrylate compounds described above as the polymerizable compound contained in the negative photosensitive resin composition. In the transfer film, when the thermoplastic resin layer and the negative photosensitive resin layer are laminated in direct contact with each other, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound, because the thermoplastic resin layer and the negative photosensitive resin layer each contain the same (meth)acrylate compound, which suppresses component diffusion between the layers and improves storage stability.

[0202] When the thermoplastic resin composition contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize even in the exposed area after exposure, from the viewpoint of adhesion between the thermoplastic resin layer and an adjacent layer. In addition, as the (meth)acrylate compound used as a plasticizer, from the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule is preferred. Furthermore, as the (meth)acrylate compound used as the plasticizer, a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound is also preferred.

[0203] The plasticizers may be used alone or in combination of two or more. From the viewpoints of the resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability, the content of the plasticizer is preferably 1 to 70 mass %, more preferably 10 to 60 mass %, and even more preferably 20 to 50 mass %, based on the total solid content of the composition.

[0204] <Sensitizer> The thermoplastic resin composition may include a sensitizer. The sensitizer is not particularly limited, and examples thereof include the sensitizers that may be contained in the negative photosensitive resin layer described above.

[0205] The sensitizers may be used alone or in combination of two or more. The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoints of improving the sensitivity to the light source and the visibility of the exposed and non-exposed areas, it is preferably 0.01 to 5 mass %, and more preferably 0.05 to 1 mass %, based on the total solid content of the composition.

[0206] <Solvent> The thermoplastic resin composition may contain a solvent. The solvent is not particularly limited, and examples thereof include the solvents that may be contained in the negative photosensitive resin layer described above. It is also preferable that the thermoplastic resin composition contains at least one solvent selected from the group consisting of alkylene glycol ethers and alkylene glycol ether acetates. The content of the solvent is preferably from 50 to 1,900 parts by mass, and more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0207] <Additives, etc.> The thermoplastic resin composition may contain known additives, if necessary, in addition to the above components. In addition, the thermoplastic resin layer is described in paragraphs

[0189] to

[0193] of JP2014-085643A, the contents of which are incorporated herein by reference.

[0208] <Physical properties of the layer formed> The thickness of the layer (thermoplastic resin layer) formed using the thermoplastic resin composition is not particularly limited, but from the viewpoint of adhesion with adjacent layers, it is preferably 1 μm or more, more preferably 2 μm or more. The upper limit is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0209] The method for forming the thermoplastic resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. The method includes coating a thermoplastic resin composition on the surface of a temporary support or the like and drying the coating film of the thermoplastic resin composition to form the protective layer.

[0210] Alternatively, after forming a photosensitive resin layer and an intermediate layer on a cover film described below, a thermoplastic resin layer may be formed on the surface of the intermediate layer.

[0211] [Colored resin composition] The composition of the present invention may be used as a pigmented resin composition. In some cases, in order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate, etc. is attached to the liquid crystal display window. The coloring composition can be used to form such a light-shielding layer. The colored resin composition is a composition that contains a pigment. That is, the composition of the present invention may be a colored resin composition further containing a pigment in addition to the compound A, the alkali-soluble resin, and the polymerizable compound. The composition of the present invention, which is a colored resin composition, preferably further contains a polymerization initiator in addition to the compound A, the alkali-soluble resin, the polymerizable compound, and the pigment.

[0212] <Pigments> The pigment contained in the colored resin composition may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and pigments of chromatic colors other than black and white. Among them, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

[0213] As the black pigment, known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected within a range that does not impair the effects of the present invention. Among them, from the viewpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black at least a part of the surface of which is coated with a resin is preferred.

[0214] The black pigment (preferably carbon black) is preferably used in the form of a pigment dispersion. The dispersion may be prepared by adding a mixture of a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant may be used. The vehicle refers to the medium portion in which the pigment is dispersed when the pigment dispersion is prepared, and is liquid, and includes 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.

[0215] The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine pulverization may be performed by utilizing frictional force through mechanical grinding. For details of dispersing machines and fine pulverization, see the description in "Encyclopedia of Pigments" (Kunizo Asakura, First Edition, Asakura Shoten, 2000, pages 438 and 310).

[0216] From the viewpoint of dispersion stability, the particle size of the black pigment is preferably from 0.001 to 0.1 μm, more preferably from 0.01 to 0.08 μm, in terms of number average particle size. Here, the particle size refers to the diameter of a circle whose area is equal to the area of ​​a pigment particle, calculated from a photograph of the pigment particle taken with an electron microscope, and the number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the particle sizes of the 100 particles thus calculated.

[0217] As a pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used. Specifically, among the white pigments, the inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, precipitated 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 the inorganic pigment, rutile or anatase titanium oxide is more preferable, and rutile titanium oxide is particularly preferable. The surface of titanium oxide may be subjected to a silica treatment, an alumina treatment, a titania treatment, a zirconia treatment, or an organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc. From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

[0218] From the viewpoint of transferability, it is also preferable that the colored resin composition further contains a chromatic pigment other than the black pigment and the white pigment. When the chromatic pigment is contained, it is preferable that the chromatic pigment is well dispersed in the colored resin layer, and from this viewpoint, the particle size is preferably 0.1 μm or less, more preferably 0.08 μm or less. Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral Fast Blue (CI Pigment Red 146 ... Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Permanent Yellow Examples of pigments include CI Pigment Blue 15), Monolight Fast 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. Of these, CI Pigment Red 177 is preferred.

[0219] The pigment content is preferably more than 3 mass% and not more than 40 mass%, more preferably more than 3 mass% and not more than 35 mass%, even more preferably more than 5 mass% and not more than 35 mass%, and particularly preferably 10 mass% or more and not more than 35 mass%, based on the total solid content of the composition.

[0220] When pigments other than the black pigment (white pigment and chromatic pigments) are contained, the amount thereof 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.

[0221] A pigment may be added to each of the above compositions to form a colored resin composition. For example, a composition obtained by adding a pigment (or a pigment dispersion liquid) to the above-mentioned negative photosensitive resin composition can be used as a colored resin composition. In other words, the above-mentioned negative photosensitive resin composition may be used as a negative photosensitive resin composition that is a colored resin composition. Similarly, each of the above-mentioned composition layers may be a colored resin layer to which a pigment is added. For example, the above-mentioned negative photosensitive resin layer may be a colored resin layer containing a pigment as described above. In other words, the above-mentioned negative photosensitive resin layer may be a negative photosensitive resin layer that is a colored resin layer.

[0222] <Physical properties of the layer formed> The method for applying 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 a negative type photosensitive resin composition, for example.

[0223] The layer thickness (film thickness) of the composition layer (colored resin layer) formed using the colored resin composition is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, even more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm, and most preferably 0.5 to 8 μm.

[0224] [Transfer film] The present invention also relates to a transfer film. The transfer film of the present invention is a transfer film having a temporary support and one or more composition layers (e.g., 1 to 5 layers), and at least one of the composition layers is a layer (composition layer) formed using the composition of the present invention. The transfer film may be laminated directly on the temporary support and the one or more composition layers without any other layer, or may be laminated through another layer. In addition, another layer may be laminated on the surface opposite to the surface facing the temporary support of the one or more composition layers. Another layer may be present between the one or more composition layers. 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 fall under the composition of the present invention (such as the "composition not containing an alkali-soluble resin, a polymerizable compound, and compound A" described below). Hereinafter, a layer formed using the composition of the present invention (composition layer) will also be referred to as "the composition layer of the present invention". In addition, a layer (composition layer) formed using a composition other than the present invention that does not fall under the category of the composition of the present invention (such as the "composition that does not contain an alkali-soluble resin, a polymerizable compound, and compound A" described below) is also referred to as a "composition layer other than the present invention." In the transfer film, of one or more (e.g., 1 to 5) composition layers, at least one layer may be made of the composition of the present invention, half or more of the layers may be made of the composition of the present invention, or all of the layers may be made of the composition of the present invention.

[0225] The composition layer of the present invention is, for example, a layer consisting only of the solid content of the composition of the present invention. More specifically, the composition layer of the present invention is, for example, a layer consisting only of the solid content of the negative photosensitive resin composition, thermoplastic resin composition, and / or colored resin composition (negative photosensitive resin layer, thermoplastic resin layer, and / or colored resin layer). As used herein, "consisting only of solids" means containing substantially only solids, and the solids content is preferably 95 to 100 mass%, more preferably 99 to 100 mass%, and even more preferably 99.5 to 100 mass%, relative to the total mass of the composition layer. The composition layer other than that of the present invention is, for example, a composition layer formed using a composition in which "alkali-soluble resin, polymerizable compound, and compound A are not contained in the above-mentioned negative photosensitive resin composition, thermoplastic resin composition, and / or colored resin composition. Such a composition layer is preferably a layer consisting only of the solid content in the above-mentioned "composition in which alkali-soluble resin, polymerizable compound, and compound A are not contained." In addition, examples of the above-mentioned "composition in which alkali-soluble resin, polymerizable compound, and compound A are not contained" include a composition in which compound A is simply removed from the composition of the present invention, and a composition in which compound A in the composition of the present invention is replaced with a surfactant that does not fall under compound A. Hereinafter, the negative photosensitive resin composition of the present invention will be distinguished from the above-mentioned negative photosensitive resin composition that does not contain an alkali-soluble resin, a polymerizable compound, and compound A, and will be referred to as the negative photosensitive resin composition of the present invention and a negative photosensitive resin composition other than the present invention. The same applies to other types of compositions. In addition, a layer formed using the negative type photosensitive resin composition of the present invention and a layer formed using a negative type photosensitive resin composition other than the present invention are also distinguished as a negative type photosensitive resin layer of the present invention and a negative type photosensitive resin composition other than the present invention. The same applies to other types of composition layers. The transfer film of the present invention preferably contains 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. In other words, it is preferable that at least one of the above-mentioned composition layers (one or more composition layers) possessed by the transfer film of the present invention is a negative type photosensitive resin layer (a negative type photosensitive resin layer of the present invention or a negative type photosensitive resin layer other than that of the present invention).

[0226] [Temporary Support] The transfer film according to the present invention has a temporary support. The temporary support is a support which supports the composition layer or a laminate including the composition layer and is peelable.

[0227] The temporary support preferably has light transmittance from the viewpoint of enabling exposure through the temporary support when the composition layer is subjected to patternwise exposure. In this specification, "having light transmittance" means that the transmittance of light of the wavelength used for patternwise exposure is 50% or more. From the viewpoint of improving exposure sensitivity, the temporary support preferably has a transmittance of light having a wavelength used for patternwise exposure (more preferably a wavelength of 365 nm) of 60% or more, more preferably 70% or more. The transmittance of the layer of the transfer film is the ratio of the intensity of the emitted light that passes 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 the MCPD Series manufactured by Otsuka Electronics Co., Ltd.

[0228] Examples of materials constituting the temporary support include a glass substrate, a resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, a resin film is preferred. Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Of these, a PET film is preferred, and a biaxially stretched PET film is more preferred.

[0229] The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the standpoints of strength as a support, flexibility required for bonding to a substrate for forming circuit wiring, and light transmittance required in the initial exposure step. The thickness of the temporary support is preferably from 5 to 100 μm, and from the viewpoints of ease of handling and versatility, it is more preferably from 10 to 50 μm, further preferably from 10 to 20 μm, and particularly preferably from 10 to 16 μm.

[0230] In addition, the film used as the temporary support is preferably free from deformations such as wrinkles, scratches, defects, and the like. From the viewpoint of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, defects, precipitates, etc. contained in the temporary support is small. The number of fine particles, foreign matter, and defects having a diameter of 1 μm or more is 50 / 10 mm. 2 Less than 10 pieces / 10mm is preferable. 2 Less than 3 pieces / 10mm is more preferable. 2 Less than 0 / 10mm is more preferable. 2 is particularly preferred.

[0231] Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of JP 2014-085643 A, paragraphs 0019 to 0026 of JP 2016-027363 A, paragraphs 0041 to 0057 of WO 2012 / 081680 A1, paragraphs 0029 to 0040 of WO 2018 / 179370 A1, and paragraphs 0012 to 0032 of JP 2019-101405 A, the contents of which are incorporated herein by reference.

[0232] [Cover film] 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. 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".

[0233] Materials constituting the cover film include resin films and paper, with resin films being preferred from the standpoints of strength and flexibility. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable.

[0234] The thickness (layer thickness) of the cover film is not particularly limited, but is preferably from 5 to 100 μm, more preferably from 10 to 50 μm. The arithmetic mean roughness Ra value of the surface of the cover film in contact with the composition layer (hereinafter also simply referred to as the "surface of the cover film") is preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less, because this provides better resolution. It is believed that the uniformity of the layer thickness of the formed resin pattern is improved by having the Ra value of the surface of the cover film in the above range. There is no particular lower limit for the Ra value of the surface of the cover film, but it is preferably 0.001 μm or more.

[0235] The Ra value of the surface of the cover film is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface of the cover film is measured under the following conditions to obtain a surface profile of the optical film. The measurement and analysis software used is Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen is displayed in the analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness is calculated, and the Ra value of the cover film surface is obtained. When a cover film is attached to the transfer film, the cover film is peeled off from the transfer film, and the Ra value of the surface on the peeled side may be measured.

[0236] [Method of manufacturing transfer film] The method for producing the transfer film according to the present invention is not particularly limited, and any known production method, for example, any known method for forming each layer, can be used. Hereinafter, a method for producing a transfer film according to the present invention will be described with reference to Fig. 1. However, the transfer film according to the present invention is not limited to the structure shown in Fig. 1. Fig. 1 is a schematic diagram showing an example of the configuration of a transfer film according to the present invention. The transfer film 100 shown in Fig. 1 has a configuration 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 laminated in this order. Furthermore, by providing the transfer film with the intermediate layer 14, it is possible to prevent mixing of components when applying multiple layers and during storage after application. The intermediate layer may be an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-072724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and productivity is improved, which is preferable. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above publications, etc. Among them, an oxygen barrier layer that exhibits low oxygen permeability and disperses or dissolves in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22° C.) is preferred. The intermediate layer and the resin composition capable of forming the intermediate layer will be described in detail later.

[0237] Examples of a method for producing the transfer film 100 include a method including the steps of applying the thermoplastic resin composition of the present invention to the surface of the temporary support 10, and then drying the coating of the thermoplastic resin composition of the present invention to form a thermoplastic resin layer 12; applying an intermediate layer-forming resin composition to the surface of the thermoplastic resin layer 12, and then drying the coating of the intermediate layer-forming resin composition to form an intermediate layer 14; and applying a negative type photosensitive resin composition of the present invention to the surface of the intermediate layer 14, and then drying the coating of the negative type photosensitive resin composition of the present invention to form a negative type photosensitive resin layer 16.

[0238] A cover film 18 is pressure-bonded to the negative photosensitive resin layer 16 of the laminate produced by the above-mentioned production method, thereby producing a transfer film 100. As a manufacturing method for the transfer film of the present invention, it is preferable to include a step of providing a cover film 18 in contact with the second surface of the photosensitive resin layer 16, thereby manufacturing a transfer film 100 having a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a cover film 18. After the transfer film 100 is manufactured by the above manufacturing method, a transfer film in a roll form may be produced and stored by winding up the transfer film 100. The transfer film in a roll form can be provided as it is to a bonding step with a substrate in a roll-to-roll system described later.

[0239] In the above-described manufacturing method, the composition of the present invention was used as both the thermoplastic resin composition and the negative photosensitive resin composition, but it is sufficient that at least one of these is the composition of the present invention, and the other 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). 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 of a material other than the present invention.

[0240] <Middle Class> The intermediate layer contains a resin, which is preferably a water-soluble resin. Examples of resins that can be used as the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. In addition, when a water-soluble resin layer containing a water-soluble resin is used as an intermediate layer, it is preferable that the water-soluble resin is a resin different from the resin contained in the adjacent layer (e.g., polymer P contained in a negative photosensitive resin layer and / or a thermoplastic resin (alkali-soluble resin) contained in a thermoplastic resin layer) in order to suppress mixing of components between multiple layers.

[0241] From the viewpoints of oxygen barrier properties and suppressing mixing of components when multiple layers are applied and during storage after application, the water-soluble resin preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone.

[0242] The intermediate layer can be formed using a water-soluble resin composition containing a water-soluble resin. The water-soluble resin may be used alone or in combination of two or more kinds. The content of the water-soluble resin is not particularly limited, but from the viewpoint of oxygen barrier properties and suppressing mixing of components when applying multiple layers and during storage after application, the content 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, even more 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, based on the total solids content of the water-soluble resin composition.

[0243] In addition, the water-soluble resin composition preferably further contains a solvent in order to improve the coating property, 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, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred. The content of the solvent is preferably from 50 to 2,500 parts by mass, more preferably from 50 to 1,900 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.

[0244] The method for applying the composition using the water-soluble resin composition and / or the method for forming the composition layer are not particularly limited, and can be carried out in the same manner as the method using the negative type photosensitive resin composition, for example. The method for forming the intermediate layer (water-soluble resin layer containing a water-soluble resin) is not particularly limited, and examples thereof include a method in which a water-soluble resin composition is applied to the surface of a thermoplastic resin layer or a photosensitive resin layer, and the coating film of the water-soluble resin composition is dried to form a water-soluble resin layer.

[0245] 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. When the thickness of the water-soluble resin layer is within the above range, the oxygen barrier property is not decreased, mixing of components during coating of multiple layers and during storage after coating can be suppressed, and an increase in the time required for removing the water-soluble resin layer during development can be suppressed.

[0246] An example of the embodiment of the transfer film is shown below. In each of the following configurations, one or more layers (such as a cover film) may be removed and / or additional layers may be added between any of the layers as desired. (1) "Temporary support / thermoplastic resin layer / intermediate layer (water-soluble resin layer) / negative photosensitive resin layer / cover film" (2) "Temporary support / negative photosensitive resin layer / refractive index adjusting layer / cover film" (3) "Temporary support / negative photosensitive resin layer / cover film" In the composition layers (layers other than the temporary support and the cover film) constituting the transfer film having each of the above configurations, at least one layer of the thermoplastic resin layer and the negative photosensitive resin layer is the composition layer of the present invention. In each of the above-mentioned configurations, it is also preferable that the negative photosensitive resin layer is a colored resin layer. In the above configuration, the refractive index adjustment layer may be a known refractive index adjustment layer, for example, the second resin layer disclosed in paragraphs

[0200] to

[0214] of JP2020-091322A.

[0247] [Laminate manufacturing method and circuit wiring manufacturing method] The present invention also relates to a method for producing a laminate. The method for producing the laminate is not particularly limited as long as it is a method for producing a laminate using the above-mentioned transfer film. A preferred method for producing a laminate includes a lamination step (hereinafter also referred to as the "lamination step") of contacting a substrate (preferably a conductive substrate) with the surface of the transfer film opposite the temporary support (the surface of the composition layer) and laminating the transfer film and the substrate (preferably a conductive substrate) to obtain a substrate with a transfer film, an exposure step (hereinafter also referred to as the "exposure step") of exposing the composition layer to a pattern, a development step (hereinafter also referred to as the "development step") of developing the exposed composition layer to form a resin pattern, and further a peeling step (hereinafter also referred to as the "peeling step") of peeling the temporary support from the substrate with the transfer film between the lamination step and the exposure step or between the exposure step and the development step. The composition layer to be patternwise exposed may consist of one layer alone or two or more layers, and at least one of the layers constituting the composition layer is the composition layer of the present invention. The composition layer to be pattern-exposed 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.

[0248] 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. As a method for manufacturing circuit wiring, a method including a step of etching the conductive layer in an area where a resin pattern is not arranged 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 laminated in this order (hereinafter also referred to as an "etching step"). In other words, the method for manufacturing circuit wiring preferably includes a lamination step (hereinafter also referred to as the "lamination step") of contacting a substrate having a conductive layer with the surface (composition layer) of the transfer film opposite the temporary support and laminating the transfer film and the substrate having a conductive layer to obtain a substrate with a transfer film, an exposure step (hereinafter also referred to as the "exposure step") of exposing the composition layer to a pattern, a development step (hereinafter also referred to as the "development step") of developing the exposed composition layer to form a resin pattern, a step (hereinafter also referred to as the "etching step") of etching the conductive layer in an area where the resin pattern is not arranged, and further a peeling step (hereinafter also referred to as the "peeling step") of peeling the temporary support from the substrate with the transfer film between the lamination step and the exposure step, or between the exposure step and the development step. The preferred form of the composition layer to be pattern-exposed is the same as that described above.

[0249] Below, we will explain each step included in the method for manufacturing a laminate and the method for manufacturing circuit wiring. Unless otherwise specified, the contents explained for each step included in the method for manufacturing a laminate also apply to each step included in the method for manufacturing circuit wiring.

[0250] [Lamination process] The method for producing the laminate preferably includes a lamination step. In the lamination step, it is preferable to bring the substrate (if a conductive layer is provided on the substrate surface) into contact with the surface of the transfer film opposite to the temporary support, and to press the transfer film and the substrate together. In the above embodiment, the adhesion between the composition layer and the substrate is improved, and the resin pattern formed after exposure and development can be used as an etching resist when etching a conductive layer.

[0251] When the transfer film has a cover film, the cover film may be removed from the surface of the transfer film before bonding.

[0252] The method for bonding the substrate and the transfer film by pressure is not particularly limited, and known transfer methods and lamination methods can be used. The transfer film is preferably bonded to the substrate by placing the substrate on the surface of the transfer film opposite to the temporary support, and applying pressure and heat using a roll or other means. For the bonding, a known laminator such as a laminator, a vacuum laminator, or an autocut laminator that can further increase productivity can be used.

[0253] The method for producing a laminate and the method for producing a circuit wiring, which include the lamination step, are preferably carried out by a roll-to-roll system. The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate or a structure including the substrate (also referred to as an "unwinding step") before any step included in the manufacturing method of a laminate or a manufacturing method of circuit wiring, and a step of winding up the substrate or the structure including the substrate (also referred to as a "winding step") after any step, in which at least any step (preferably all steps, or all steps other than the heating step) is performed while transporting the structure including the substrate or the substrate. 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 that employs a roll-to-roll system.

[0254] <Substrate> As the substrate used in forming a resin pattern using the transfer film according to the present invention, a known substrate may be used, but a substrate having a conductive layer is preferred, and a substrate having a conductive layer on the surface thereof is more preferred. The substrate may have any layer other than the conductive layer, if necessary.

[0255] Examples of the base material that constitutes the substrate include glass, silicon, and films. The base material constituting the substrate is preferably transparent. In this specification, the term "transparent" means that the transmittance of light with a wavelength of 400 to 700 nm is 80% or more. The refractive index of the base material constituting the substrate is preferably 1.50 to 1.52.

[0256] Examples of the transparent glass substrate include tempered glass, such as Gorilla Glass from Corning Inc. In addition, the materials used in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.

[0257] When a film substrate is used as the substrate, it is preferable to use a film substrate having small optical distortion and / or high transparency. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[0258] When the substrate is manufactured by a roll-to-roll process, the substrate is preferably a film substrate. When the substrate is manufactured by a roll-to-roll process, the substrate is preferably a sheet-shaped resin composition.

[0259] The conductive layer of the substrate may be a conductive layer used for general circuit wiring or touch panel wiring. From the viewpoints of electrical conductivity and fine line formability, the conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The substrate may have one conductive layer or two or more conductive layers. When the substrate has two or more conductive layers, the conductive layers are preferably made of different materials.

[0260] Materials for the conductive layer include metals and conductive metal oxides. Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au. Examples of conductive metal oxides include indium tin oxide (ITO), indium zinc oxide (IZO), and SiO2. In this specification, "conductive" means a material having a volume resistivity of 1×10 6 The volume resistivity of conductive metal oxides is less than 1×10 4 Less than Ωcm is preferred.

[0261] 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. The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition portion used in a capacitive touch panel or wiring of a peripheral extraction portion.

[0262] [Exposure process] The method for producing the laminate preferably includes, after the laminating step, a step of pattern-exposing the composition layer (exposure step).

[0263] The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. In order to improve the display quality of a display device (e.g., a touch panel) equipped with an input device having a circuit wiring manufactured by the manufacturing method for circuit wiring and to reduce the area occupied by the lead wiring, at least a part of the pattern (preferably the electrode pattern of the touch panel and / or the lead wiring part) preferably includes a thin line having a width of 20 μm or less, more preferably includes a thin line having a width of 10 μm or less.

[0264] The light source used for exposure can be appropriately selected and used as long as it irradiates light with a wavelength (e.g., 365 nm or 405 nm) that can expose the photosensitive resin layer. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

[0265] The exposure dose is 5 to 200 mJ / cm 2 is preferable, and 10 to 100 mJ / cm 2 is more preferred.

[0266] [Peeling process] The peeling step is a step of peeling off 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 below. The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs

[0161] to

[0162] of JP2010-072589A can be used. Therefore, in the exposure step, the temporary support may be peeled off from the composition layer and then pattern exposure may be performed through the temporary support before peeling off the temporary support, and then the temporary support may be peeled off. When the temporary support is peeled off before exposure, the mask may be exposed in contact with the composition layer, or may be exposed in close proximity without contact. When exposing without peeling off the temporary support, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent mask contamination due to contact between the composition layer and the mask, and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. In addition, the exposure method can be appropriately selected from the contact exposure method in the case of contact exposure, and the proximity exposure method, the projection exposure method of the lens system and the mirror system, and the direct exposure method using the exposure laser, etc. in the case of the projection exposure of the lens system and the mirror system, depending on the required resolution and focal depth, an exposure machine having an appropriate lens numerical aperture (NA) can be used. In the case of the direct exposure method, drawing may be performed directly on the photosensitive layer, or reduction projection exposure may be performed on the photosensitive layer through a lens. Exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum, and exposure may be performed by interposing a liquid such as water between the light source and the photosensitive layer.

[0267] [Development process] The method for producing a laminate preferably includes, after the above-mentioned exposure step, a step of developing the exposed composition layer to form a resin pattern (development step). When the composition layer contains a negative type photosensitive resin layer (a negative type photosensitive resin layer of the present invention or a negative type photosensitive resin layer other than that of the present invention), the composition layer undergoes a curing reaction according to the exposed pattern to become a cured film (a patterned cured film), and it becomes possible to remove only the unexposed parts of the composition layer with a developer (an alkaline developer, etc.).

[0268] When the transfer film has a negative photosensitive resin layer and a composition layer different from the negative photosensitive resin layer, the different composition layer may be removed only in the same portion as the portion to be removed in the negative photosensitive resin layer, or may be removed entirely including the portion other than the portion to be removed in the negative photosensitive resin layer. For example, when the transfer film has a thermoplastic resin layer and / or a water-soluble resin layer together with a negative photosensitive resin layer, in the development step, only the thermoplastic resin layer and / or the water-soluble resin layer in the non-exposed area may be removed together with the negative photosensitive resin layer in the non-exposed area. In addition, in the development step, the thermoplastic resin layer and / or the water-soluble resin layer in both the exposed and non-exposed areas may be removed in a form dissolved or dispersed in the developer. In the resin pattern obtained after development, a part or all of it may be a layer formed by the composition layer of the present invention or a change of the composition of the present invention through a curing reaction, etc. For example, when the composition layer of the transfer film contains the negative type photosensitive resin layer of the present invention, a part or all of the resin pattern is a material formed by a curing reaction of the negative type photosensitive resin layer of the present invention. 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 consist only of 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.

[0269] In the development step, the exposed composition layer can be developed using an alkaline developer. As the alkaline developer, for example, a known developer such as the developer described in JP-A-5-072724 can be used. The alkaline developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L (liter). The alkaline developer may contain a water-soluble organic solvent and / or a surfactant. The alkaline developer is also preferably the developer described in paragraph 0194 of WO 2015 / 093271. The content of the organic solvent in the alkaline developer is preferably 0% by mass or more and less than 90% by mass with respect to the total mass of the developer.

[0270] The development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development treatment in which a developer is sprayed by shower onto the photosensitive resin layer after exposure to remove the unexposed area. After the development step, it is preferable to remove development residues by spraying a cleaning agent by showering and scrubbing with a brush. The temperature of the developer is not particularly limited, but is preferably from 20 to 40°C.

[0271] [Etching process] The method for manufacturing circuit wiring preferably includes a step of etching the conductive layer in an area where the resin pattern is not arranged in a laminate 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 lamination step, the exposure step, and the development step) are laminated in this order (etching step).

[0272] In the etching process, the conductive layer is etched using the resin pattern formed from the photosensitive resin layer as an etching resist. As the etching method, known methods can be applied, for example, the method described in paragraphs 0209 to 0210 of JP 2017-120435 A, the method described in paragraphs 0048 to 0054 of JP 2010-152155 A, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching can be mentioned.

[0273] The etching solution used in the wet etching may be an acidic or alkaline etching solution that is appropriately selected depending on the target to be etched. Examples of the acidic etching solution include an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an aqueous solution of a mixture of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of a plurality of acidic components. Examples of the alkaline etching solution include an aqueous solution of an alkaline component selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), and an aqueous solution of a mixture of an alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of a plurality of alkaline components.

[0274] [Removal process] In the method for producing circuit wiring, it is preferable to carry out a step of removing the remaining resin pattern (removal step). The removal step is not particularly limited and may be carried out as necessary, but is preferably carried out after the etching step. The method for removing the remaining resin pattern is not particularly limited, but includes a method of removing it by chemical treatment, and a method of removing it by using a removing liquid is preferable. The photosensitive resin layer can be removed by immersing the substrate having the remaining resin pattern in a stirring removal liquid having a liquid temperature of preferably 30 to 80°C, more preferably 50 to 80°C, for 1 to 30 minutes.

[0275] Examples of the removal liquid include removal liquids in which an inorganic or organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixture 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. Alternatively, the removal may be performed by a known method such as a spray method, a shower method, or a paddle method using a removal liquid.

[0276] [Other steps] The method for producing a circuit wiring may include any steps (other steps) other than the steps described above, such as, but not limited to, the following steps. Moreover, examples of the exposure step, development step and other steps that can be applied to the method for producing circuit wiring include the steps described in paragraphs 0035 to 0051 of JP-A No. 2006-023696.

[0277] <Cover film peeling process> 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.

[0278] <Step of reducing visible light reflectance> The method for producing circuit wiring may include a step of performing a treatment to reduce the visible light reflectance of some or all of the multiple conductive layers of the substrate. Examples of treatments for reducing the visible light reflectance include oxidation treatments. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to copper oxide and blackening the conductive layer. Treatments for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A, and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, and the contents of these publications are incorporated herein by reference.

[0279] <Step of forming an insulating film, step of forming a new conductive layer on the surface of the insulating film> The method for producing the circuit wiring preferably includes the steps of forming an insulating film on the surface of the circuit wiring, and forming a new conductive layer on the surface of the insulating film. By the above steps, a second electrode pattern insulated from the first electrode pattern can be formed. The step of forming the insulating film is not particularly limited, and may be a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[0280] In the method for producing the circuit wiring, a substrate having a plurality of conductive layers on both surfaces of the substrate is used, and circuits are formed on the conductive layers formed on both surfaces of the substrate, either sequentially or simultaneously. With this configuration, a touch panel circuit wiring can be formed in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.

[0281] [Circuit wiring applications] The circuit wiring manufactured by the manufacturing method of the circuit wiring can be applied to various devices. An example of a device having the circuit wiring manufactured by the manufacturing method is an input device, preferably a touch panel, more preferably a capacitive touch panel. The input device can also be applied to a display device such as an organic EL display device and a liquid crystal display device.

[0282] [Electronic device manufacturing method] The present invention also relates to a method for manufacturing an electronic device. As the method for producing the electronic device, a method for producing an electronic device using the above-mentioned transfer film is preferable. In particular, the method for producing an electronic device preferably includes the method for producing the laminate described above. The electronic device may be, for example, an input device, preferably a touch panel, and may be applied to a display device such as an organic electroluminescence display device or a liquid crystal display device.

[0283] As a method for manufacturing a touch panel, a method including a step of forming wiring for a touch panel by etching the conductive layer in an area where the resin pattern is not arranged 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 laminated in this order is also preferred, and 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.

[0284] In the method for manufacturing a touch panel including a step of forming wiring for a touch panel, specific aspects of each step and the order in which each step is performed are as described above in the section "Method for manufacturing circuit wiring," and the same applies to preferred aspects. Furthermore, the method for manufacturing a touch panel including the step of forming wiring for a touch panel may include any step (other step) other than those described above. As a method for forming wiring for a touch panel, the method shown in FIG. 1 of WO 2016 / 190405 can also be referred to.

[0285] The above-mentioned method for producing a touch panel produces a touch panel having at least a wiring for a touch panel. The touch panel preferably has a transparent substrate, an electrode, and an insulating layer or a protective layer. Examples of detection methods for touch panels include known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method, etc. Among these, the capacitive method is preferable.

[0286] Examples of touch panels include so-called in-cell types (e.g., those shown in Figures 5, 6, 7, and 8 of JP-T 2012-517051), so-called on-cell types (e.g., those shown in Figure 19 of JP-A 2013-168125 and those shown in Figures 1 and 5 of JP-A 2012-89102), OGS (One Glass Solution) types, TOL (Touch-on-Lens) types (e.g., those shown in Figure 2 of JP-A 2013-54727), various out-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.), and other configurations (e.g., those shown in Figure 6 of JP-A 2013-164871). An example of the touch panel is described in paragraph 0229 of JP2017-120345A. EXAMPLES

[0287] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. In the following examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0288] Hereinafter, first, synthesis examples of compound A and preparation of various compositions will be described, and then the evaluation results of each composition will be shown.

[0289] [Synthesis of compound A] [Synthesis Examples 1 to 4: Synthesis of Polymer Compound A] <Synthesis Example 1> A 300-milliliter three-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 25.0 g of cyclohexanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and heated to 80° C. Next, a mixed solution consisting of 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 (Blenmer AE-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 Industries, Ltd.) was added dropwise at a constant rate so that the dropwise addition was completed in 180 minutes. After the dropwise addition was completed, stirring was continued for another hour, and then a solution consisting of 0.342 g of "V-601" and 1.00 g of cyclohexanone was further added. Then, immediately after the addition, the temperature was raised to 93°C, and stirring was continued for another 2 hours, obtaining 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 polystyrene equivalent by gel permeation chromatography (EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)) using THF as eluent, a flow rate of 0.35 ml / min, and a temperature of 40°C, and the columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation)).

[0290] <Synthesis Examples 2 to 4> Polymers A-5, A-6, and A-9 were synthesized in the same manner as in Synthesis Example 1, except that the monomers and composition ratios used in Synthesis Example 1 were changed.

[0291] The structures of polymers A-1, A-5, A-6, and A-9 are shown below. The numerical values ​​attached to the structural units in the polymers indicate the content (mass %) relative to the total mass of the polymer.

[0292] [ka]

[0293] The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of each polymer are shown in Table 1 below.

[0294] [Table 1]

[0295] [Synthesis Example 5: Synthesis of low molecular weight compound A] With reference to the literature ("Tatematsu et al., Oil Chemistry, 1980, Vol. 29(1), p. 23" and "Tatematsu et al., Pharmacy, 1976, Vol. 25(5), p. 287"), the low molecular weight compound B-1 shown below was synthesized by a known method.

[0296] [ka]

[0297] [Examples 1 to 8 and Comparative Example 1 (Tests in which the composition is a negative-type photosensitive resin composition)] [Production of resin] In the following synthesis examples, the following abbreviations represent the following compounds, respectively. St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) BzMA: benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) AA: Acrylic acid (Tokyo Chemical Industry Co., Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko) MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0298] <Synthesis of Resin P-1> PGMEA (116.5 parts) was placed in a three-neck 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 flask solution maintained at 90° C.±2° C. After the dropwise addition, the solution in the flask was stirred at 90° C.±2° C. for 2 hours to obtain resin P-1 (solid content concentration 30.0% by mass).

[0299] <Synthesis of resins P-2 and P-3> The types and compositions of the monomers used were changed as shown in Table 2 below, and other conditions were the same as for resin P-1 to obtain a solution containing resin P-2 and a solution containing resin P-3. The solid content concentration of the solution containing resin P-2 and the solution containing resin P-3 was 30 mass%.

[0300] Table 2 below shows the composition (mass %) and weight average molecular weight of each resin. All of the resins P-1 to P-3 are alkali-soluble resins. In Table 2, "St" means a structural unit derived from styrene, "BzMA" means a structural unit derived from benzyl methacrylate, "MAA" means a structural unit derived from methacrylic acid, and "MMA" means a structural unit derived from methyl methacrylate.

[0301] [Table 2]

[0302] [Preparation of Photosensitive Resin Compositions 1 to 9] Photosensitive resin compositions 1 to 9 were prepared by mixing these components with stirring according to the formulations shown in Table 3 below. The formulations of each of the photosensitive resin compositions 1 to 9 are shown below. In the table, the numerical value for each component in each photosensitive resin composition indicates the amount (parts by mass) of each component added. The resin was added to each photosensitive resin composition in the form of a solution containing the resin. The numerical values ​​in the table indicating the amount of resin added are the mass of the "solution containing the resin" added. Hereinafter, the same applies to components added to the composition in the form of a mixed solution unless otherwise specified. In the table, the column "Average thickness of photosensitive resin layer (μm)" indicates the average thickness of the photosensitive resin layer formed when a test was conducted using each photosensitive resin composition. The details of the test will be described later.

[0303] [Table 3]

[0304] In Table 3, the details of each component are as follows. BPE-500: 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-200: 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd. A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR-454: Ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema SR-502: Ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema A-9300-CL1: Caprolactone-modified (meth)acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd. B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Hampford SB-PI 701: 4,4′-bis(diethylamino)benzophenone, Sanyo Trading Co., Ltd. Leuco Crystal Violet: Tokyo Chemical Industry Co., Ltd. Brilliant Green: Tokyo Chemical Industry Co., Ltd. N-Phenylglycine: Tokyo Chemical Industry Co., Ltd. CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Co., Ltd. TDP-G: Phenothiazine, manufactured by Kawaguchi Chemicals Irganox 245: Hindered phenolic antioxidant, manufactured by BASF N-nitrosophenylhydroxylamine aluminum salt: Fujifilm Wako Pure Chemical Industries, Ltd. Phenidone: manufactured by Tokyo Chemical Industry Co., Ltd. F552: Megafac F552, manufactured by DIC, a fluorosurfactant not corresponding to Compound A A-1, A-5, A-6, A-9, B-1: Polymers (A-1), (A-5), (A-6), (A-9), (B-1) produced by the above-mentioned methods, respectively (all of which correspond to compound A)

[0305] 〔test〕 <Example 1> The prepared photosensitive resin composition 1 was applied to a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) having a thickness of 16 μm using a slit nozzle with a width of 1.0 m so that the average film thickness of the resulting photosensitive resin layer would be the specified film thickness. Thereafter, the polyethylene terephthalate film (temporary support) was passed through a 3 m drying zone over 60 seconds, where the temperature was 80°C and the air intake and exhaust volumes were adjusted to give a film surface wind speed of 3 m / sec, thereby obtaining a photosensitive resin layer (negative photosensitive resin layer) on the temporary support.

[0306] <Examples 2 to 8 and Comparative Example 1> Photosensitive resin layers were prepared in the same manner as in Photosensitive Resin Composition 1, except that the photosensitive resin compositions used were changed as shown in Table 3, and then evaluated.

[0307] [Examples 9, 10, and Comparative Example 2 (Tests in which the composition is a thermoplastic resin composition)] [Synthesis of Resin P-4] The type and composition of the monomers used were changed as shown in Table 4 below, and the other conditions were the same as for Resin P-1, to obtain a solution containing Resin P-4. The solid content of the solution containing Resin P-4 was 30 mass%. Resin P-4 corresponds to an alkali-soluble resin. The composition (mass%) of Resin P-4 is shown in Table 4. In Table 4, "BzMA" means a structural unit derived from benzyl methacrylate, "MAA" means a structural unit derived from methacrylic acid, and "AA" means a structural unit derived from acrylic acid.

[0308] [Table 4]

[0309] [Preparation of Thermoplastic Resin Compositions 1 to 3] Thermoplastic resin compositions 1 to 3 were prepared by mixing the ingredients in the formulations and amounts (parts by mass) shown in Table 5 below. In the table, the column "Average thickness of thermoplastic resin layer (μm)" indicates the average thickness of the thermoplastic resin layer formed when a test was performed using each thermoplastic resin composition. The details of the test will be described later.

[0310] [Table 5]

[0311] In Table 5, the abbreviations represent the following compounds:

[0312] P-4: A resin containing 75 mass%, 10 mass%, and 15 mass% of structural units based on benzyl methacrylate, structural units based on methyl methacrylate, and structural units based on acrylic acid, respectively, relative to the total mass of the resin, and having a weight average molecular weight of 30,000. P-4 corresponds to a resin that is an alkali-soluble thermoplastic resin. P-4 was added to the thermoplastic resin composition in the form of a solution containing P-4 (solid concentration 30.0 mass%, solvent: PGMEA). Acrybase FF187: A solution containing an alkali-soluble thermoplastic resin, solids concentration 40% by mass, solvent: PGMEA, manufactured by Fujikura Chemical Co., Ltd.

[0313] BB-1: Compound with the structure shown below (a dye that changes color when exposed to acid) [ka]

[0314] C-1: Compound with the structure shown below (photoacid generator, compound described in paragraph 0227 of JP2013-047765A, synthesized according to the method described in paragraph 0227) [ka]

[0315] A-1: Polymer (A-1) produced by the above-mentioned method

[0316] 〔test〕 <Example 9> The prepared thermoplastic resin composition 1 was applied to a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) having a thickness of 16 μm using a slit nozzle so that the average film thickness of the thermoplastic resin layer obtained over a width of 1.0 m was the specified film thickness. The polyethylene terephthalate film (temporary support) was then passed through a 3 m drying zone over 60 seconds at a temperature of 80°C and with the intake and exhaust volumes adjusted to give a film surface wind speed of 3 m / sec, thereby obtaining a thermoplastic resin layer 1 on the temporary support.

[0317] <Example 10 and Comparative Example 2> Thermoplastic resin layers were prepared and evaluated in the same manner as for thermoplastic resin composition 1, except that the thermoplastic resin composition used and the average film thickness of the thermoplastic resin layer formed were changed as shown in Table 5.

[0318] [Example 11 and Comparative Example 3 (Tests in an embodiment in which the composition is a colored resin composition that is also a negative-type photosensitive resin composition)] [Preparation of Photosensitive Resin Compositions 10 to 11] Photosensitive resin compositions 10 and 11 were prepared by stirring and mixing these components according to the formulations shown in the following Table 6. The unit of the amount of each component is parts by mass. In the table, the column "Average thickness of photosensitive resin layer (μm)" indicates the average thickness of the photosensitive resin layer formed when a test was conducted using each photosensitive resin composition. The details of the test will be described later.

[0319] [Table 6]

[0320] Details of the components listed in Table 6 are as follows:

[0321] -Pigments- Black pigment dispersion FDK-T-11: Aqueous solution with a solid content of 27% by mass, Pigment: Carbon black, manufactured by Tokyo Ink Co., Ltd. -Polymerizable compound- A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. 8UX-015A: Urethane acrylate, Taisei Fine Chemical Co., Ltd. · 75 mass % PGMEA solution of KAYARAD DPHA: 75 mass % propylene glycol monomethyl ether acetate solution of KAYARAD DPHA (product name: manufactured by Nippon Kayaku Co., Ltd.). The composition of KAYARAD DPHA is shown below.

[0322] [ka]

[0323] - Binder (alkali-soluble resin) - Acrylic 8KB-001: non-crosslinkable acrylic binder, solid content 38% by mass, solvent: PGMEA, manufactured by Taisei Fine Chemical Co., Ltd., Acrylic (registered trademark) 8KB-001) -Photopolymerization initiator- Irgacure OXE-02: BASF, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) -solvent- 1-Methoxy-2-propyl acetate Methyl ethyl ketone -Additives- 1,2,4-Triazole: Tokyo Chemical Industry Co., Ltd. -Compound A or Comparative Compound- Aa-1: Polymer (A-1) produced by the above-mentioned method Megafac F555A: Manufactured by DIC, a fluorosurfactant that does not fall under Compound A

[0324] 〔test〕 <Example 11> 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 with a width of 1.0 m so that the average film thickness of the resulting photosensitive resin layer would be the specified film thickness. Thereafter, the polyethylene terephthalate film (temporary support) was passed through a 3 m drying zone over 60 seconds, where the temperature was set to 80°C and the intake and exhaust volumes were adjusted so that the film surface wind speed was 3 m / sec, thereby obtaining a photosensitive resin layer (colored resin layer) on the temporary support.

[0325] <Comparative Example 3> Except for changing the photosensitive resin composition used and the average film thickness of the formed photosensitive resin composition as shown in Table 6, coating films were prepared in the same manner as for Photosensitive Resin Composition 10 and evaluated.

[0326] [Examples 12 and 13, Comparative Example 4 (Tests in which the composition is a negative-type photosensitive resin composition)] [Production of resin] <Synthesis of Resin P-5> Propylene glycol monomethyl ether acetate (60 g, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and propylene glycol monomethyl ether (240 g, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were introduced into a 2000 mL flask. The obtained liquid was heated to 90° C. while being stirred at a stirring speed of 250 rpm (rounds per minute; the same applies below). To prepare the dropping liquid (1), methacrylic acid (107.1 g, manufactured by Mitsubishi Rayon Co., Ltd., product name ACRYSTER M), methyl methacrylate (5.46 g, manufactured by Mitsubishi Gas Chemical Co., Ltd., product name MMA), and cyclohexyl methacrylate (231.42 g, manufactured by Mitsubishi Gas Chemical Co., Ltd., product name CHMA) were mixed and diluted with propylene glycol monomethyl ether acetate (60.0 g) to obtain the dropping liquid (1). To prepare the dropping liquid (2), dimethyl 2,2'-azobis(2-methylpropionate) (9.637 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name V-601) was dissolved in propylene glycol monomethyl ether acetate (136.56 g) to obtain the dropping liquid (2). Droplet (1) and Droplet (2) were simultaneously dropped into the above-mentioned 2000 mL flask (specifically, the 2000 mL flask containing the liquid heated to 90°C) over a period of 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 another 3 hours. The solution (reaction solution) obtained in the flask was then diluted with propylene glycol monomethyl ether acetate (178.66 g). Next, tetraethylammonium bromide (1.8 g, Fujifilm Wako Pure Chemical Industries, Ltd.) and hydroquinone monomethyl ether (0.8 g, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the reaction solution. The temperature of the reaction solution was then raised to 100°C. Next, glycidyl methacrylate (76.03 g, NOF Corp., product name Blenmer G) was added dropwise to the reaction solution over 1 hour. The reaction solution was reacted at 100° C. for 6 hours to obtain 1158 g of a solution of resin P-5 (solid content concentration 36.3 mass%). The weight average molecular weight of the obtained resin P-5 was 27000, the number average molecular weight was 15000, and the acid value was 95 mg KOH / g. The amount of residual monomer measured by gas chromatography was less than 0.1 mass% based on the polymer solid content.

[0327] <Synthesis of Resin P-6> Resin P-6 was obtained by referring to the synthesis method of Resin P-5. Specifically, in the dropping solution (1) used in the synthesis of resin P-5, methacrylic acid (107.1 g), methyl methacrylate (5.46 g), and cyclohexyl methacrylate (231.42 g) were used as monomers, but the composition was changed to use the monomers shown in Table 7 below. In addition, the amount of glycidyl methacrylate (76.03 g) added was also changed so that the composition would be MAA-GMA in Table 7 below. The solid content 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. The composition (mass%) of resin P-6 is shown in Table 7. In Table 7, "St" means a structural unit derived from styrene, "MAA" means a structural unit derived from methacrylic acid, and "MMA" means a structural unit derived from methyl methacrylate. "MAA-GMA" represents a structural unit in which glycidyl methacrylate is added to a structural unit derived from methacrylic acid.

[0328] [Table 7]

[0329] Resins P-5 and P-6 correspond to either of the alkali-soluble resins. Resins P-5 and P-6 were added to the photosensitive resin composition in the form of a solution containing the resin.

[0330] [Synthesis of blocked isocyanate compound] <Synthesis of blocked isocyanate compound Q-1> Butanone oxime (Idemitsu Kosan Co., Ltd.) (453 g) was dissolved in methyl ethyl ketone (700 g) under a nitrogen gas flow. 1,3-bis(isocyanatomethyl)cyclohexane (cis, trans isomer mixture, Mitsui Chemicals Co., Ltd., Takenate 600) (500 g) was added dropwise to the resulting solution over 1 hour under ice cooling, and the mixture was allowed to react for another 1 hour after the dropwise addition. The solution was then heated to 40°C and allowed to react 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. The blocked isocyanate compound Q-1 was added to the photosensitive resin composition in the form of a solution containing the blocked isocyanate compound Q-1.

[0331] [ka]

[0332] <Synthesis of blocked isocyanate compound Q-8> Using the synthesis method of blocked isocyanate compound Q-1 as a reference, a methyl ethyl ketone solution (solid content concentration 75.0% by mass) of blocked isocyanate compound Q-8 (see the formula below) was prepared. obtained. The blocked isocyanate compound Q-8 was added to the photosensitive resin composition in the form of a solution containing the blocked isocyanate compound Q-8.

[0333] [ka]

[0334] [Preparation of Photosensitive Resin Compositions 12 to 14] Photosensitive resin compositions 12 to 14 were prepared by stirring and mixing these components according to the formulations shown in the following Table 8. The unit of the amount of each component is parts by mass. In the table, the column "Average thickness of photosensitive resin layer (μm)" indicates the average thickness of the photosensitive resin layer formed when a test was conducted using each photosensitive resin composition. The details of the test will be described later.

[0335] [Table 8]

[0336] 〔test〕 <Example 12> Photosensitive resin composition 12 was applied onto a temporary support of a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.)) having a thickness of 16 μm using a slit nozzle, adjusting the amount of photosensitive resin composition applied so that the average film thickness of the photosensitive composition layer after drying would be a specified film thickness. Next, the temporary support was passed through a 3 m drying zone for 60 seconds, in which the temperature was set to 80°C and the air intake and exhaust volumes were adjusted to give a film surface wind speed of 3 m / sec, thereby forming a photosensitive resin layer (negative photosensitive resin layer) on the temporary support.

[0337] <Example 13, Comparative Example 4> Except for changing the photosensitive resin composition and the average film thickness of the formed photosensitive resin layer as shown in Table 8, coating films were prepared in the same manner as for Photosensitive Resin Composition 12 and evaluated.

[0338] [Evaluation of coating properties] As described above, when a composition layer (photosensitive resin layer, etc.) was formed using each composition (photosensitive resin composition, etc.), the coatability of the composition was evaluated on a 5-level scale from A to E by observing the state from application to drying. The meanings of A to E are as follows. Note that C and above are practical levels. A: Immediately after application, the coating is completely uniform over the entire surface, and the coating properties are extremely good. B: Immediately after application, the coating liquid is slightly thick at only a few mm on both ends, but it levels out before drying and the coating properties are good. C: Slight unevenness is observed immediately after application, but the coating liquid leveled out except for a few millimeters at both ends before drying, and the coating properties were normal. D: There is no repelling immediately after application, but unevenness is observed, and there is no leveling until drying, and the application properties are poor. E: Immediately after application, repelling occurred over the entire surface, the coating was not applied, or the coating properties were extremely poor.

[0339] The evaluation results are shown in Table 9. In the following, "compound used" refers to the type of compound A or comparative compound contained in the composition.

[0340] [Table 9]

[0341] From the results of the examples, it was confirmed that the composition of the present invention has excellent coatability and can form a film with high uniformity. In particular, it was confirmed that when the composition contains a polymer compound A having a poly(oxyalkylene) structure, the coating property is more excellent. In particular, it was confirmed that the coating properties were superior when the composition was a polymer compound A having a poly(oxyalkylene) structure and having a weight average molecular weight of 5,000 to 11,500.

[0342] [Production of transfer film and its use example] [Preparation of transfer film and its use example 1: Example 14] 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.)) using a slit-shaped nozzle with a width of 1.0 m so that the average film thickness of the composition layer after drying would be 2.0 μm. The film was passed through a 3 m drying zone set at 80°C and with the intake and exhaust volumes adjusted to give a film surface wind speed of 0.2 m / sec over 60 seconds, to obtain a laminate A of a temporary support and a thermoplastic resin layer. Next, a water-soluble resin composition described below was applied to the thermoplastic resin layer of the prepared laminate A using a slit nozzle with a width of 1.0 m, adjusting the amount of coating so that the average film thickness of the composition layer after drying would be 1.0 μm. Thereafter, the laminate A was passed through a 3 m drying zone set at a temperature of 100° C. and with an air intake and exhaust volume adjusted to a film surface wind speed of 3 m / sec for 60 seconds, to obtain a laminate B in which a water-soluble resin layer was formed on the thermoplastic resin layer.

[0343] (Water-soluble resin composition) According to the following recipe, these components were mixed with stirring to prepare a water-soluble resin composition. Water-soluble resin (PVA 205, manufactured by Kuraray Co., Ltd.) 32.2 parts by weight Water-soluble resin (polyvinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd.) 14.9 parts by weight Megafac F444 (DIC) 0.01 parts by weight Ion-exchanged water 524.0 parts by weight Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 429.0 parts by mass

[0344] Next, the photosensitive resin composition 1 prepared in Example 1 was applied onto the water-soluble resin layer of the prepared laminate B using a slit nozzle with a width of 1.0 m, adjusting the amount of application so that the average film thickness of the composition layer after drying would be 2.0 μm. Thereafter, the laminate B was passed through a 3 m drying zone for 60 seconds, in which the temperature was 80° C. and the intake and exhaust volumes were adjusted so that the film surface wind speed was 0.2 m / sec, to obtain a laminate in which a photosensitive resin layer was formed on the water-soluble resin layer. Finally, a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.) having a thickness of 16 μm was pressed as a cover film to prepare a transfer film (Example 14).

[0345] A copper layer having a thickness of 200 nm was formed by sputtering on a polyethylene terephthalate (PET) film having a thickness of 100 μm, to prepare a PET substrate with a copper layer. After unwinding the prepared transfer film, it was laminated on the above-mentioned copper-layered PET substrate under lamination conditions of lamination roll temperature 100°C, linear pressure 1.0MPa, and linear speed 4.0m / min. At that time, the cover film was peeled off, and lamination was performed so that the photosensitive resin layer in the transfer film contacted the copper layer. After exposing to an ultra-high pressure mercury lamp through a line and space pattern mask (duty ratio 1:1, line width 20μm) without peeling off the temporary support, the temporary support was peeled off and development was performed. Development was performed by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25°C. When a line and space pattern was formed by the above method, good resolution was shown.

[0346] [Preparation of transfer film and its use example 2: Example 15] On a temporary support of a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.) having a thickness of 16 μm, the photosensitive resin composition 12 prepared in Example 12 was applied using a slit nozzle over a width of 1.0 m, adjusting the amount of the photosensitive resin composition applied so that the thickness of the photosensitive composition layer after drying would be 8.0 μm. Next, the resulting temporary support was passed through a 3 m drying zone set at 80° C. and with the intake and exhaust volumes adjusted so that the film surface wind speed was 0.2 m / sec, over a period of 60 seconds, to obtain a laminate C of the temporary support and the photosensitive resin layer. Next, a resin composition (composition for forming a refractive index adjusting layer) described below was applied to the photosensitive resin layer of the prepared laminate C using a slit nozzle with a width of 1.0 m, adjusting the amount of coating so that the average film thickness of the composition layer after drying would be 80 nm. Then, the laminate C was passed through a 3 m drying zone set at a temperature of 80° C. and a film surface wind speed of 3 m / sec by adjusting the intake and exhaust amounts for 60 seconds, to obtain a laminate in which a refractive index adjusting layer was formed on the photosensitive resin layer.

[0347] Finally, a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.) having a thickness of 16 μm was pressed as a cover film to prepare a transfer film (Example 15).

[0348] (Composition for forming refractive index adjusting layer) These components were mixed by stirring according to the following recipe to prepare a composition for forming a refractive index adjusting layer. The composition for forming a refractive index adjusting layer described below is used to form a refractive index adjusting layer. Nanouse OZS-30M (ZrO2 particles (containing tin oxide) methanol dispersion (non-volatile content 30.5% by mass), manufactured by Nissan Chemical Industries, Ltd.) 4.34 parts by mass Ammonia water (25% by weight) 7.84 parts by weight 0.21 parts by weight of polymer P-7 obtained by the synthesis method described below Alphon UC-3920 (manufactured by Toagosei Co., Ltd.) 0.08 parts by weight Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) 0.03 parts by weight Benzotriazole BT-LX (Johoku Chemical Industry Co., Ltd.) 0.03 parts by mass Monoisopropanolamine 0.02 parts by mass Megafac F444 (DIC) 0.01 parts by weight Ion-exchanged water: 21.7 parts by weight Methanol 65.8 parts by weight

[0349] (Synthesis of Polymer P-7) Propylene glycol monomethyl ether (270.0 g) was introduced into a three-neck flask, and the temperature was raised to 70° C. under a nitrogen stream with stirring. On the other hand, allyl methacrylate (45.6 g, FUJIFILM Wako Pure Chemical Industries, Ltd.) and methacrylic acid (14.4 g) were dissolved in propylene glycol monomethyl ether (270.0 g), and V-65 (3.94 g, FUJIFILM Wako Pure Chemical Industries, Ltd.) was further dissolved to prepare a dropping solution, which was dropped into the flask over 2.5 hours. The mixture was stirred for 2.0 hours and reacted. Thereafter, the temperature of the contents of the flask was returned to room temperature, and the contents of the flask were dropped into 2.7 L of stirred ion-exchanged water to perform reprecipitation, and a suspension was obtained. The suspension was filtered using a Nutsche (Buchner funnel) with filter paper, and the filtrate was further washed with ion-exchanged water to obtain a wet powder. The mixture was subjected to air drying at 45°C, and it was confirmed that the weight had reached a constant value, and Resin A-7 was obtained as a powder with a yield of 70%. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass relative to the polymer solid content.

[0350] After peeling off the protective film from the obtained transfer film, the film was laminated on both sides of a polyethylene terephthalate film, Cosmoshine A4300 (thickness 50 μm), manufactured by Toyobo Co., Ltd., which had been heat-treated at 145° C. for 30 minutes, to form a laminate having a layer structure of temporary support / photosensitive composition layer / refractive index adjustment layer / Cosmoshine A4300 (thickness 50 μm) / refractive index adjustment layer / photosensitive composition layer / temporary support. The lamination conditions were a lamination roll temperature of 110° C., a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. Thereafter, a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp was used to expose the film through a temporary support at a dose of 100 mJ / cm. 2 After peeling off the temporary supports on both sides, the film was exposed to 400 mJ / cm 2 After exposure to i-line on both sides, the photosensitive composition layer was cured by post-baking at 145° C. for 25 minutes to form a cured film. In this way, samples were obtained consisting of a 10 μm thick cured film / refractive index adjustment layer / Cosmoshine A4300 (50 μm thick) / refractive index adjustment layer / 10 μm thick cured film. They had excellent film uniformity and no surface reflection unevenness was observed, which was good.

[0351] [Preparation of transfer film and its use example 3: Example 16] 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.)) using a slit-shaped nozzle with a width of 1.0 m so that the average film thickness of the composition layer after drying would be 2.0 μm. The film was passed through a 3 m drying zone set at 80° C. and with the intake and exhaust volumes adjusted to give a film surface wind speed of 0.2 m / sec over 60 seconds, to obtain a laminate A of a temporary support and a photosensitive resin layer. Next, a polyethylene terephthalate film (Lumirror 16KS40 (manufactured by Toray Industries, Inc.) having a thickness of 16 μm was pressed as a cover film to prepare a transfer film (Example 16).

[0352] A copper layer having a thickness of 200 nm was formed by sputtering on a polyethylene terephthalate (PET) film having a thickness of 100 μm, to prepare a PET substrate with a copper layer. After unwinding the prepared transfer film, it was laminated on the above-mentioned copper-layered PET substrate under lamination conditions of lamination roll temperature 100°C, linear pressure 1.0MPa, and linear speed 4.0m / min. At that time, the cover film was peeled off, and lamination was performed so that the photosensitive resin layer in the transfer film contacted the copper layer. After exposing to an ultra-high pressure mercury lamp through a line and space pattern mask (duty ratio 1:1, line width 20μm) without peeling off the temporary support, the temporary support was peeled off and development was performed. Development was performed by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25°C. When a line and space pattern was formed by the above method, good resolution was shown. [Explanation of symbols]

[0353] 10 Temporary support 12 Thermoplastic resin layer 14 Middle Class 16 Negative photosensitive resin layer 18 Cover film 100 Transfer Film

Claims

1. An alkali-soluble resin, a polymerizable compound, and compound A, The compound A is a compound having a group represented by the following general formula (1), The compound A is a polymer compound, and the polymer compound contains a constituent unit derived from a monomer represented by the following general formula (4A) and a constituent unit derived from a monomer represented by the following general formula (5), or The composition, wherein the compound A is a compound represented by the following general formula (6A) (excluding the polymer compound): General formula (1): *-CF ２ -H In the formula, * represents a bonding position. 【Chemistry 1】 In the formula, 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. ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 【Chemistry 2】 In the formula, 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 of 2 or more. ４ represents a hydrogen atom or a substituent. ５ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 【Chemistry 3】 In the formula, Z represents a monovalent organic group containing a poly(oxyalkylene) structural portion which may have a substituent. ３ is an oxygen atom, a sulfur atom, or -N(R ６ m and n each independently represent an integer of 1 to 6. ６ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the compound A does not include a dye compound having a dye structure having a cationic moiety, and an anionic moiety containing at least one of a structure represented by the following general formula (A1), a structure represented by the following general formula (A2), and a structure containing a boron atom, in which the anionic moiety and the cationic moiety are bonded to each other via a covalent bond and exist in the same molecule. 【Chemistry 4】 In general formula (A1), R １ and R ２ Each independently represents -SO ２ - or -CO-. 【Chemistry 5】 In general formula (A2), R ３ is -SO ２ - or -CO-. ４ and R ５ Each independently represents -SO ２ It represents --, --CO-- or --CN.

2. The composition according to claim 1 , wherein the compound A is a polymer compound having a weight average molecular weight of 5,000 or more.

3. The composition according to claim 1, wherein the compound A is a compound represented by the general formula (6A) having a molecular weight of 2,000 or less.

4. The composition according to any one of claims 1 to 3, further comprising a polymerization initiator.

5. The composition according to any one of claims 1 to 3, wherein the alkali-soluble resin is a thermoplastic resin.

6. The composition according to any one of claims 1 to 5, further comprising black particles.

7. A transfer film having a temporary support and one or more composition layers, A transfer film, wherein at least one of the composition layers is a layer formed using the composition according to any one of claims 1 to 6.

8. a bonding step of contacting a substrate with a surface of the transfer film according to claim 7 opposite to the temporary support, and bonding the transfer film and the substrate to obtain a substrate with a transfer film; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed composition layer to form a resin pattern; The method for producing a laminate further comprises 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.

9. a bonding step of contacting a surface of the transfer film according to claim 7 opposite to the temporary support with a substrate having a conductive layer, and bonding the transfer film and the substrate having a conductive layer to obtain a substrate with a transfer film; an exposure step of pattern-exposing the composition layer; a developing step of developing the exposed composition layer to form a resin pattern; an etching step of etching the conductive layer in an area where the resin pattern is not disposed; The method for producing circuit wiring further comprises 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.

10. A method for producing an electronic device, comprising the method for producing a laminate according to claim 8, The electronic device includes the resin pattern as a cured film.

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