Photosensitive material, transfer film, method for manufacturing circuit wiring, method for manufacturing touch panel, method for forming pattern

Abstract

The present invention provides a photosensitive material capable of forming a film with a low relative permittivity. Further provided are a method for forming a pattern using the above photosensitive material, a method for manufacturing a circuit wiring, a method for manufacturing a touch panel, and a transfer film. The photosensitive material of the present invention satisfies at least one of the following requirements (V01) and (W01). (V01) It contains a polymer A having a carboxyl group and a compound β having a structure b0 that reduces the amount of the carboxyl group of the polymer A by exposure. (W01) It contains a polymer Ab0, which is the above polymer A and further has a structure b0 that reduces the amount of the carboxyl group of the polymer A by exposure.

Description

Technical Field

[0001] The present invention relates to a photosensitive material, a transfer film, a method for manufacturing a circuit wiring, a method for manufacturing a touch panel, and a method for forming a pattern. Background Art

[0002] In a display device including a touch panel such as a capacitive input device (as the display device, specifically, an organic electroluminescence (EL) display device, a liquid crystal display device, etc.), a conductive pattern such as an electrode pattern of a sensor corresponding to a visual recognition unit, wiring of a peripheral wiring portion, and a lead-out wiring portion is provided inside the touch panel.

[0003] Generally, for the purpose of preventing defects such as corrosion of a metal, an increase in resistance between an electrode and a driving circuit, and disconnection, a resin pattern is disposed on the conductive pattern as a protective film (permanent film). In the process of forming the resin pattern, a photosensitive material is generally used.

[0004] For example, in Patent Document 1, there is disclosed "a photosensitive resin composition containing an adhesive polymer having a carboxyl group with an acid value of 75 mgKOH / g or more on a substrate, a photopolymerizable compound, and a polymerization initiator".

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2013 / 084886 Summary of the Invention

[0008] Technical Problem to be Solved by the Invention

[0009] In the photosensitive resin composition (photosensitive material) in Patent Document 1, in a film for protecting an electrode such as a sensor film, a low relative dielectric constant is sometimes required.

[0010] As a result of the inventors' research on the above photosensitive material, it has been found that there is still room for improvement in the relative dielectric constant of the formed film.

[0011] Therefore, an object of the present invention is to provide a photosensitive material capable of forming a film having a low relative dielectric constant. Further, an object of the present invention is to provide a pattern forming method, a method for manufacturing a circuit wiring, a method for manufacturing a touch panel, and a transfer film for the above photosensitive material.

[0012] Means for Solving the Technical Problem

[0013] As a result of the inventors' intensive research on the above problems, it has been found that the above problems can be solved by the following configuration.

[0014] [1]

[0015] A photosensitive material that satisfies at least one of the following requirements (V01) and the following requirement (W01):

[0016] (V01) It contains a polymer A having a carboxyl group and a compound β having a structure b0 that reduces the amount of the carboxyl group possessed by the polymer A upon exposure.

[0017] (W01) It contains a polymer Ab0, which is the above polymer A and further has a structure b0 that reduces the amount of the carboxyl group possessed by the polymer A upon exposure.

[0018] [2]

[0019] The photosensitive material according to [1], wherein

[0020] In the above requirement (V01), the compound β is a compound B, and the compound B is a compound having a structure b in which the structure b0 can accept electrons from the carboxyl group in the photoexcited state.

[0021] In the above requirement (W01), the polymer Ab0 is a polymer Ab, and the polymer Ab is a polymer having a structure b in which the structure b0 can accept electrons from the carboxyl group in the photoexcited state.

[0022] [3]

[0023] The photosensitive material according to [1] or [2], which satisfies at least the above requirement (V01),

[0024] The compound β is an aromatic compound.

[0025] [4]

[0026] The photosensitive material according to any one of [1] to [3], which satisfies at least the above requirement (V01),

[0027] The compound β is a substituted aromatic compound.

[0028] [5]

[0029] The photosensitive material according to any one of [1] to [4], which satisfies at least the above requirement (V01),

[0030] The compound β is a compound that satisfies one or more of the following requirements (1) to (4).

[0031] (1) It has a polycyclic aromatic ring.

[0032] (2) It has a heteroaromatic ring.

[0033] (3) It has an aromatic carbonyl group.

[0034] (4) It has an aromatic imide group.

[0035] [6]

[0036] The photosensitive material according to any one of [1] to [5] satisfies at least the above-mentioned requirement (V01).

[0037] The molar extinction coefficient ε of the above compound β at 365 nm is 1×10 3 (cm·mol / L) -1 or less.

[0038] [7]

[0039] The photosensitive material according to any one of [1] to [6] satisfies at least the above-mentioned requirement (V01).

[0040] The ratio of the molar extinction coefficient ε of the above compound β at 365 nm to the molar extinction coefficient ε' of the above compound β at 313 nm is 3 or less.

[0041] [8]

[0042] The photosensitive material according to any one of [1] to [7] satisfies at least the above-mentioned requirement (V01).

[0043] The pKa of the above compound β in the ground state is 2.0 or more.

[0044] [9]

[0045] The photosensitive material according to any one of [1] to [8] satisfies at least the above-mentioned requirement (V01).

[0046] The pKa of the above compound β in the ground state is 9.0 or less.

[0047]

[10]

[0048] The photosensitive material according to any one of [1] to [9] satisfies at least the above-mentioned requirement (V01).

[0049] The above compound β is one or more selected from pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives.

[0050]

[11]

[0051] The photosensitive material according to any one of [1] to

[10] , wherein

[0052] The above polymer A has a repeating unit based on (meth)acrylic acid.

[0053]

[12]

[0054] The photosensitive material according to any one of [1] to

[11] , wherein,

[0055] The above polymer A has a repeating unit having a polymerizable group.

[0056]

[13]

[0057] The photosensitive material according to any one of [1] to

[12] satisfies at least the above requirement (V01).

[0058] In the above requirement (V01), the above compound β is compound B, and the above compound B is a compound having the above structure b0 that can accept electrons from the above carboxyl group in the photoexcited state.

[0059] In the above photosensitive material, the total number of the above structures b possessed by the above compound B is 5 mol% or more with respect to the total number of carboxyl groups possessed by the above polymer A.

[0060]

[14]

[0061] The photosensitive material according to any one of [1] to

[13] further contains a polymerizable compound.

[0062]

[15]

[0063] The photosensitive material according to any one of [1] to

[14] further contains a photopolymerization initiator.

[0064]

[16]

[0065] The photosensitive material according to

[15] , wherein,

[0066] The above photopolymerization initiator is one or more selected from oxime ester compounds and aminobenzophenone compounds.

[0067]

[17]

[0068] A pattern forming method, which successively includes:

[0069] A step of forming a photosensitive layer on a substrate using the photosensitive material according to

[15] or

[16] ;

[0070] A step of exposing the photosensitive layer into a pattern;

[0071] A step of developing the exposed photosensitive layer with an alkali developer to form a patterned photosensitive layer; and

[0072] A step of exposing the patterned photosensitive layer.

[0073]

[18]

[0074] A manufacturing method of circuit wiring, which successively includes:

[0075] A step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material described in

[15] or

[16] ;

[0076] A step of exposing the photosensitive layer into a pattern;

[0077] A step of developing the exposed photosensitive layer with an alkali developer to form a patterned photosensitive layer;

[0078] A step of exposing the patterned photosensitive layer to form an etching resist film; and

[0079] A step of etching the conductive layer in an area where the etching resist film is not disposed.

[0080]

[19]

[0081] A manufacturing method of a touch panel, which successively includes:

[0082] A step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material described in

[15] or

[16] ;

[0083] A step of exposing the photosensitive layer into a pattern;

[0084] A step of developing the exposed photosensitive layer with an alkali developer to form a patterned photosensitive layer; and

[0085] A step of exposing the patterned photosensitive layer to form a protective film or an insulating film of the conductive layer.

[0086]

[20]

[0087] A transfer film, which has a temporary support and a photosensitive layer formed using the photosensitive material described in any one of [1] to

[16] .

[0088]

[21]

[0089] The transfer film according to

[20] , wherein the transmittance of the photosensitive layer at 365 nm is 65% or more.

[0090]

[22]

[0091] The transfer film according to

[20] or

[21] , wherein,

[0092] The ratio of the transmittance of the photosensitive layer at 365 nm to the transmittance of the photosensitive layer at 313 nm is 1.5 or more.

[0093] 〔23〕

[0094] The transfer film according to any one of 〔20〕 to 〔22〕, wherein

[0095] the content of carboxyl groups in the photosensitive layer is reduced at a reduction rate of 5 mol% or more due to irradiation with actinic rays or radiation.

[0096] Advantages of the Invention

[0097] According to the present invention, it is possible to provide a photosensitive material capable of forming a film having a low relative dielectric constant. Further, it is possible to provide a pattern forming method, a method for manufacturing a circuit wiring, a method for manufacturing a touch panel, and a transfer film related to the above photosensitive material. BRIEF DESCRIPTION OF THE DRAWINGS

[0098] Figure 1 is a schematic diagram showing an example of the layer structure of the transfer film of the embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0099] Hereinafter, the present invention will be described in detail.

[0100] In addition, in this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as a lower limit value and an upper limit value.

[0101] Further, in the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described within a certain numerical range can be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. Further, within the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the value shown in the examples.

[0102] In addition, the term "process" in this specification includes not only an independent process but also a process that is included in this term even when it cannot be clearly distinguished from other processes and achieves the intended purpose of the process.

[0103] In this specification, "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. Therefore, for example, a "transparent resin layer" means a resin layer having an average transmittance of visible light with a wavelength of 400 to 700 nm of 80% or more.

[0104] The average transmittance of visible light is a value measured using a spectrophotometer. For example, it can be measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0105] In this specification, "actinic ray" or "radiation ray" means, for example, bright line spectra of mercury lamps such as g-ray, h-ray, i-ray, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). In the present invention, light means actinic ray or radiation ray.

[0106] In this specification, "exposure", unless otherwise specified, includes not only exposure using mercury lamps, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams is included in the exposure.

[0107] In this specification, unless otherwise specified, the content ratio of each structural unit of the polymer is a molar ratio.

[0108] In this specification, unless otherwise specified, the refractive index is a value measured at a wavelength of 550 nm using an ellipsometer.

[0109] In this specification, unless otherwise specified, the molecular weight in the case of having a molecular weight distribution is a weight-average molecular weight.

[0110] In this specification, the weight-average molecular weight of the resin is a weight-average molecular weight obtained by conversion to polystyrene based on gel permeation chromatography (GPC).

[0111] In this specification, "(meth)acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth)acryloyl" is a concept including both acryloyl and methacryloyl.

[0112] In this specification, unless otherwise specified, the thickness (film thickness) of the layer is as follows: for a thickness of 0.5 μm or more, it is an average thickness measured using a scanning electron microscope (SEM), and for a thickness less than 0.5 μm, it is an average thickness measured using a transmission microscope (TEM). The above average thickness is an average thickness obtained by forming a slice of the measurement object using an ultramicrotome, measuring the thickness at any 5 points, and arithmetically averaging them.

[0113] [Photosensitive material]

[0114] The photosensitive material of the present invention satisfies at least one of the following requirements (V01) and the following requirement (W01).

[0115] (V01) It contains a polymer A having a carboxyl group and a compound β having a structure b0 that reduces the amount of the carboxyl group possessed by the polymer A by exposure.

[0116] (W01) contains polymer Ab0, which is the above-mentioned polymer A and further has a structure b0 that reduces the amount of the above-mentioned carboxyl groups possessed by the above-mentioned polymer A upon exposure.

[0117] Although the mechanism for solving the problems of the present invention by this structure is not yet clear, the present inventors believe as follows.

[0118] That is, structure b0 is introduced by including at least one of compound β and polymer Ab0 in the photosensitive material of the present invention. Structure b0 reduces the amount of the above-mentioned carboxyl groups possessed by the above-mentioned polymer A upon exposure. More specifically, for example, structure b0 causes the carboxyl groups that become acid groups to detach from polymer A as carbon dioxide. In addition, since polymer Ab0 is a form of polymer A, the detached carboxyl groups can be the carboxyl groups in polymer Ab0. And the above-mentioned carboxyl groups that are the objects of the action of structure b0 can also become anions.

[0119] If structure b0 reduces the amount of the above-mentioned carboxyl groups possessed by the above-mentioned polymer A, the polarity of this part is reduced. That is, in the layer (photosensitive layer) formed using the photosensitive material of the present invention, a change in polarity caused by the detachment of the carboxyl groups of polymer A occurs in the exposed part. At the site where the change in polarity has occurred, the solubility in the developer changes. In particular, the solubility in the developer (alkali developer or organic solvent-based developer) changes in the exposed part. For example, in the exposed part, the solubility in the alkali developer decreases, and the solubility in the organic solvent-based developer increases. Utilizing this change in solubility generated in the exposed part, a positive or negative pattern-like film can be formed using the photosensitive material of the present invention. Hereinafter, the pattern-like film is also simply referred to as a pattern.

[0120] And it is considered as follows: Since the presence of carboxyl groups contributes to an increase in the relative dielectric constant of the film, in the film (pattern) formed by negative development using the photosensitive material of the present invention, at least a part of the carboxyl groups in the exposed part detaches as carbon dioxide, so the relative dielectric constant of the obtained film is also reduced. In addition, in the film (pattern) formed by positive development, after development, the remaining film (pattern) is further exposed, so that as described above, at least a part of the carboxyl groups of polymer A in the film becomes carbon dioxide and detaches. Therefore, it is considered that in the film (pattern) formed by positive development, the relative dielectric constant of the obtained film can also be reduced.

[0121] And, as described later, the photosensitive material of the present invention also preferably contains a polymerizable compound.

[0122] If the above carboxyl group dissociates as carbon dioxide, radicals are generated at the site on polymer A where the carboxyl group dissociates as carbon dioxide. Through these radicals, radical polymerization of the polymerizable compound is initiated, enabling the polymerization of polymer A in the exposed area. It is considered that since at least a part of the carboxyl groups in the exposed area of the film formed in this manner also dissociate as carbon dioxide, the relative dielectric constant is reduced.

[0123] As described later, the photosensitive material of the present invention also preferably further contains a polymerizable compound and a photoinitiator.

[0124] When the photosensitive material of the present invention contains a photoinitiator, the dissociation of the carboxyl group and the polymerization initiation reaction as described above can occur at different times. For example, for the photosensitive layer formed using such a photosensitive material, first, the first exposure can be performed at a wavelength or exposure amount at which the dissociation of the carboxyl group hardly occurs, and polymerization based on the photoinitiator can be carried out to cure it. Then, the cured photosensitive layer can be subjected to a second exposure to cause the dissociation of the carboxyl group. In this case, the carboxyl group can also dissociate, and a film with a reduced relative dielectric constant can be obtained.

[0125] Alternatively, the first exposure can be a patterned exposure, and a developing step of removing the unexposed portion or the exposed portion can be performed before the second exposure, and then a pattern (patterned film) can be obtained by further performing the second exposure.

[0126] As described above, the relative dielectric constant of the film formed from the photosensitive material of the present invention is reduced. Also, the moisture permeability (water vapor transmission rate, WVTR) of the above film is reduced. Moreover, the photosensitive material of the present invention not only has good pattern formability but also can suppress film reduction of the film formed during pattern formation.

[0127] It can be said that the present invention has the following effects: The characteristics of being able to reduce the relative dielectric constant of the film formed from the photosensitive material, being able to reduce the moisture permeability of the film formed from the photosensitive material, excellent pattern formability of the photosensitive material, and being able to suppress film reduction of the film formed during pattern formation by the photosensitive material. One or more of these characteristics can also be said to have more excellent effects of the present invention.

[0128] <Requirement (V01), Requirement (W01)>

[0129] The photosensitive material of the present invention satisfies at least one of the following requirement (V01) and the following requirement (W01).

[0130] (V01) It contains polymer A having a carboxyl group and compound β having a structure b0 that reduces the amount of the carboxyl group possessed by the polymer A through exposure.

[0131] (W01) contains polymer Ab0, which is the polymer A and further has a structure b0 that reduces the amount of the carboxyl group possessed by the polymer A upon exposure.

[0132] The photosensitive material of the present invention may satisfy only the requirement (V01) without satisfying the requirement (W01), may not satisfy the requirement (V01) but only satisfy the requirement (W01), or may satisfy both the requirement (V01) and the requirement (W01). Among them, it is preferred to satisfy at least the requirement (V01).

[0133] The above-mentioned structure b0 refers to a structure that exhibits the effect of reducing the amount of the carboxyl group contained in the polymer A when exposed. As the structure b0, a structure that transitions from the ground state to the excited state upon exposure and exhibits the effect of reducing the carboxyl group in the polymer A in the excited state is preferred. As the structure b0, for example, a structure that becomes photoexcited upon exposure and accepts electrons from the carboxyl group contained in the polymer A (structure b) etc. is preferred.

[0134] When the structure b is exposed, the electron acceptance performance increases, and electrons are transferred from the carboxyl group possessed by the polymer A. Additionally, when transferring electrons, the above-mentioned carboxyl group can become an anion. And since the polymer Ab0 is a form of the polymer A, the carboxyl group that transfers electrons to the structure b can also be the carboxyl group in the polymer Ab0.

[0135] If the carboxyl group transfers electrons to the structure b, the above-mentioned carboxyl group becomes unstable, becomes carbon dioxide, and detaches. Thus, the amount of the carboxyl group possessed by the polymer A can be reduced by exposure.

[0136] Among them, in the above-mentioned requirement (V01), the compound β is preferably the compound B. The compound B is a preferred form of the compound β, and it is a compound in which the structure b0 in the compound β becomes the structure b (a structure that can accept electrons from the above-mentioned carboxyl group in the photoexcited state).

[0137] And in the above-mentioned requirement (W01), the above-mentioned polymer Ab0 is also preferably the polymer Ab. The polymer Ab is a preferred form of the polymer Ab0, and it is a polymer in which the structure b0 in the polymer Ab0 becomes the structure b (a structure that can accept electrons from the above-mentioned carboxyl group in the photoexcited state).

[0138] Hereinafter, as an example, polyacrylic acid as the polymer A and quinoline as the compound B are cited, and the inference mechanism of the process (decarboxylation process) of becoming the above-mentioned carbon dioxide (an inference mechanism starting from the structure b and capable of reducing the content of the carboxyl group from the polymer A by exposure) is described in detail.

[0139] In the following attached drawings, the carboxyl group of polyacrylic acid and the nitrogen atom of quinoline coexist to form a hydrogen bond. If quinoline is exposed to light, its electron-accepting property increases, and electrons are transferred from the carboxyl group of polyacrylic acid (Step 1: Photoexcitation). If the carboxyl group of polyacrylic acid transfers electrons to quinoline, it becomes unstable and dissociates as carbon dioxide (Step 2: Decarboxylation reaction). After the above decarboxylation reaction, free radicals are generated in the residues of polyacrylic acid, and radical reactions occur. Radical reactions can occur between the residues of polyacrylic acid, between the residues of polyacrylic acid and a polymerizable compound (monomer (M)) arbitrarily included, and hydrogen atoms in the atmosphere (Step 3: Polarity conversion · Crosslinking · Polymerization reaction). Moreover, after the radical reaction ends, compound B is regenerated and can contribute to the decarboxylation process of polymer A again (Step 4: Regeneration of compound B (catalyst)).

[0140] [Chemical formula 1]

[0141]

[0142] <Requirement (V), Requirement (W)>

[0143] As described above, structure b0 is preferably structure b.

[0144] That is, requirement (V01) is preferably the following requirement (V), and requirement (W01) is preferably the following requirement (W).

[0145] (V) Comprising a polymer A having a carboxyl group and a compound B having a structure b capable of accepting electrons from the carboxyl group of the polymer A in a photoexcited state.

[0146] (W) Comprising a polymer Ab, which is the polymer A and further has a structure b that reduces the amount of the carboxyl group of the polymer A by exposure to light.

[0147] The photosensitive material of the present invention preferably satisfies at least one of the above requirements (V) and the above requirement (W).

[0148] The photosensitive material of the present invention may only satisfy requirement (V) and not satisfy requirement (W), may not satisfy requirement (V) and only satisfy requirement (W), or may satisfy both requirement (V) and requirement (W). Among them, it is preferably to satisfy at least requirement (V).

[0149] Regarding polymer A (including polymer Ab0 and polymer Ab) and compound β (including compound B), detailed descriptions will be given in the following section.

[0150] <Mode>

[0151] The photosensitive material of the present invention is preferably, for example, the following mode.

[0152] Method 1: A method in which the photosensitive material satisfies at least one of the requirements (V01) and (W01) (preferably requirements (V) and (W)), and does not contain a polymerizable compound and a photoinitiator.

[0153] Method 2: A method in which the photosensitive material satisfies at least one of the requirements (V01) and (W01) (preferably requirements (V) and (W)), and further contains a polymerizable compound and does not contain a photoinitiator.

[0154] Method 3: A method in which the photosensitive material satisfies at least one of the requirements (V01) and (W01) (preferably requirements (V) and (W)), and further contains a polymerizable compound and a photoinitiator.

[0155] In addition, in the above Method 1, that the photosensitive material does not contain a polymerizable compound means that the photosensitive material substantially does not contain a polymerizable compound, and the content of the polymerizable compound is less than 3% by mass relative to the total solid content of the photosensitive material, preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass.

[0156] In the above Methods 1 and 2, that the photosensitive material does not contain a photoinitiator means that the photosensitive material substantially does not contain a photoinitiator, and the content of the photoinitiator is less than 0.1% by mass relative to the total solid content of the photosensitive material, preferably 0 to 0.05% by mass, more preferably 0 to 0.01% by mass.

[0157] In this specification, the solid content of the photosensitive material refers to the components in the photosensitive material other than the solvent. And even if it is a liquid component, as long as it is not a solvent, it is regarded as a solid component.

[0158] Hereinafter, the components contained in the photosensitive material of the present invention will be described in detail.

[0159] <Polymer A>

[0160] The photosensitive material contains Polymer A.

[0161] Polymer A is a polymer having a carboxyl group.

[0162] In addition, some or all of the carboxyl groups (-COOH) in Polymer A may be anionized or non-anionized in the photosensitive material. The anionized carboxyl groups (-COO - ) and the non-anionized carboxyl groups are collectively referred to as carboxyl groups.

[0163] That is, in the photosensitive material, polymer A can be anionized or not anionized. The anionized polymer A and the non-anionized polymer A are collectively referred to as polymer A.

[0164] Generally, polymer A is an alkali-soluble resin.

[0165] In the present invention, "alkali-soluble" means that the dissolution rate obtained by the following method is 0.01 μm / second or more.

[0166] A solution of propylene glycol monomethyl ether acetate with a concentration of 25% by mass of the target compound (e.g., resin) is coated on a glass substrate, and then heated in an oven at 100 °C for 3 minutes to form a coating film (thickness 2.0 μm) of the target compound. The dissolution rate (μm / second) of the coating film is determined by immersing the coating film in a 1% by mass aqueous solution of sodium carbonate (liquid temperature 30 °C).

[0167] In addition, when the target compound is insoluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent with a boiling point less than 200 °C other than propylene glycol monomethyl ether acetate (e.g., tetrahydrofuran, toluene, or ethanol).

[0168] Polymer A may further have an acid group other than a carboxyl group as an acid group. Examples of the acid group other than a carboxyl group include a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group.

[0169] From the viewpoint of developability, the acid value of polymer A is preferably 60 to 300 mgKOH / g, more preferably 60 to 275 mgKOH / g, and further preferably 75 to 250 mgKOH / g.

[0170] In this specification, the acid value of the resin is a value measured by the titration method specified in JIS K0070 (1992).

[0171] Polymer A may have structure b0 (preferably structure b). As described above, when structure b0 is exposed, it shows a structure that reduces the amount of carboxyl groups contained in polymer A. As structure b0, it is preferably a structure that transitions from the ground state to the excited state by exposure and shows a function of reducing carboxyl groups in polymer A in the excited state.

[0172] Examples of structure b0 possessed by polymer A include a structure (structure b) that can accept electrons from the carboxyl groups contained in polymer A in the photoexcited state.

[0173] The polymer A having the structure b0 is also particularly referred to as polymer Ab0. The polymer A having the structure b is also particularly referred to as polymer Ab. Further, the polymer A not having the structure b0 (including the structure b) is also particularly referred to as polymer Aa. The polymer A may be polymer Aa or polymer Ab0 (preferably polymer Ab). When the photosensitive material contains two or more kinds of polymer A, it may contain either polymer Aa and polymer Ab0 (preferably polymer Ab), or both. When the photosensitive material of the present invention satisfies the requirement (W01) (preferably requirement (W)), the photosensitive material contains at least polymer Ab0 (preferably polymer Ab).

[0174] That the polymer Aa does not have the structure b0 means that the polymer A substantially does not have the structure b0. For example, the content of the structure b0 in the polymer Aa may be less than 1% by mass, preferably 0 to 0.5% by mass, more preferably 0 to 0.05% by mass, relative to the total mass of the polymer Aa.

[0175] The content of the structure b0 in the polymer Ab0 is preferably 1% by mass or more, more preferably 1 to 50% by mass, still more preferably 5 to 40% by mass, relative to the total mass of the polymer Ab0.

[0176] The content of the structure b in the polymer Ab is preferably 1% by mass or more, more preferably 1 to 50% by mass, still more preferably 5 to 40% by mass, relative to the total mass of the polymer Ab.

[0177] When the polymer A contains polymer Ab0 (preferably polymer Ab), the content of polymer Ab0 (preferably polymer Ab) is preferably 5 to 100% by mass relative to the total mass of the polymer A.

[0178] The structure b0 reduces the amount of carboxyl groups contained in the polymer A by light irradiation. For example, the structure b, which is a preferred form of the structure b0, is excited by light irradiation and accepts electrons from the carboxyl groups (preferably anionized carboxyl groups) in the polymer A in the excited state. Thereby, the carboxyl groups of the polymer A decarboxylate after becoming carboxyl radicals.

[0179] It is considered that through the action of such a structure b0 (preferably structure b), a change in the solubility of the polymer A in the developer (such as insolubilization in a relative alkali developer) occurs in the exposed portion, thereby enabling pattern formation.

[0180] Among them, as the structure b0 (preferably structure b) possessed by the polymer A, a heteroaromatic ring can be cited.

[0181] The above-mentioned heteroaromatic ring may be a monocyclic ring or a polycyclic ring, and is preferably a polycyclic ring. The polycyclic heteroaromatic ring is formed by the fusion of a plurality of (for example, 2 to 5) aromatic ring structures, and at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom.

[0182] The heteroaromatic ring has more than 1 heteroatom (such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.) as a ring member atom, and preferably has 1 to 4 heteroatoms. Moreover, the heteroaromatic ring preferably has more than 1 (for example, 1 to 4) nitrogen atoms as ring member atoms.

[0183] The number of ring member atoms of the above-mentioned heteroaromatic ring is preferably 5 to 15.

[0184] Examples of the above-mentioned heteroaromatic ring include: monocyclic heteroaromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; heteroaromatic rings obtained by the fusion of 2 rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; heteroaromatic rings obtained by the fusion of 3 rings such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenazine ring.

[0185] The above-mentioned heteroaromatic ring may have more than 1 (for example, 1 to 5) substituents. Examples of the above-mentioned substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, and a nitro group. Moreover, when the aromatic ring has more than 2 substituents, the plurality of substituents may be bonded to each other to form a non-aromatic ring.

[0186] Moreover, the above-mentioned heteroaromatic ring is also preferably directly bonded to a carbonyl group.

[0187] It is also preferred that the above-mentioned heteroaromatic ring is bonded to an imide group to form a heteroaromatic imide group in Compound B. In addition, the imide group in the heteroaromatic imide group may or may not form an imide ring together with the heteroaromatic ring.

[0188] In addition, in Polymer A, a plurality of aromatic rings (for example, 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by a structure selected from a single bond, a carbonyl group, and multiple bonds (for example, a vinylidene group which may have a substituent, -C≡C-, -N=N-, etc.). When one or more of the plurality of aromatic rings constituting the above-mentioned series of aromatic ring structures are the above-mentioned heteroaromatic rings, the entire series of aromatic ring structures is regarded as one structure b0 (including structure b).

[0189] The weight-average molecular weight of Polymer A is preferably 5000 or more, and more preferably 10000 or more. The upper limit value of the weight-average molecular weight of Polymer A is not particularly limited and may be set to 100000, preferably 50000 or less.

[0190] As a preferred embodiment of the weight-average molecular weight of Polymer A, it is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000, and still more preferably from 11,000 to 49,000.

[0191] (Repeating unit having a carboxyl group)

[0192] Polymer A preferably has a repeating unit having a carboxyl group.

[0193] As the repeating unit having a carboxyl group, for example, the repeating unit represented by the following general formula (A) can be cited.

[0194] [Chemical formula 2]

[0195]

[0196] In general formula (A), R A1 represents a hydrogen atom, a halogen atom or an alkyl group. The above alkyl group may be linear or branched. The number of carbon atoms of the above alkyl group is preferably from 1 to 5, and more preferably 1.

[0197] A 1 represents a single bond or a divalent linking group. As the above divalent linking group, for example, -CO-, -O-, -S-, -SO-, -SO2-, -NR N -(R N is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group such as a phenylene group, etc.) and a linking group formed by linking a plurality of these.

[0198] As the monomer derived from the repeating unit having a carboxyl group, for example, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-(meth)acryloyloxyethyl succinic acid, styrene carboxylic acid can be cited, and (meth)acrylic acid is preferred.

[0199] That is, the repeating unit having a carboxyl group is preferably a repeating unit based on (meth)acrylic acid.

[0200] Polymer A is preferably a polymer having a repeating unit based on (meth)acrylic acid.

[0201] In addition, in this specification, when representing a repeating unit based on a specific monomer or a repeating unit derived from a specific monomer, etc., the repeating unit only needs to be a repeating unit of a structure formed by polymerization of its specific monomer. For example, in the case where a repeating unit formed by using a monomer different from the specific monomer is modified or deprotected, etc. to be a repeating unit having the same structure as the repeating unit of the structure formed by polymerization of the specific monomer, the repeating unit obtained in this way is also represented as a repeating unit based on the specific monomer and a repeating unit derived from the specific monomer.

[0202] In polymer A, the content of the repeating unit having a carboxyl group is preferably 5 to 100 mol%, more preferably 10 to 65 mol%, and still more preferably 15 to 45 mol% relative to all the repeating units of polymer A.

[0203] Moreover, in polymer A, the content of the repeating unit having a carboxyl group is preferably 1 to 100 mass%, more preferably 5 to 70 mass%, and still more preferably 12 to 50 mass% relative to all the repeating units of polymer A.

[0204] In addition, all the repeating units of the above-mentioned polymer A may be only all the repeating units of polymer Aa, or may be only all the repeating units of polymer Ab0 (preferably polymer Ab), or may be all the repeating units including both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0205] The repeating unit having a carboxyl group may be used alone or in combination of two or more.

[0206] (Repeating unit having a polymerizable group)

[0207] In addition to the above-mentioned repeating units, polymer A preferably has a repeating unit having a polymerizable group.

[0208] Examples of the polymerizable group include ethylenically unsaturated groups (such as (meth)acryloyl group, vinyl group, styryl group, etc.) and cyclic ether groups (such as epoxy group, oxetanyl group, etc.), preferably ethylenically unsaturated groups, and more preferably (meth)acryloyl group.

[0209] Examples of the repeating unit having a polymerizable group also include, for example, a repeating unit represented by the following general formula (B).

[0210] [Chemical formula 3]

[0211]

[0212] In general formula (B), X B1 and X B2 each independently represents -O- or -NRN -R N represents a hydrogen atom or an alkyl group. The above alkyl group may be linear or branched, and preferably has 1 to 5 carbon atoms.

[0213] L represents an alkylene group or an arylene group. The above alkylene group may be linear or branched, and preferably has 1 to 5 carbon atoms. The above arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. The above alkylene group and arylene group may have substituents, and examples of the above substituents include a hydroxyl group.

[0214] R B1 and R B2 each independently represents a hydrogen atom or an alkyl group. The above alkyl group may be linear or branched. The number of carbon atoms of the above alkyl group is preferably 1 to 5, more preferably 1.

[0215] When the polymer A has a repeating unit having a polymerizable group, its content is preferably 3 to 60 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 30 mol% relative to all the repeating units of the polymer A.

[0216] In the polymer A, the content of the repeating unit having a polymerizable group is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, and further preferably 12 to 45% by mass relative to all the repeating units of the polymer A.

[0217] In addition, all the repeating units of the above polymer A may be only all the repeating units of the polymer Aa, or may be only all the repeating units of the polymer Ab0 (preferably the polymer Ab), or may be all the repeating units including both the polymer Aa and the polymer Ab0 (preferably the polymer Ab).

[0218] The repeating units having a polymerizable group may be used alone or in combination of two or more.

[0219] (Repeating unit having structure b0)

[0220] In addition to the above repeating units, the polymer A preferably further has a repeating unit having a structure b0 (preferably a structure b).

[0221] Regarding the structure b0 and the structure b, as described above.

[0222] In the repeating unit having a structure b0 (preferably a structure b), the structure b0 (preferably a structure b) may be present in the main chain or in the side chain, and is preferably present in the side chain. When the structure b0 (preferably a structure b) is present in the side chain, the structure b0 (preferably a structure b) is bonded to the polymer main chain via a single bond or a linking group.

[0223] The repeating unit having structure b0 (preferably structure b) is, for example, a repeating unit based on a monomer having a heteroaromatic ring (specifically, vinylpyridine, vinyl(iso)quinoline and other vinyl heteroaromatic rings, (meth)acrylate monomers having a heteroaromatic ring, etc.).

[0224] Hereinafter, specific examples of the repeating unit having structure b0 (preferably structure b) are shown, but are not limited thereto.

[0225] [Chemical formula 4]

[0226]

[0227] When polymer A has a repeating unit having structure b0 (preferably structure b), its content is preferably 3 to 75 mol%, more preferably 5 to 60 mol%, and still more preferably 10 to 50 mol% relative to all repeating units of polymer A.

[0228] When polymer A has a repeating unit having structure b0 (preferably structure b), its content is preferably 1 to 75% by mass, more preferably 3 to 60% by mass, and still more preferably 5 to 30% by mass relative to all repeating units of polymer A.

[0229] In addition, when polymer A contains polymer Aa and polymer Ab0 (preferably polymer Ab), all repeating units of the above polymer A may be only all repeating units of polymer Ab0 (preferably polymer Ab), or may be all repeating units including both polymer Aa and polymer Ab.

[0230] The repeating unit having structure b0 (preferably structure b) may be used alone or in combination of two or more.

[0231] (Repeating unit having an aromatic ring)

[0232] In addition to the above repeating units, polymer A preferably also has a repeating unit having an aromatic ring (preferably an aromatic hydrocarbon ring).

[0233] As the repeating unit having an aromatic ring, for example, repeating units based on (meth)acrylate having an aromatic ring, styrene and polymerizable styrene derivatives can be cited.

[0234] Examples of the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate.

[0235] Examples of styrene and polymerizable styrene derivatives include methylstyrene, vinyltoluene, tert - alkoxystyrene, acetoxystyrene, 4 - vinylbenzoic acid, styrene dimers, and styrene trimers.

[0236] As the repeating unit having an aromatic ring, the repeating unit represented by the following general formula (C) is also preferred.

[0237] [Chemical formula 5]

[0238]

[0239] In general formula (C), R C1 represents a hydrogen atom, a halogen atom, or an alkyl group. The above - mentioned alkyl group may be linear or branched. The number of carbon atoms of the above - mentioned alkyl group is preferably 1 to 5, more preferably 1.

[0240] Ar C represents a phenyl group or a naphthyl group. The above - mentioned phenyl group and naphthyl group may have one or more substituents. Examples of the above - mentioned substituents include an alkyl group, an alkoxy group, an aryl group, a halogen atom, and a hydroxyl group.

[0241] Hereinafter, repeating units having an aromatic ring are exemplified.

[0242] [Chemical formula 6]

[0243]

[0244] As the repeating unit having an aromatic ring, among them, the following structure is preferred.

[0245] [Chemical formula 7]

[0246]

[0247] When polymer A has a repeating unit having an aromatic ring, its content is preferably 5 to 80 mol%, more preferably 15 to 75 mol%, and further preferably 30 to 70 mol% based on all the repeating units of polymer A.

[0248] When polymer A has a repeating unit having an aromatic ring, its content is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and further preferably 30 to 70 mass% based on all the repeating units of polymer A.

[0249] In addition, all the repeating units of the above - mentioned polymer A may be only all the repeating units of polymer Aa, or only all the repeating units of polymer Ab0 (preferably polymer Ab), or may be all the repeating units including both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0250] The repeating units having an aromatic ring may be used alone or in combination of two or more.

[0251] (Repeating units having an alicyclic structure)

[0252] In addition to the above repeating units, polymer A preferably has repeating units having an alicyclic structure. The alicyclic structure may be a monocyclic or polycyclic structure.

[0253] Examples of the alicyclic structure include a dicyclopentane ring structure, a dicyclopentene ring structure, an isobornyl ring structure, an adamantane ring structure, and a cyclohexyl ring structure.

[0254] Examples of the monomers derived from the repeating units having an alicyclic structure include dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0255] When polymer A contains repeating units having an alicyclic structure, the content thereof is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, and still more preferably 10 to 55 mol% based on all the repeating units of polymer A.

[0256] When polymer A contains repeating units having an alicyclic structure, the content thereof is preferably 3 to 90 mass%, more preferably 5 to 70 mass%, and still more preferably 25 to 60 mass% based on all the repeating units of polymer A.

[0257] In addition, all the repeating units of the above polymer A may be all the repeating units of only polymer Aa, or all the repeating units of only polymer Ab0 (preferably polymer Ab), or all the repeating units including both polymer Aa and polymer Ab0 (preferably polymer Ab).

[0258] The repeating units having an alicyclic structure may be used alone or in combination of two or more.

[0259] (Other repeating units)

[0260] In addition to the above repeating units, polymer A may have other repeating units.

[0261] As the above other repeating units, (meth)acrylic acid alkyl esters can be cited. As the alkyl group, an alkyl group having a chain structure can be cited. As the chain structure, it can be a straight-chain structure or a branched-chain structure. The alkyl group may also have substituents such as a hydroxyl group. As the number of carbon atoms of the alkyl group, 1 to 50 can be cited, and more preferably 1 to 10. As specific examples, repeating units based on methyl methacrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate can be cited.

[0262] When the polymer A contains other repeating units, its content is preferably 1 to 70 mol%, more preferably 2 to 50 mol%, and further preferably 3 to 20 mol% with respect to all the repeating units of the polymer A.

[0263] When the polymer A contains other repeating units, its content is preferably 1 to 70 mass%, more preferably 2 to 50 mass%, and further preferably 5 to 35 mass% with respect to all the repeating units of the polymer A.

[0264] In addition, all the repeating units of the above polymer A may be only all the repeating units of the polymer Aa, or only all the repeating units of the polymer Ab0 (preferably the polymer Ab), or may be all the repeating units including both the polymer Aa and the polymer Ab0 (preferably the polymer Ab).

[0265] The other repeating units may be used alone or in combination of two or more.

[0266] In the photosensitive material of the present invention, the content of the polymer A is preferably 25 to 100 mass% with respect to the total solid content of the photosensitive material. Among them, when the photosensitive material of the present invention does not satisfy the requirement (W01) and / or the requirement (W), the content of the polymer A is preferably 25 to 99 mass% with respect to the total solid content of the photosensitive material.

[0267] Among them, in the photosensitive material of Mode 1, the content of the polymer A is preferably 40 to 98 mass%, more preferably 50 to 96 mass%, and further preferably 60 to 93 mass% with respect to the total solid content of the photosensitive material.

[0268] In the photosensitive material of Mode 2, the content of the polymer A is preferably 30 to 85 mass%, more preferably 45 to 75 mass% with respect to the total solid content of the photosensitive material.

[0269] In the photosensitive material of Mode 3, the content of the polymer A is preferably 30 to 85 mass%, more preferably 45 to 75 mass% with respect to the total solid content of the photosensitive material.

[0270] The content of the above-mentioned polymer A refers to the total content of polymer Aa and polymer Ab0 (preferably polymer Ab) when polymer A contains them.

[0271] From the viewpoints of patterning property and reliability, in the photosensitive material, the content of the residual monomer of the monomer used to form each repeating unit in polymer A is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, based on the total mass of polymer A. The lower limit is not particularly limited, and is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.

[0272] From the viewpoints of patterning property and reliability, the content of the above-mentioned residual monomer is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, based on the total solid content of the photosensitive material. The lower limit is not particularly limited, and is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

[0273] The amount of the above-mentioned residual monomer during the synthesis of polymer A by polymer reaction is also preferably set within the above range. For example, in the case of synthesizing polymer A by reacting glycidyl acrylate on the carboxyl side chain, the content of glycidyl acrylate is preferably set within the above range.

[0274] <Compound β>

[0275] The photosensitive material preferably contains compound β.

[0276] Compound β is a compound having a structure (structure b0) that reduces the amount of carboxyl groups possessed by polymer A upon exposure. In addition, structure b0 is as described above.

[0277] As structure b0, preferably, it is a structure (structure b) that can accept electrons from the carboxyl groups possessed by polymer A in the photoexcited state. That is, as compound β, preferably, it is compound B having a structure (structure b) that can accept electrons from the carboxyl groups possessed by polymer A in the photoexcited state.

[0278] Compound β reduces the amount of carboxyl groups contained in polymer A upon being irradiated with light. For example, compound B, which is a preferred form of compound β, is excited upon light irradiation and accepts electrons from the carboxyl groups (preferably anionic carboxyl groups) in polymer A in the excited state. Thereby, the carboxyl groups of polymer A decarboxylate after becoming carboxyl radicals.

[0279] It is considered that by the action of this compound β (preferably compound B), a change in solubility in the developer of polymer A (insolubilization in a relative alkali developer, etc.) is generated in the exposure part, and thus a pattern can be formed.

[0280] The structure b0 (preferably structure b) possessed by compound β (preferably compound B) can be the overall structure constituting compound β (preferably compound B), or can be a partial structure that is a part of compound β (preferably compound B).

[0281] Compound β (preferably compound B) can be a high molecular compound or a low molecular compound, and is preferably a low molecular compound.

[0282] The molecular weight of compound β (preferably compound B) as a low molecular compound is preferably less than 5000, more preferably less than 1000, further preferably 65 - 300, and particularly preferably 75 - 250.

[0283] From the viewpoint of more excellent effects of the present invention, compound β (preferably compound B) is preferably an aromatic compound. The above aromatic compound is also preferably an aromatic compound having substituents.

[0284] Among them, an aromatic compound refers to a compound having one or more aromatic rings.

[0285] The aromatic ring can exist only one in compound β (preferably compound B), or can exist in plural. In the case of existing in plural, for example, the above aromatic ring can exist in the side chain of the resin, etc.

[0286] In compound β (preferably compound B), the aromatic ring can be used as the structure b that can accept electrons from the carboxyl group of polymer A in the above photoexcited state. The above aromatic ring can be the overall structure constituting compound β (preferably compound B), or can be a partial structure that is a part of compound β (preferably compound B).

[0287] The above aromatic ring can be a monocyclic ring or a polycyclic ring, and is preferably a polycyclic ring. The polycyclic aromatic ring is, for example, an aromatic ring formed by condensing plural (for example, 2 - 5) aromatic ring structures, and at least one of the above plural aromatic ring structures preferably has a heteroatom as a ring member atom.

[0288] The above aromatic ring can be a heteroaromatic ring, preferably has one or more (for example, 1 - 4) heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as ring member atoms, and more preferably has one or more (for example, 1 - 4) nitrogen atoms as ring member atoms.

[0289] The number of ring member atoms of the above aromatic ring is preferably 5 - 15.

[0290] Compound β (preferably compound B) preferably has an aromatic ring with a 6-membered ring having a nitrogen atom as a ring member atom.

[0291] Examples of the above aromatic ring include monocyclic aromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring; bicyclic condensed aromatic rings such as quinoline ring, isoquinoline ring, quinoxaline ring, and quinazoline ring; and tricyclic condensed aromatic rings such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.

[0292] The above aromatic ring may have one or more (e.g., 1 to 5) substituents. Examples of the above substituents include alkyl, aryl, halogen atom, acyl, alkoxycarbonyl, arylcarbonyl, carbamoyl, hydroxyl, cyano, amino, and nitro. Further, when the above aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring.

[0293] Moreover, it is also preferable that the above aromatic ring is directly bonded to a carbonyl group to form an aromatic carbonyl in compound β (preferably compound B). It is also preferable that multiple aromatic rings are bonded via a carbonyl group.

[0294] It is also preferable that the above aromatic ring is bonded to an imide group to form an aromatic imide group in compound β (preferably compound B). In addition, the imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring.

[0295] In addition, when multiple aromatic rings (e.g., 2 to 5 aromatic rings) form a series of aromatic ring structures bonded by a structure selected from a single bond, a carbonyl group, and multiple bonds (e.g., a vinylidene group which may have a substituent, -C≡C-, -N=N-, etc.), the entire series of aromatic ring structures is regarded as one structure b.

[0296] Moreover, it is preferable that one or more of the multiple aromatic rings constituting the above series of aromatic ring structures are the above heteroaromatic rings.

[0297] From the viewpoint of more excellent effects of the present invention, compound β (preferably compound B) is preferably a compound that satisfies one or more (e.g., 1 to 4) of the following requirements (1) to (4). Among them, it is preferable to satisfy at least requirement (2), and as the heteroatom of the heteroaromatic ring, it is preferable to have at least a nitrogen atom.

[0298] (1) Having a polycyclic aromatic ring,

[0299] (2) Having a heteroaromatic ring,

[0300] (3) Having an aromatic carbonyl,

[0301] (4) having an aromatic imide group.

[0302] As specific examples of compound β (preferably compound B), there can be mentioned monocyclic aromatic compounds such as pyridine and pyridine derivatives, pyrazine and pyrazine derivatives, pyrimidine and pyrimidine derivatives, and triazine and triazine derivatives; compounds formed by the condensation of two rings to form an aromatic ring such as quinoline and quinoline derivatives, isoquinoline and isoquinoline derivatives, quinoxaline and quinoxaline derivatives, and quinazoline and quinazoline derivatives; compounds formed by the condensation of three or more rings to form an aromatic ring such as acridine and acridine derivatives, phenanthridine and phenanthridine derivatives, phenanthroline and phenanthroline derivatives, and phenazine and phenazine derivatives.

[0303] Among them, compound β (preferably compound B) is preferably one or more selected from pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives, more preferably one or more selected from quinoline and quinoline derivatives and isoquinoline and isoquinoline derivatives, and still more preferably one or more selected from isoquinoline and isoquinoline derivatives.

[0304] These compounds and their derivatives may further have substituents. As the above-mentioned substituents, alkyl, aryl, halogen atom, acyl, alkoxycarbonyl, arylcarbonyl, carbamoyl, hydroxy, cyano, amino or nitro are preferred, alkyl, aryl, halogen atom, acyl, alkoxycarbonyl, arylcarbonyl, carbamoyl, hydroxy, cyano or nitro are more preferred, alkyl, aryl, acyl, alkoxycarbonyl, arylcarbonyl, carbamoyl, hydroxy, cyano or nitro are still more preferred, and alkyl (for example, linear or branched alkyl having 1 to 10 carbon atoms) is particularly preferred.

[0305] Furthermore, from the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower, compound β (preferably compound B) is preferably an aromatic compound having a substituent (a compound having a substituent at the structural atoms of the aromatic ring contained in compound β (preferably compound B)), more preferably a compound satisfying one or more (for example, 1 to 4) of the above-mentioned requirements (1) to (4) and further having a substituent.

[0306] As for the position of the substituent, for example, in the case of compound β (preferably compound B) quinoline and quinoline derivatives, from the viewpoint of better pattern forming ability and / or lower moisture permeability of the formed pattern, it is preferred that there be a substituent at least at the 2nd and 4th positions on the quinoline ring. And, for example, in the case of compound β (preferably compound B) isoquinoline and isoquinoline derivatives, from the viewpoint of better pattern forming ability and / or lower moisture permeability of the formed pattern, it is preferred that there be a substituent at least at the 1st position on the isoquinoline ring. In addition, as a substituent, an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms) is preferred.

[0307] When the compound β (preferably the compound B) is a polymer, the structure b0 (preferably the structure b) may be a polymer bonded to the polymer main chain via a single bond or a linking group.

[0308] The polymerized compound β (preferably compound B) is obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a (meth)acrylate monomer having a vinyl heteroaromatic ring and / or structure b0 (preferably structure b, more preferably a heteroaromatic ring). It can be copolymerized with other monomers as needed.

[0309] From the viewpoint of better pattern forming ability and / or lower moisture permeability of the formed pattern, the molar absorption coefficient (molar absorption coefficient ε) of compound β (preferably compound B) for light of wavelength 365 nm is, for example, 1×10 3 (cm·mol / L) -1 Below, preferably 1×10 3 (cm·mol / L) -1 less than 5×10 2 (cm·mol / L) -1 , more preferably 1×10 2 (cm·mol / L) -1 The lower limit of the molar absorption coefficient ε is not particularly limited, for example, more than 0 (cm·mol / L) -1 .

[0310] When the photosensitive layer formed using the photosensitive material is exposed via a temporary support (preferably a PET film), the advantage of the molar absorption coefficient ε of the compound β (preferably the compound B) being within the above range is particularly advantageous. That is, since the molar absorption coefficient ε is moderately low, even if the exposure is performed via a temporary support, the generation of bubbles caused by decarboxylation can be controlled, thereby preventing the degradation of the pattern shape.

[0311] Moreover, when the photosensitive material of the present invention is used for the production of a permanent film, by setting the molar extinction coefficient ε of compound β (preferably compound B) within the above range, coloring of the film can be suppressed.

[0312] As the compound having such a molar extinction coefficient ε, the above-mentioned monocyclic aromatic compound or the aromatic compound formed by condensing two rings to form an aromatic ring is preferred, and pyridine or a pyridine derivative, quinoline or a quinoline derivative, or isoquinoline or an isoquinoline derivative is preferred.

[0313] Furthermore, from the viewpoint of more excellent pattern forming ability and / or lower moisture permeability of the formed pattern, the ratio of the molar extinction coefficient (molar extinction coefficient ε) of compound β (preferably compound B) at 365 nm to the molar extinction coefficient (molar extinction coefficient ε') of compound β (preferably compound B) at 313 nm (i.e., the ratio represented by molar extinction coefficient ε / molar extinction coefficient ε') is preferably 3 or less, more preferably 2 or less, and further preferably less than 1. As the lower limit value, there is no particular limitation, for example, it is 0.01 or more.

[0314] In addition, the molar extinction coefficient (molar extinction coefficient ε) of compound β (preferably compound B) for light with a wavelength of 365 nm and the molar extinction coefficient (molar extinction coefficient ε') for light with a wavelength of 313 nm are the molar extinction coefficients measured by dissolving compound β (preferably compound B) in acetonitrile. When compound β (preferably compound B) is not soluble in acetonitrile, the solvent for dissolving compound β (preferably compound B) can be appropriately changed.

[0315] Specific examples of compound β (preferably compound B) include 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, 1-phenylisoquinoline, 1-n-butylisoquinoline, 1-n-butyl-4-methylisoquinoline, 1-methylisoquinoline, 2,4,5,7-tetramethylquinoline, 2-methyl-4-methoxyquinoline, 2,4-dimethylquinoline, phenanthridine, 9-methylacridine, 9-phenylacridine, pyridine, isoquinoline, quinoline, acridine, 4-aminopyridine, 2-chloropyridine, and the like.

[0316] As the lower limit value of the pKa of compound β (preferably compound B) in the ground state, it is preferably 0.5 or more, and more preferably 2.0 or more from the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower. Further, as the upper limit value of the pKa of compound β (preferably compound B) in the ground state, it is preferably 10.0 or less, and more preferably 9.0 or less from the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower. From the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower, the smaller the upper limit value of the pKa of compound β (preferably compound B) in the ground state is, the more preferable it is, further preferably 8.0 or less, and particularly preferably 7.0 or less. In addition, the pKa of compound β (preferably compound B) in the ground state represents the pKa of compound β (preferably compound B) in the unexcited state, and can be obtained by acid titration. Further, when compound β (preferably compound B) is a nitrogen-containing aromatic compound, the pKa of compound β (preferably compound B) in the ground state represents the pKa of the conjugate acid of compound β (preferably compound B) in the ground state.

[0317] Further, when a photosensitive layer is formed by coating the photosensitive material of the present invention, from the viewpoint that it is not easily volatilized in the coating process and the residual rate in the photosensitive layer is more excellent (further, from the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower), the molecular weight of compound β (preferably compound B) is preferably 120 or more, more preferably 130 or more, and further preferably 180 or more. In addition, there is no particular limitation on the upper limit value of the molecular weight of compound β (preferably compound B), and for example, it is 50,000 or less.

[0318] Further, when compound β (preferably compound B) is a compound showing a cationic state (for example, a nitrogen-containing aromatic compound), as the energy level of the HOMO (highest occupied molecular orbital) of compound β (preferably compound B) in the cationic state, it is preferably -8.5 eV or less, and more preferably -7.8 eV or less from the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower. In addition, there is no particular limitation on the lower limit value, and it is more preferably -13.6 eV or more.

[0319] In this specification, the energy level of the HOMO (HOMO in the first electronically excited state) of compound β (preferably compound B) in the cationic state is calculated by the quantum chemical calculation program Gaussian09 (Gaussian09, Revision A.02, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, and D.J. Fox, Gaussian, Inc., Wallingford CT, 2009.).

[0320] As a calculation method, a time-dependent density functional method using B3LYP in the universal functional and 6-31+G(d,p) in the basis function was employed. Also, in order to facilitate the solvent effect, the PCM method based on the parameters of chloroform set in Gaussian09 was used. The structural optimization calculation of the first electronic excited state was carried out using this method to obtain the structure with the minimum energy, and the energy of the HOMO in this structure was calculated.

[0321] Hereinafter, regarding a representative example of compound β (preferably compound B), the HOMO energy level (eV) in its cationic state is shown. In addition, the molecular weight is also shown together.

[0322] [Table 1]

[0323] Table 1

[0324]

[0325] From the viewpoint of more excellent effects of the present invention, in the photosensitive material of the present invention, the content of compound β (preferably compound B) is preferably 0.1 to 50% by mass relative to the total solid content of the photosensitive material.

[0326] Among them, in the photosensitive material of Mode 1, the content of compound β (preferably compound B) is, for example, 0.2 to 45% by mass, preferably 2.0 to 40% by mass, more preferably 4 to 35% by mass, and further preferably 8 to 30% by mass relative to the total solid content of the photosensitive material.

[0327] In the photosensitive material of Mode 2, the content of compound β (preferably compound B) is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass relative to the total solid content of the photosensitive material.

[0328] In the photosensitive material of Mode 3, the content of compound β (preferably compound B) is preferably 0.3 to 20% by mass, more preferably 0.5 to 8% by mass relative to the total solid content of the photosensitive material.

[0329] Compound β (preferably compound B) can be used alone or in combination of two or more.

[0330] Moreover, the preferred range of the total content of compound β (preferably compound B) and the repeating unit having structure b0 (preferably structure b) in polymer A is also the same as the above-mentioned preferred range of the content of compound β (preferably compound B).

[0331] From the viewpoint of more excellent effects of the present invention, in the photosensitive material, the total number of the structures b0 (preferably the structure b) possessed by the compound β (preferably the compound B) is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, particularly preferably 10 mol% or more, and most preferably 20 mol% or more with respect to the total number of carboxyl groups possessed by the polymer A.

[0332] There is no particular limitation on the upper limit of the total number of the structures b0 (preferably the structure b) possessed by the compound β (preferably the compound B), but from the viewpoint of the film quality of the obtained film, it is preferably 200 mol% or less, more preferably 100 mol% or less, and still more preferably 80 mol% or less with respect to the total number of carboxyl groups possessed by the polymer A.

[0333] In addition, when the photosensitive material contains a compound having a carboxyl group in addition to the polymer A, the total number of the structures b0 (preferably the structure b) possessed by the compound β (preferably the compound B) is preferably within the above range with respect to the total number of all carboxyl groups in the photosensitive material.

[0334] Moreover, the preferred range of the total number obtained by adding the total number of the structures b0 (preferably the structure b) possessed by the compound β (preferably the compound B) and the total number of the structures b0 (preferably the structure b) that the polymer A can have is also the same as the above range which is the preferred range of the total number of the structures b0 (the structure b possessed by the compound B) possessed by the compound β.

[0335] <Polymerizable compound>

[0336] The photosensitive material of the present invention also preferably contains a polymerizable compound.

[0337] Among them, in the photosensitive materials of Mode 2 and Mode 3, a polymerizable compound is contained as an essential component.

[0338] The polymerizable compound is preferably a component different from the polymer A. For example, it is preferably a compound having a molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of less than 5000, and is also preferably a polymerizable monomer.

[0339] The polymerizable compound is a polymerizable compound having 1 or more (for example, 1 to 15) ethylenically unsaturated groups in one molecule.

[0340] The polymerizable compound preferably contains a polymerizable compound having two or more functional groups.

[0341] Among them, the polymerizable compound having two or more functional groups means a polymerizable compound having 2 or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.

[0342] As the ethylenically unsaturated group, for example, (meth)acryloyl group, vinyl group and styryl group can be mentioned, and (meth)acryloyl group is preferred.

[0343] As the polymerizable compound, (meth)acrylate is preferred.

[0344] The photosensitive material preferably contains a bifunctional polymerizable compound (preferably a bifunctional (meth)acrylate) and a polymerizable compound having three or more functional groups (preferably a (meth)acrylate having three or more functional groups).

[0345] As the bifunctional polymerizable compound, there is no particular limitation, and it can be appropriately selected from known compounds.

[0346] As the bifunctional polymerizable compound, for example, tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate can be mentioned.

[0347] More specifically, as the bifunctional polymerizable compound, for example, tricyclodecane dimethanol diacrylate (manufactured by A-DCPShin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (manufactured by DCPShin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by A-NOD-NShin-Nakamura Chemical Co., Ltd.) and 1,6-hexanediol diacrylate (manufactured by A-HD-NShin-Nakamura Chemical Co., Ltd.), etc.

[0348] As the polymerizable compound having three or more functional groups, there is no particular limitation, and it can be appropriately selected from known compounds.

[0349] As the polymerizable compound having three or more functional groups, for example, dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton, etc.

[0350] Among them, the concept of "(tri / tetra / penta / hexa)(meth)acrylate" includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and the concept of "(tri / tetra)(meth)acrylate" includes tri(meth)acrylate and tetra(meth)acrylate.

[0351] In addition, as the polymerizable compound, for example, a caprolactone-modified compound of a (meth)acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), an alkylene oxide-modified compound of a (meth)acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM=35E, A=9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glycerol triacrylate (A-GLY=9E manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. can also be cited.

[0352] As the polymerizable compound, a urethane (meth)acrylate (preferably a urethane (meth)acrylate having 3 or more functional groups) can also be cited. The lower limit of the number of functional groups is more preferably 6 or more, and further preferably 8 or more. The upper limit of the number of functional groups can be set to 20 or less, for example.

[0353] As the urethane (meth)acrylate having 3 or more functional groups, for example, 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO,., LTD.); UA-32P, U-15HA, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by KYOEISHA CHEMICAL Co., LTD.); UA-306H, UA-306T, UA-306I, UA-510H, UX-5000 (manufactured by Nippon Kayaku Co., Ltd.), etc. can be cited.

[0354] Moreover, from the viewpoints of improving developability and the sweat resistance of the cured film, the polymerizable compound preferably contains a polymerizable monomer having an acid group.

[0355] As the acid group, for example, a phosphoric acid group, a sulfonic acid group, and a carboxyl group can be cited, and a carboxyl group is preferred.

[0356] As a polymerizable compound having an acid group, for example, a 3- to 4-functional polymerizable compound having an acid group (a compound in which a carboxyl group is introduced into the skeletons of pentaerythritol triacrylate and pentaerythritol tetraacrylate [PETA] (acid value = 80 to 120 mgKOH / g)) and a 5- to 6-functional polymerizable compound having an acid group (a compound in which a carboxyl group is introduced into the skeletons of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [DPHA] (acid value = 25 to 70 mgKOH / g)) can be mentioned, etc.

[0357] These polymerizable compounds having 3 or more functional groups with an acid group can be used in combination with a 2-functional polymerizable compound having an acid group as needed.

[0358] As the polymerizable compound having an acid group, at least one selected from polymerizable compounds having 2 or more functional groups with a carboxyl group and their carboxylic anhydrides is preferable. Thereby, the sweat resistance of the cured film is enhanced.

[0359] The polymerizable compound having 2 or more functional groups with a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0360] As the polymerizable compound having 2 or more functional groups with a carboxyl group, for example, ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.) etc. can be mentioned.

[0361] As the polymerizable compound having an acid group, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese Patent Application Laid-Open No. 2004-239942 can also be mentioned. The content of this publication is incorporated into this specification.

[0362] As the weight average molecular weight (Mw) of the polymerizable compound that can be contained in the photosensitive material, it is preferably 200 to 3000, more preferably 250 to 2600, and further preferably 280 to 2200.

[0363] When the photosensitive material contains a polymerizable compound, among all the polymerizable compounds contained in the photosensitive material, the molecular weight of the polymerizable compound having the smallest molecular weight is preferably 250 or more, and more preferably 280 or more.

[0364] When the photosensitive material of the present invention contains a polymerizable compound, its content is preferably 3 to 70% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 55% by mass with respect to the total solid content of the photosensitive material.

[0365] When the photosensitive material of the present invention contains a polymerizable compound, the mass ratio of the polymerizable compound to polymer A (mass of polymerizable compound / mass of polymer A) is preferably 0.2 to 2.0, more preferably 0.4 to 0.9.

[0366] The polymerizable compound can be used alone or in combination of two or more.

[0367] Moreover, when the photosensitive material of the present invention contains a bifunctional polymerizable compound and a trifunctional or higher-functional polymerizable compound, the content of the bifunctional polymerizable compound is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and still more preferably 30 to 80% by mass, relative to all the polymerizable compounds contained in the photosensitive material.

[0368] Moreover, in this case, the content of the trifunctional or higher-functional polymerizable compound is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and still more preferably 20 to 70% by mass, relative to all the polymerizable compounds contained in the photosensitive material.

[0369] Moreover, when the photosensitive material of the present invention contains a polymerizable compound having two or more functional groups, the photosensitive material may further contain a monofunctional polymerizable compound.

[0370] Among them, when the photosensitive material of the present invention contains a polymerizable compound having two or more functional groups, it is preferred that the polymerizable compound having two or more functional groups is the main component among the polymerizable compounds contained in the photosensitive material.

[0371] Specifically, when the photosensitive material of the present invention contains a polymerizable compound having two or more functional groups, the content of the polymerizable compound having two or more functional groups is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, relative to the total content of the polymerizable compounds contained in the photosensitive material.

[0372] Moreover, when the photosensitive material of the present invention contains a polymerizable compound having an acid group (preferably a bifunctional or higher-functional polymerizable compound having a carboxyl group or its carboxylic anhydride), the content of the polymerizable compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 10% by mass, relative to the total solid content of the photosensitive material.

[0373] <Photoinitiator>

[0374] The photosensitive material of the present invention also preferably contains a photoinitiator.

[0375] Among them, in the photosensitive material of Mode 3, a photoinitiator is contained as an essential component.

[0376] The photoinitiator can be a photo radical polymerization initiator, a photo cationic polymerization initiator, or a photo anionic polymerization initiator, and is preferably a photo radical polymerization initiator.

[0377] There is no particular limitation as the photoinitiator, and known photoinitiators can be used.

[0378] As the photoinitiator, it is preferably at least one selected from oxime ester compounds (photoinitiators having an oxime ester structure) and aminobenzophenone compounds (photoinitiators having an aminobenzophenone structure), and more preferably a compound containing both of them. In the case of a compound containing both of them, the content of the oxime ester compound is preferably 5 to 90% by mass, more preferably 15 to 50% by mass, based on the total content of the two compounds. Other photoinitiators can be further used in combination. For example, hydroxyacetophenone compounds, acylphosphine oxide compounds, bis(triphenylimidazole) compounds, etc. can be mentioned.

[0379] And, as the photoinitiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Laid-Open No. 2011-095716 and paragraphs 0064 to 0081 of Japanese Patent Laid-Open No. 2015-014783 can be used.

[0380] Specific examples of the photoinitiator can include the following photoinitiators.

[0381] As oxime ester compounds, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime) (trade name: [RGACURE OXE-01, IRGACURE series is a product manufactured by BASF), acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyl oxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentan-1-one-(O-acetyl oxime) (trade name: IRGACURE OXE-04, manufactured by BASF, trade name: Lunar6, manufactured by DKSH Japan K.K.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Qiangli 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-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0382] As aminophenone compounds, for example, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series is a product manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad907) and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0383] As other photoinitiators, for example, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819) can be cited.

[0384] When the photosensitive material of the present invention contains a photoinitiator, its content is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass based on the total solid content of the photosensitive material.

[0385] The photoinitiator can be used alone or in combination of two or more.

[0386] <Surfactant>

[0387] The photosensitive material of the present invention may contain a surfactant.

[0388] As the surfactant, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be cited, and nonionic surfactants are preferred.

[0389] As the nonionic surfactant, for example, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycols, silicone-based surfactants, and fluorine-based surfactants can be cited.

[0390] As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640 can also be used.

[0391] Furthermore, as the surfactant, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Application Publication No. 2009-237362 can also be used.

[0392] As commercially available products of fluorosurfactants, for example, MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation above), Fluorad FC 430, FC431, FC171 (manufactured by Sumitomo 3M Limited above), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc. above), Poly Fox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc. above), FTERGENT 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by ENEOS Corporation above), etc.

[0393] Moreover, as the fluorosurfactant, an acrylic compound can also be preferably used. The acrylic compound has a molecular structure having a functional group containing a fluorine atom, and when heated, the functional group part containing a fluorine atom is cut off and the fluorine atom volatilizes. As such a fluorosurfactant, the MEGAFAC EDS series manufactured by DIC Corporation can be cited (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)). For example, MEGAFACE DS-21 can be cited.

[0394] Moreover, as the fluorosurfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used.

[0395] Also, as the fluorosurfactant, block polymers can also be used.

[0396] Also, as the fluorosurfactant, a fluorine-containing polymer compound preferably containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) can also be used.

[0397] Also, as the fluorosurfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in the side chain can also be used. Examples include MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation above), etc.

[0398] As the fluorosurfactant, from the viewpoint of improving environmental adaptability, a surfactant which is a substitute material for a compound having a linear perfluoroalkyl group with 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) is preferred.

[0399] Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Puronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF above), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF above), Solsperse 20000 (manufactured by Japan Lubrizol Corporation above), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation above), PIONIND-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd. above), OLFINE1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd. above), etc.

[0400] As the silicone surfactant, a linear polymer composed of siloxane bonds and a modified silicone polymer obtained by introducing an organic group into a side chain or a terminal can be mentioned.

[0401] As specific examples of the surfactant, DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd. above), and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd. above), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc. above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH above), etc. can be mentioned.

[0402] The content of the surfactant is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0.005 to 3% by mass with respect to the total solid content of the photosensitive material.

[0403] The surfactant can be used alone or in combination of two or more.

[0404] <Solvent>

[0405] From the viewpoint of forming a photosensitive layer by coating, the photosensitive material of the present invention may contain a solvent.

[0406] As the solvent, a commonly used solvent can be used without particular limitation.

[0407] As the solvent, an organic solvent is preferred.

[0408] As the organic solvent, for example, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, 2-propanol, and their mixed solvents can be cited.

[0409] As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate is preferred.

[0410] When the photosensitive material of the present invention contains a solvent, the solid content of the photosensitive material is preferably 5 to 80% by mass, more preferably 8 to 40% by mass, and further preferably 10 to 30% by mass. That is, when the photosensitive material of the present invention contains a solvent, the content of the solvent is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and further preferably 70 to 95% by mass relative to the total mass of the photosensitive material.

[0411] When the photosensitive material of the present invention contains a solvent, from the viewpoint of coatability, the viscosity (25°C) of the photosensitive material is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and further preferably 3 to 30 mPa·s.

[0412] The viscosity is measured, for example, using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO., LTD.).

[0413] When the photosensitive material of the present invention contains a solvent, from the viewpoint of coatability, the surface tension (25°C) of the photosensitive material is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and further preferably 15 to 40 mN / m.

[0414] The surface tension is measured, for example, using Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa InterfaceScience Co., LTD.).

[0415] As the solvent, Solvent described in paragraphs 0054 and 0055 of U.S. Patent Application Publication No. 2005 / 282073 can also be used, and the content of this specification is incorporated into this specification.

[0416] Furthermore, as the solvent, an organic solvent (high-boiling solvent) having a boiling point of 180 to 250°C can also be used as needed.

[0417] In addition, when the photosensitive material of the present invention is formed using a photosensitive layer (a photosensitive layer formed using the photosensitive material) in a transfer film or the like described later, it is also preferable that the photosensitive layer substantially does not contain a solvent. Substantially not containing a solvent means that as long as the content of the solvent is less than 1% by mass relative to the total mass of the photosensitive material (photosensitive layer), preferably 0 to 0.5% by mass, more preferably 0 to 0.001% by mass.

[0418] <Other components>

[0419] The photosensitive material of the present invention may contain other components in addition to the above components.

[0420] As other components, for example, it may further contain known additives such as metal oxidation inhibitors, metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors described later.

[0421] Regarding the preferred forms of these components, they are respectively described in paragraphs 0165 to 0184 of Japanese Patent Application Laid-Open No. 2014-085643, and the content of this publication is incorporated into this specification.

[0422] The photosensitive material may contain impurities.

[0423] As impurities, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and their ions can be cited. Among them, since halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, the following contents are particularly preferably set.

[0424] The content of impurities in the photosensitive material is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less relative to the total mass of the photosensitive material. The content of impurities in the photosensitive material can be set to 1 mass ppb or more, or can also be set to 0.1 mass ppm or more.

[0425] As a method for setting the impurities within the above range, for example, a method of selecting a raw material with a small content of impurities as the raw material of the photosensitive material, a method of preventing the mixing of impurities when forming the photosensitive material, and a method of cleaning and removing impurities can be cited. By this method, the amount of impurities can be set within the above range.

[0426] For example, known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography can be used to quantify impurities.

[0427] Preferably, 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 photosensitive material is low. As the content of these compounds in the photosensitive material, it is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and still more preferably 4 mass ppm or less, respectively, based on the total mass of the photosensitive material.

[0428] The lower limit of the above content can be set to 10 mass ppb or more, or 100 mass ppb or more, respectively, based on the total mass of the photosensitive material. The content of these compounds can be suppressed by the same method as the impurities of the above metals. And it can be quantified by a known measurement method.

[0429] From the viewpoint of improving patterning properties, the content of water in the photosensitive material is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, based on the total mass of the photosensitive material.

[0430] [Transfer film]

[0431] The transfer film of the present invention has a temporary support and a photosensitive layer (hereinafter, also simply referred to as "photosensitive layer") formed using the photosensitive material of the present invention.

[0432] The transfer film of the present invention can be preferably used for forming a film (pattern) on a substrate. When forming a film on a substrate using the transfer film of the present invention, for example, the photosensitive layer of the transfer film of the present invention is transferred to the substrate on which the film (pattern) is to be formed, and processes such as exposure and development are performed on the photosensitive layer transferred onto the substrate, thereby forming a film (pattern) on the substrate.

[0433] The same effects as those obtained by using the photosensitive material of the present invention can be achieved by the transfer film of the present invention. That is, a film with a reduced relative dielectric constant can be formed on a substrate.

[0434] Therefore, the transfer film of the present invention is particularly suitable for use as a film for forming a protective film for a touch panel.

[0435] Hereinafter, the transfer film of the present invention will be described in detail.

[0436] Figure 1 It is a cross-sectional schematic view showing an example of an embodiment of the transfer film of the present invention.

[0437] Figure 1 The transfer film 100 shown in is configured to have a structure in which a temporary support 12, a photosensitive layer (a photosensitive layer formed using the photosensitive material of the present invention) 14, and a cover film 16 are laminated in this order.

[0438] The covering film 16 can be omitted.

[0439] <Temporary support>

[0440] The temporary support is a support that supports the photosensitive layer and can be peeled off from the photosensitive layer.

[0441] From the viewpoint of being able to expose the photosensitive layer through the temporary support during pattern exposure of the photosensitive layer, the temporary support preferably has light transmittance.

[0442] Herein, "having light transmittance" means that the transmittance of the main wavelength of the light used for exposure (which can be pattern exposure or overall surface exposure) is 50% or more. From the viewpoint of more excellent exposure sensitivity, the transmittance of the main wavelength of the light used for exposure is preferably 60% or more, and more preferably 70% or more. As a method for measuring the transmittance, a method of measuring using MCPD Series manufactured by Otsuka Flectronics Co., Ltd. can be cited.

[0443] Specific examples of the temporary support include a glass substrate, a resin film, paper, etc. From the viewpoint of more excellent strength, flexibility, etc., a resin film is preferred. Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferred.

[0444] From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferred that the number of particles, foreign matters, and defects contained in the temporary support is small. The number of fine particles, foreign matters, and defects having a diameter of 2 μm or more is preferably 50 pieces / 10 mm 2 Hereinafter, more preferably 10 pieces / 10 mm 2 Hereinafter, even more preferably 3 pieces / 10 mm 2 Hereinafter. The lower limit is not particularly limited and can be set to 1 piece / 10 mm 2 or more.

[0445] From the viewpoint of further improving operability, it is preferred that there is a layer having particles with a diameter of 0.5 to 5 μm present at 1 piece / mm 2 or more on the surface of the temporary support on the side opposite to the side where the photosensitive layer is formed, and more preferably 1 to 50 pieces / mm 2 .

[0446] From the viewpoints of easy operation and excellent versatility, the thickness of the temporary support is not particularly limited, and is preferably 5 to 200 μm, and more preferably 10 to 150 μm.

[0447] In view of factors such as the strength as a support, the flexibility required when bonding to a substrate for forming circuit wiring, and the light transmittance required in the initial exposure process, the thickness of the temporary support can be appropriately selected according to the material.

[0448] As a preferred embodiment of the temporary support, for example, it is described in paragraphs 0017 to 0018 of Japanese Patent Laid-Open No. 2014-085643, paragraphs 0019 to 0026 of Japanese Patent Laid-Open No. 2016-027363, paragraphs 0041 to 0057 of WO2012 / 081680A1, and paragraphs 0029 to 0040 of WO2018 / 179370A1. The contents of these publications are incorporated herein by reference.

[0449] As the temporary support, for example, Cosmo Shine (registered trademark) A4100 manufactured by TOYOBO CO., LTD., Lumirror (registered trademark) 16FB40 manufactured by Toray Industries, Inc., or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by Toray Industries, Inc. can be used.

[0450] Moreover, as a particularly preferred embodiment of the temporary support, biaxially stretched polyethylene terephthalate films with a thickness of 16 μm, biaxially stretched polyethylene terephthalate films with a thickness of 12 μm, and biaxially stretched polyethylene terephthalate films with a thickness of 9 μm can be cited.

[0451] <Photosensitive layer>

[0452] The photosensitive layer in the transfer film is a layer formed using the photosensitive material of the present invention. For example, the photosensitive layer is preferably a layer consisting essentially of only the solid components of the above-mentioned photosensitive material. That is, the photosensitive material constituting the photosensitive layer preferably contains the solid components (components other than the solvent) that the above-mentioned photosensitive material can contain in the above-mentioned content.

[0453] Among them, in cases where the photosensitive layer is formed by coating and drying a photosensitive material containing a solvent, etc., due to the fact that a solvent, etc. remains in the photosensitive layer even after drying, the photosensitive layer may contain a solvent.

[0454] The photosensitive layer contains polymer A and has a mechanism for reducing the content of carboxyl groups derived from polymer A upon exposure.

[0455] Due to the irradiation of actinic rays or radiation, the content of carboxyl groups in the photosensitive layer preferably decreases at a reduction rate of 5 mol% or more, more preferably at a reduction rate of 10 mol% or more, further preferably at a reduction rate of 20 mol% or more, still more preferably at a reduction rate of 31 mol% or more, particularly preferably at a reduction rate of 40 mol% or more, more particularly preferably at a reduction rate of 51 mol% or more, and most preferably at a reduction rate of 71 mol% or more, relative to the content of carboxyl groups in the photosensitive layer before irradiation. Additionally, as the upper limit value, there is no particular limitation, for example, it is 100 mol% or less.

[0456] In addition, the reduction rate of the content of carboxyl groups derived from polymer A in the photosensitive layer can be calculated by measuring the amount of carboxyl groups in the photosensitive layer before and after exposure. When measuring the amount of carboxyl groups in the photosensitive layer before exposure, for example, analysis and quantification can be carried out by potentiometric titration. And when measuring the amount of carboxyl groups in the photosensitive layer after exposure, the hydrogen atoms of the carboxyl groups can be replaced with metal ions such as lithium, and analysis and quantification can be carried out using ICP-OES (Inductively coupled plasma optical emission spectrometer) to calculate the amount of these metal ions.

[0457] Moreover, the reduction rate of the content of carboxyl groups derived from polymer A in the photosensitive layer can also be obtained by measuring the IR (infrared) spectra of the photosensitive layer before and after exposure and calculating the reduction rate of the peak derived from carboxyl groups. Additionally, the reduction rate of the content of carboxyl groups can be obtained by calculating the reduction rate of the peak of the C=O stretching of carboxyl groups (1710 cm -1 of the peak).

[0458] (Average thickness of the photosensitive layer)

[0459] As the average thickness of the photosensitive layer, it is preferably 0.5 to 20 μm. If the average thickness of the photosensitive layer is 20 μm or less, the resolution of the pattern is more excellent. If the average thickness of the photosensitive layer is 0.5 μm or more, it is preferred from the perspective of pattern linearity. As the average thickness of the photosensitive layer, it is more preferably 0.8 to 15 μm, and further preferably 1.0 to 10 μm. Specific examples of the average thickness of the photosensitive layer include 3.0 μm, 5.0 μm, and 8.0 μm.

[0460] (Method for forming the photosensitive layer)

[0461] For example, a photosensitive material containing the above solid components (components other than the solvent) and a solvent can be prepared, and a photosensitive layer can be formed by coating and drying. It is also possible to prepare a photosensitive material by separately dissolving each component in a solvent in advance to form a solution and then mixing the obtained solutions in a predetermined ratio. The photosensitive material containing a solvent prepared in the above manner is preferably filtered using a filter with a pore size of 0.2 to 30 μm, for example.

[0462] A photosensitive layer can be formed by coating a photosensitive material containing a solvent on a temporary support or a cover film and drying it.

[0463] As the coating method, there is no particular limitation, and known methods such as slit coating, spin coating, curtain coating, and inkjet coating can be cited.

[0464] Moreover, when a high refractive index layer and / or other layers described later are formed on the temporary support or the cover film, the photosensitive layer can be formed on the high refractive index layer and / or other layers.

[0465] From the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower, the transmittance of the photosensitive layer at 365 nm (the transmittance of light with a wavelength of 365 nm) is preferably 20% or more, more preferably 65% or more, and further preferably 90% or more. In addition, as the upper limit value, there is no particular limitation, and it is 100% or less.

[0466] Moreover, from the viewpoint of more excellent pattern forming ability and / or the viewpoint that the moisture permeability of the formed pattern becomes lower, the ratio of the transmittance of the photosensitive layer at 365 nm (the transmittance of light with a wavelength of 365 nm) to the transmittance of the photosensitive layer at 313 nm (the transmittance of light with a wavelength of 313 nm) (the ratio represented by the transmittance of the photosensitive layer at 365 nm / the transmittance of the photosensitive layer at 313 nm) is preferably 1 or more, more preferably 1.5 or more. In addition, as the upper limit value, there is no particular limitation, and it is, for example, 1000 or less.

[0467] As such a photosensitive layer, a photosensitive layer formed using a photosensitive material that satisfies at least one of the above requirements (V) and (W) is more preferably used.

[0468] Moreover, regarding the photosensitive layer, a photosensitive layer formed using a photosensitive material that satisfies any one of the above-described methods 1 to 3 is more preferably used.

[0469] The visible light transmittance per 1.0 μm film thickness of the photosensitive layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.

[0470] As the visible light transmittance, the average transmittance in the wavelength range of 400 to 800 nm, the minimum value of the transmittance in the wavelength range of 400 to 800 nm, and the transmittance at a wavelength of 400 nm preferably all satisfy the above conditions.

[0471] As a preferred value of the visible light transmittance per 1.0 μm film thickness of the photosensitive layer, for example, 87%, 92%, 98%, etc. can be cited.

[0472] From the viewpoint of suppressing residues during development, with respect to the dissolution rate of the photosensitive layer in a 1.0 mass% aqueous solution of sodium carbonate, it is preferably 0.01 μm / second or more, more preferably 0.10 μm / second or more, and still more preferably 0.20 μm / second or more. Also, from the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm / second or less. As specific preferred values, for example, 1.8 μm / second, 1.0 μm / second, 0.7 μm / second, etc. can be cited.

[0473] The dissolution rate per unit time of the photosensitive layer with respect to a 1.0 mass% aqueous solution of sodium carbonate is measured as follows.

[0474] For the photosensitive layer formed on a glass substrate from which the solvent has been sufficiently removed (in the film thickness range of 1.0 to 10 μm), a 1.0 mass% aqueous solution of sodium carbonate is used, and spray development is carried out at 25°C until the photosensitive layer is completely dissolved (wherein, it is set to a maximum of 2 minutes).

[0475] The dissolution rate is obtained by dividing the film thickness of the photosensitive layer by the time required for the photosensitive layer to be completely dissolved. Additionally, in the case where it is not completely dissolved within 2 minutes, the dissolution rate is calculated in the same manner based on the film thickness change amount up to that point.

[0476] During development, a spray nozzle of 1 / 4MINJJX030PP manufactured by H.IKEUCHI&CO., LTD. is used, and the spraying pressure of the spray is set to 0.08 MPa. Under the above conditions, the spray flow rate per unit time is set to 1,800 mL / minute.

[0477] From the viewpoint of pattern formability, the number of foreign substances with a diameter of 1.0 μm or more in the photosensitive layer is preferably 10 per mm 2 Hereinafter, more preferably 5 per mm 2 Hereinafter.

[0478] The number of foreign substances is measured as follows.

[0479] Using an optical microscope, visually observe five arbitrary regions (1 mm × 1 mm) on the surface of the photosensitive layer in the normal direction, measure the number of foreign substances with a diameter of 1.0 μm or more in each region, and calculate the number of foreign substances by taking their arithmetic mean.

[0480] As specific preferred values, for example, 0 pieces / mm 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 etc.

[0481] From the viewpoint of suppressing the generation of aggregates during development, in 1.0 L of a 30°C aqueous solution of 1.0 mass% sodium carbonate, 1.0 cm 3 of the photosensitive layer is dissolved, and the haze of the obtained solution is preferably 60% or less, more preferably 30% or less, still more preferably 10% or less, and most preferably 1% or less.

[0482] The haze is measured as follows.

[0483] First, a 1.0 mass% aqueous solution of sodium carbonate is prepared, and the liquid temperature is adjusted to 30°C. 1.0 cm 3 of the photosensitive layer is added to 1.0 L of the aqueous sodium carbonate solution. While taking care to avoid mixing of air bubbles, it is stirred at 30°C for 4 hours. After stirring, the haze of the solution in which the photosensitive resin layer is dissolved is measured. Using a haze meter (product name "NDH4000", manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD), and using a liquid measurement unit and a liquid measurement dedicated cell with an optical path length of 20 mm to measure the haze.

[0484] As specific preferred values, for example, 0.4%, 1.0%, 9%, 24%, etc. can be cited.

[0485] <High refractive index layer>

[0486] The transfer film also preferably further has a high refractive index layer.

[0487] Preferably, the high refractive index layer is disposed adjacent to the photosensitive layer, and when viewed from the photosensitive layer, it is also preferably disposed on the side opposite to the temporary support.

[0488] The high refractive index layer is not particularly limited except that the refractive index at a wavelength of 550 nm is 1.50 or more.

[0489] The above refractive index of the high refractive index layer is preferably 1.55 or more, more preferably 1.60 or more.

[0490] The upper limit of the refractive index of the high refractive index layer is not particularly limited, preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less, and particularly preferably 1.74 or less.

[0491] Moreover, the refractive index of the high refractive index layer is preferably higher than the refractive index of the photosensitive layer.

[0492] The high refractive index layer may be photocurable (i.e., photosensitive), may be thermocurable, or may have both photocurability and thermocurability.

[0493] The method in which the high refractive index layer has photosensitivity has the following advantages: after transfer, the photosensitive layer and the high refractive index layer transferred onto the substrate can be patterned together by one lithography.

[0494] The high refractive index layer preferably has alkali solubility (for example, solubility in a weakly alkaline aqueous solution).

[0495] Moreover, the high refractive index layer is preferably a transparent layer.

[0496] As the film thickness of the high refractive index layer, it is preferably 500 nm or less, more preferably 110 nm or less, and further preferably 100 nm or less.

[0497] Moreover, the film thickness of the high refractive index layer is preferably 20 nm or more, more preferably 55 nm or more, further preferably 60 nm or more, and particularly preferably 70 nm or more.

[0498] The high refractive index layer sometimes forms a laminate with the transparent electrode pattern (preferably an ITO pattern) and the photosensitive layer by being sandwiched between them after transfer. In this case, by reducing the refractive index difference between the transparent electrode pattern and the high refractive index layer and the refractive index difference between the high refractive index layer and the photosensitive layer, light reflection is further reduced. Thereby, the concealability of the transparent electrode pattern is further improved.

[0499] For example, in the case where a transparent electrode pattern, a high refractive index layer, and a photosensitive layer are laminated in this order, when observed from the transparent electrode pattern side, it is difficult to identify the transparent electrode pattern.

[0500] The refractive index of the high refractive index layer is preferably adjusted according to the refractive index of the transparent electrode pattern.

[0501] For example, in the case where it is formed using oxides of In and Sn (ITO), when the refractive index of the transparent electrode pattern is in the range of 1.8 to 2.0, the refractive index of the high refractive index layer is preferably 1.60 or more. The upper limit of the refractive index of the high refractive index layer at this time is not particularly limited, preferably 2.1 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

[0502] For example, in the case where it is formed using oxides of In and Zn (IZO; Indium Zinc Oxide), when the refractive index of the transparent electrode pattern exceeds 2.0, the refractive index of the high refractive index layer is preferably 1.70 or more and 1.85 or less.

[0503] The method for controlling the refractive index of the high refractive index layer is not particularly limited. For example, methods such as using a resin with a predetermined refractive index alone, using a resin and metal oxide particles or metal particles, and using a composite of a metal salt and a resin can be cited.

[0504] The types of metal oxide particles or metal particles are not particularly limited, and known metal oxide particles or metal particles can be used. Among the metals in the metal oxide particles or metal particles, metalloids such as B, Si, Ge, As, Sb, and Te are also included.

[0505] For example, from the viewpoint of transparency, the average primary particle diameter of the particles (metal oxide particles or metal particles) is preferably 1 to 200 nm, more preferably 3 to 80 nm.

[0506] The average primary particle diameter of the particles is calculated by measuring the particle diameters of any 200 particles using an electron microscope and taking the arithmetic mean of the measurement results. In addition, when the shape of the particles is not spherical, the longest side is taken as the particle diameter.

[0507] Specifically, as the metal oxide particles, at least one selected from zirconia particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silica particles (SiO2 particles), and their composite particles is preferably used.

[0508] Among these, as the metal oxide particles, for example, from the viewpoint of easily adjusting the refractive index of the high refractive index layer to 1.6 or more, at least one selected from zirconia particles and titanium oxide particles is more preferably used.

[0509] When the high refractive index layer contains metal oxide particles, the high refractive index layer may contain only one type of metal oxide particle or may contain two or more types.

[0510] From the viewpoints of being able to make the concealment of concealed objects such as electrode patterns good and effectively improving the visibility of the concealed objects, the content of the particles (metal oxide particles or metal particles) is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 40 to 85% by mass with respect to the total mass of the high refractive index layer.

[0511] When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 40 to 85% by mass with respect to the total mass of the high refractive index layer.

[0512] As commercially available products of metal oxide particles, for example, fired zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), fired zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), fired zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), fired zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (Nanouse OZ-S30M, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), zirconia particles (Nanouse OZ-S30K, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.) can be cited.

[0513] The high refractive index layer preferably contains one or more selected from inorganic particles (such as metal oxide particles or metal particles) having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more), a resin having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more), and a polymerizable compound having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more).

[0514] In this case, it is easy to adjust the refractive index of the high refractive index layer to 1.50 or more (more preferably 1.55 or more, particularly preferably 1.60 or more).

[0515] Moreover, the high refractive index layer preferably contains a binder polymer, a polymerizable monomer, and particles.

[0516] Regarding the components of the high refractive index layer, reference can be made to the components of the curable transparent resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of Japanese Unexamined Patent Application Publication No. 2014-108541, the components of the transparent layer described in paragraphs 0024 to 0035 and 0110 to 0112 of Japanese Unexamined Patent Application Publication No. 2014-010814, the components of the composition having an ammonium salt described in paragraphs 0034 to 0056 of International Publication No. 2016 / 009980, etc.

[0517] Furthermore, the high refractive index layer also preferably contains a metal oxidation inhibitor.

[0518] The metal oxidation inhibitor is a compound (except for compound β) that can perform surface treatment on a member (for example, a conductive member formed on a substrate) in direct contact with the layer it contains.

[0519] When the high refractive index layer contains a metal oxidation inhibitor, when transferring the high refractive index layer onto a substrate (i.e., the object to be transferred), it is possible to perform surface treatment on the member in direct contact with the high refractive index layer (for example, the conductive member formed on the substrate). This surface treatment imparts a metal oxidation inhibition function (protective property) to the member in direct contact with the high refractive index layer.

[0520] The metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom. The compound having an aromatic ring containing a nitrogen atom may have a substituent.

[0521] The metal oxidation inhibitor is preferably a compound having an aromatic ring with a 5-membered ring containing a nitrogen atom as a ring member atom.

[0522] As the aromatic ring containing a nitrogen atom, an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, or a fused ring of any one of them with another aromatic ring is preferred, and an imidazole ring, a triazole ring, a tetrazole ring, or a fused ring of any one of them with another aromatic ring is more preferred.

[0523] The "other aromatic ring" forming the fused ring may be a monocyclic ring or a heterocyclic ring, but a monocyclic ring is preferred, a benzene ring or a naphthalene ring is more preferred, and a benzene ring is further preferred.

[0524] As the metal oxidation inhibitor, imidazole, benzimidazole, tetrazole, 5-amino-1H-tetrazole, mercaptothiadiazole, or benzotriazole is preferred, and imidazole, benzimidazole, 5-amino-1H-tetrazole, or benzotriazole is more preferred.

[0525] As the metal oxidation inhibitor, commercially available products can be used. As commercially available products, for example, BT120 manufactured by JOHOKU CHEMICAL CO., LTD. containing benzotriazole can be preferably used.

[0526] When the high refractive index layer contains a metal oxidation inhibitor, the content of the metal oxidation inhibitor is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass based on the total solid content of the high refractive index layer.

[0527] The high refractive index layer may contain other components in addition to the above components.

[0528] As other components that can be contained in the high refractive index layer, the same components as those that can be contained in the photosensitive material of the present invention can be cited.

[0529] The high refractive index layer also preferably contains a surfactant.

[0530] The method for forming the high refractive index layer is not particularly limited.

[0531] As a method for forming the high refractive index layer, for example, there can be mentioned a method of forming a high refractive index layer by coating a composition for forming a high refractive index layer containing an aqueous solvent on the above-described photosensitive layer formed on a temporary support and drying as needed.

[0532] The composition for forming a high refractive index layer can contain each component of the above-described high refractive index layer.

[0533] The composition for forming a high refractive index layer contains, for example, a binder polymer, a polymerizable monomer, particles, and an aqueous solvent.

[0534] Moreover, as the composition for forming a high refractive index layer, a composition having an ammonium salt described in paragraphs 0034 to 0056 of International Publication No. 2016 / 009980 is also preferred.

[0535] The photosensitive layer and the high refractive index layer are preferably colorless. Specifically, in the CIE1976 (L*, a*, b*) color space of total reflection (incident angle 8°, light source: D - 65 (2° field of view)), the L * value is preferably 10 to 90, the a * value is preferably -1.0 to 1.0, and the b * value is preferably -1.0 to 1.0.

[0536] <Covering film>

[0537] When viewed from the photosensitive layer, the transfer film of the present invention can further have a covering film on the side opposite to the temporary support.

[0538] When the transfer film of the present invention has a high refractive index layer, when viewed from the high refractive index layer, it is preferred that the covering film is disposed on the side opposite to the temporary support (i.e., the side opposite to the photosensitive layer). In this case, the transfer film is, for example, a laminate laminated in the order of "temporary support / photosensitive layer / high refractive index layer / covering film".

[0539] Regarding the covering film, the number of fish eyes having a diameter of 80 μm or more contained in the covering film is preferably 5 pieces / m 2 or less. In addition, "fish eye" means a substance formed by incorporating foreign substances, undissolved substances, and / or oxidation degradation products of a material into a film when manufacturing the film by methods such as heat melting, kneading, extrusion, and / or biaxial stretching and casting of the material.

[0540] The number of particles having a diameter of 3 μm or more contained in the covering film is preferably 30 pieces / mm 2 or less, more preferably 10 pieces / mm 2 or less, and still more preferably 5 pieces / mm 2As described below, it is thus possible to suppress defects caused by the transfer of irregularities due to particles contained in the cover film to the photosensitive resin layer.

[0541] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. When Ra is within these ranges, for example, in the case where the transfer film is in a long strip shape, the winding property when winding the transfer film can be improved.

[0542] Also, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

[0543] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film.

[0544] As the cover film, for example, the films described in paragraphs 0083 to 0087 and 0093 of Japanese Patent Application Laid-Open No. 2006-259138 can be used.

[0545] As the cover film, for example, Alfan (registered trademark) FG-201 manufactured by Oji F-Tex Co., Ltd., Alfan (registered trademark) E-201F manufactured by Oji F-Tex Co., Ltd., Cerapeel (registered trademark) 25WZ manufactured by TORAY ADVANCED FILM CO., LTD., or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by TORAY INDUSTRIES, INC. can be used.

[0546] <Other Layers>

[0547] The transfer film may include other layers (hereinafter, also referred to as "other layers") in addition to the above-described layers. Examples of the other layers include an intermediate layer and a thermoplastic resin layer, and known layers can be appropriately employed.

[0548] Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-085643, and preferred embodiments of other layers other than the above are described in paragraphs 0194 to 0196 of Japanese Patent Application Laid-Open No. 2014-085643. The content of this publication is incorporated herein by reference.

[0549] <Manufacturing Method of Transfer Film>

[0550] The manufacturing method of the transfer film is not particularly limited, and known manufacturing methods can be applied.

[0551] As a method for manufacturing a transfer film, it preferably includes a step of forming a photosensitive layer by coating a photosensitive material containing a solvent on a temporary support and drying it, and more preferably includes a step of further disposing a cover film on the photosensitive layer after the step of forming the above photosensitive layer.

[0552] Moreover, after the step of forming the above photosensitive layer, it may further include a step of forming a high refractive index layer by coating a composition for forming a high refractive index layer and drying it. In this case, it is more preferably further included a step of disposing a cover film on the above high refractive index layer after the step of forming the above high refractive index layer.

[0553] [Pattern formation method]

[0554] As the pattern formation method according to the present invention (also referred to as "the pattern formation method of the present invention"), as long as it is a pattern formation method using the photosensitive material of the present invention, there is no particular limitation, and it preferably sequentially includes a step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention, a step of pattern-exposing the above photosensitive layer, and a step of developing (alkali development or organic solvent development) the exposed photosensitive layer. In addition, when the above development is organic solvent development, it preferably includes a step of further exposing the obtained pattern.

[0555] In addition, when forming a photosensitive layer on a substrate using the photosensitive material of the present invention, it may be a method of manufacturing the above transfer film using the photosensitive material and forming a photosensitive layer on the substrate using such a transfer film. As such a method, specifically, a method of bringing the surface of the photosensitive layer in the above transfer film opposite to the temporary support side into contact with the substrate and laminating the transfer film and the substrate, and setting the photosensitive layer in the transfer film as the photosensitive layer on the above substrate can be cited.

[0556] As specific embodiments of the pattern formation method of the present invention, the pattern formation methods of Embodiment 1 and Embodiment 2 can be cited.

[0557] Hereinafter, each step of the pattern formation methods of Embodiment 1 and Embodiment 2 will be described in detail.

[0558] <Pattern formation method of Embodiment 1>

[0559] The pattern formation method of Embodiment 1 has steps X1 to X3. In addition, the following step X2 corresponds to a step of reducing the content of carboxyl groups from polymer A in the photosensitive layer by exposure. Among them, when the developer in step X3 is an organic solvent-based developer, step X4 is further provided after step X3.

[0560] Step X1: A step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention

[0561] Step X2: A step of pattern-exposing the photosensitive layer

[0562] Step X3: A step of developing the pattern-exposed photosensitive layer using a developer

[0563] Step X4: A step of further exposing the pattern formed by development after the developing step of Step X3

[0564] When an alkali developer is used as the developer in Step X3, it is preferable that the photosensitive material layer is the photosensitive material of Method 1 or Method 2. When an organic solvent-based developer is used as the developer in Step X3, it is preferable that the photosensitive material layer is the photosensitive material of Method 1.

[0565] Moreover, the pattern formation method of Embodiment 1 is preferably applied to a transfer film including a photosensitive layer X formed using the photosensitive material of the above Method 1 or Method 2.

[0566] (Step X1)

[0567] The pattern formation method of Embodiment 1 has a step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention.

[0568] · Substrate

[0569] The substrate is not particularly limited. For example, a glass substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer can be cited. As the substrate included in the substrate having a conductive layer, a glass substrate, a silicon substrate, and a resin substrate can be cited.

[0570] The above substrate is preferably transparent.

[0571] The refractive index of the above substrate is preferably 1.50 to 1.52.

[0572] The above substrate may be composed of a light-transmitting substrate such as a glass substrate. For example, strengthened glass represented by Gorilla Glass of Corning Incorporated Co., Ltd. can also be used. Moreover, as the material included in the above substrate, the materials described in Japanese Unexamined Patent Application Publication No. 2010-086684, Japanese Unexamined Patent Application Publication No. 2010-152809, and Japanese Unexamined Patent Application Publication No. 2010-257492 are also preferably used.

[0573] When the above-mentioned base material includes a resin substrate, as the resin substrate, it is more preferable to use a resin film with small optical deformation and / or high transparency. As specific raw materials, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, etc. can be cited.

[0574] As the substrate included in the substrate having a conductive layer, from the viewpoint of manufacturing in a roll-to-roll manner, a resin substrate is preferred, and a resin film is more preferred.

[0575] As the conductive layer, any conductive layer used in general circuit wiring or touch panel wiring can be cited.

[0576] As the conductive layer, from the viewpoints of conductivity and fine line formation property, one or more layers selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer are preferred, a metal layer is more preferred, and a copper layer or a silver layer is further preferred.

[0577] Moreover, the conductive layer in the substrate having a conductive layer may be one layer or two or more layers.

[0578] When the substrate having a conductive layer includes two or more conductive layers, it is preferred that each conductive layer is a conductive layer of a different material from each other.

[0579] As materials for the conductive layer, metal monomers and conductive metal oxides can be cited.

[0580] As metal monomers, Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, Au, etc. can be cited.

[0581] As conductive metal oxides, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), SiO2, etc. can be cited. In addition, "conductive" means that the volume resistivity is less than 1×10 6 Ωcm, and preferably the volume resistivity is less than 1×10 4 Ωcm.

[0582] When the conductive layer in the substrate having a conductive layer is two or more layers, it is preferred that at least one of the conductive layers contains a conductive metal oxide.

[0583] As the conductive layer, it is preferably an electrode pattern equivalent to a sensor of a visual recognition unit used in a capacitive touch panel or a wiring of a peripheral lead-out portion.

[0584] Moreover, the conductive layer is preferably a transparent layer.

[0585] · The order of process X1

[0586] The process X1 is not particularly limited as long as it can form a photosensitive layer on a substrate using the photosensitive material of the present invention.

[0587] For example, a photosensitive material containing a solvent can be coated on a substrate to form a coating film, and the coating film can be dried to form a photosensitive layer on the substrate. As a method for forming a photosensitive layer on such a substrate, for example, the same method as the method for forming the photosensitive layer described above in the description of the transfer film can be cited.

[0588] Moreover, in the process X1, the photosensitive material used to form the photosensitive layer on the substrate is also preferably the photosensitive material contained in the above transfer film (the photosensitive layer of the transfer film). That is, the photosensitive layer formed in the process X1 is also preferably a layer formed using the above transfer film.

[0589] When forming a photosensitive layer on a substrate using a transfer film, the process X1 is preferably a process of bringing the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support side into contact with the substrate and bonding the transfer film to the substrate. This process is also particularly referred to as the process X1b.

[0590] The process X1b is preferably a bonding process using pressing with a roller or the like and bonding using heating. A known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator can be used during bonding.

[0591] The process X1b is preferably performed by a roll-to-roll method. Therefore, the substrate to be bonded with the transfer film is preferably a resin film or a resin film having a conductive layer.

[0592] Hereinafter, the roll-to-roll method will be described.

[0593] The roll-to-roll method means using a substrate that can be wound and unwound as the substrate, and including a process of unwinding the substrate (also referred to as the "unwinding process") before any process included in the pattern forming method of the present invention and a process of winding the substrate (also referred to as the "winding process") after any process, and performing at least any process (preferably all processes or all processes except the heating process) while conveying the substrate.

[0594] There is no particular limitation on the unwinding method in the unwinding process and the winding method in the winding process, as long as a known method is used in the manufacturing method applying the roll-to-roll method.

[0595] (Process X2)

[0596] The pattern formation method of Embodiment 1 includes a step of pattern-exposing the photosensitive layer after the above-mentioned step X1 (step X2). Step X2 corresponds to a step of reducing the content of carboxyl groups derived from polymer A in the photosensitive layer by exposure. More specifically, it is preferable to pattern-expose the photosensitive layer using light having a wavelength that excites structure b0 (preferably structure b) in the photosensitive layer.

[0597] In addition, structure b0 (preferably structure b) in the above-mentioned photosensitive layer may be a structure possessed by compound β (preferably compound B) contained in the photosensitive layer, may be a structure possessed by polymer A (polymer Ab0, preferably polymer Ab) contained in the photosensitive layer, or may be both.

[0598] In the exposure step, there are no particular limitations on the detailed configuration and specific dimensions of the pattern.

[0599] For example, when applying the pattern formation method of Embodiment 1 to the manufacture of circuit wirings, from the viewpoint of improving the display quality of a display device (e.g., a touch panel) having circuit wirings manufactured by the pattern formation method of Embodiment 1 and from being able to minimize the area occupied by lead wirings as much as possible, at least a part of the pattern (especially, the part corresponding to the electrode pattern and the lead wiring part of the touch panel) is preferably a fine line of 100 μm or less, more preferably a fine line of 70 μm or less.

[0600] As the light source used for exposure, as long as it is a light source that irradiates light in a wavelength range capable of reducing the content of carboxyl groups derived from polymer A in the photosensitive layer (light having a wavelength that excites structure b0 (preferably structure b) in the photosensitive layer. For example, light in wavelength ranges such as 254 nm, 313 nm, 365 nm, 405 nm, etc.) can be appropriately selected. Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode) can be cited.

[0601] As the exposure amount, it is preferably 10 to 10000 mJ / cm 2 and more preferably 50 to 3000 mJ / cm 2 .

[0602] When process X1 is process X1b, in process X2, pattern exposure can be performed after peeling the temporary support from the photosensitive layer, or pattern exposure can be performed through the temporary support before peeling the temporary support, and then the temporary support is peeled. To prevent mask contamination caused by contact between the photosensitive layer and the mask and to avoid the influence on exposure caused by foreign matter attached to the mask, it is preferable to perform pattern exposure without peeling the temporary support. In addition, the pattern exposure can be exposure through a mask or direct exposure using a laser or the like.

[0603] (Process X3)

[0604] The pattern formation method of Embodiment 1 includes, after the above-mentioned process X2, a process (process X3)+ of developing the photosensitive layer that has been pattern-exposed using a developer (an alkali developer or an organic solvent-based developer).

[0605] The content of carboxyl groups in the photosensitive layer of the photosensitive layer that has passed through process X2 decreases through the exposure section, and a difference in solubility (dissolution contrast) in the developer is generated between the exposed section and the unexposed section. By forming a dissolution contrast in the photosensitive layer, a pattern can be formed in process X3. In addition, when the developer in the above-mentioned process X3 is an alkali developer, the unexposed section is removed by performing the above-mentioned process X3 to form a negative pattern. On the other hand, when the developer in the above-mentioned process X3 is an organic solvent-based developer, the exposed section is removed by performing the above-mentioned process X3 to form a positive pattern. The obtained positive pattern needs to be subjected to a treatment that reduces the content of carboxyl groups from polymer A through process X4 described later.

[0606] ·Alkali developer

[0607] As the alkali developer, as long as it can remove the unexposed section of the photosensitive resin layer, there is no particular limitation. For example, known developers such as the developer described in Japanese Patent Laid-Open No. 5-072724 can be used.

[0608] As the alkali developer, for example, an aqueous alkali solution-based developer containing a compound with pKa = 7 - 13 at a concentration of 0.05 - 5 mol / L (liter) is preferably used.

[0609] In addition, the alkali developer can further contain a water-soluble organic solvent, a surfactant, and the like. As the alkali developer, for example, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 is preferably used.

[0610] ·Organic solvent-based developer

[0611] As an organic solvent-based developer, as long as it can remove the exposed portion of the photosensitive resin layer, there is no particular limitation. For example, a developer containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

[0612] In the organic solvent-based developer, multiple organic solvents can be mixed, or it can be used by mixing with organic solvents or water other than the above. Among them, in order to fully exert the effects of the present invention, the water content of the organic solvent-based developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. The concentration of the organic solvent (the total in the case of mixing multiple) in the organic solvent-based developer is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. In addition, as the upper limit value, for example, it is 100% by mass or less.

[0613] As the developing method, there is no particular limitation, and it can be any one of spin immersion development, spray development, spin development, dip coating development, etc. Among them, when spray development is described, the developer can be blown onto the exposed photosensitive resin layer by spraying to remove unnecessary parts. And after development, it is also preferable to blow a cleaning agent or the like by spraying and wipe while using a brush or the like to remove development residues. The liquid temperature of the developer is preferably 20 to 40 °C.

[0614] The pattern forming method of Embodiment 1 can further have a baking step after heating the pattern including the photosensitive layer obtained by development.

[0615] Post-baking is preferably carried out in an environment of 8.1 to 121.6 kPa, more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferably carried out in an environment of 111.46 kPa or less, and further preferably in an environment of 101.3 kPa or less.

[0616] The temperature of post-baking is preferably 80 to 250 °C, more preferably 110 to 170 °C, and further preferably 130 to 150 °C.

[0617] The time of post-baking is preferably 1 to 60 minutes, more preferably 2 to 50 minutes, and further preferably 5 to 40 minutes.

[0618] Post-baking can be carried out in an air environment or in a nitrogen-substituted environment.

[0619] (Process X4)

[0620] When the developer for the above-described step X3 is an organic solvent-based developer, step X4 is performed on the obtained positive pattern. Step X4 is a step corresponding to exposing the positive pattern obtained in step X3 and reducing the content of the carboxyl group derived from polymer A. More specifically, it is preferable to perform pattern exposure on the photosensitive layer using light having a wavelength that excites structure b0 (preferably structure b) in the photosensitive layer.

[0621] As the light source and exposure amount used for exposure, they are the same as those described in step X1, and the preferred modes are also the same.

[0622] <Pattern formation method of Embodiment 2>

[0623] The pattern formation method of Embodiment 2 sequentially includes step Y1, step Y2P, and step Y3, and further includes step Y2Q (a step of further exposing the exposed photosensitive layer) between step Y2P and step Y3 or after step Y3.

[0624] Step Y1: A step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention

[0625] Step Y2P: A step of exposing the photosensitive layer

[0626] Step Y2Q: A step of further exposing the exposed photosensitive layer

[0627] Step Y3: A step of developing the photosensitive layer using a developer

[0628] As the pattern formation method of Embodiment 2, it is preferably applied when the photosensitive layer further contains a photoinitiator and a polymerizable compound. Thus, the pattern formation method of Embodiment 2 is preferably applied to the photosensitive material of the above-described Mode 3.

[0629] Hereinafter, the pattern formation method of Embodiment 2 will be described. Regarding steps Y1 and Y3, they are the same as steps X1 and X3 respectively, and the description thereof is omitted.

[0630] In addition, step Y3 may be performed at least after step Y2P, and step Y3 may be performed between step Y2P and step Y2Q.

[0631] In addition, the pattern forming method of Embodiment 2 may further include a post-baking step of heating the pattern of the photosensitive layer obtained by development after Step Y3. Regarding the post-baking step, it can be implemented by the same method as the post-baking step that the pattern forming method of Embodiment 1 described above may have. When Step Y3 is implemented between Step Y2P and Step Y2Q, the post-baking step may be implemented before Step Y2Q or after Step Y2Q as long as it is implemented after Step Y3.

[0632] (Step Y2P, Step Y2Q)

[0633] The pattern forming method of Embodiment 2 includes a step of exposing the photosensitive layer that has undergone Step Y1 (Step Y2P) and a step of further exposing the exposed photosensitive layer (Step Y2Q).

[0634] Any one of the exposure processes (Step Y2P and Step Y2Q) is mainly an exposure for reducing the content of the carboxyl group of Polymer A by exposure, and any one of the exposure processes (Step Y2P and Step Y2Q) corresponds to an exposure mainly for causing a polymerization reaction of the polymerizable compound based on the photoinitiator. Also, the exposure processes (Step Y2P and Step Y2Q) can each be either a full-surface exposure or a pattern exposure, but any one of the exposure processes is a pattern exposure.

[0635] For example, when Step Y2P is a pattern exposure for reducing the content of the carboxyl group of Polymer A by exposure, the developer used in Step Y3 can be an alkaline developer or an organic solvent-based developer. Among them, when developing with an organic solvent-based developer, Step Y2Q is usually implemented after Step Y3, and in the developed photosensitive layer (pattern), while causing a polymerization reaction of the polymerizable compound based on the photoinitiator, the content of the carboxyl group from Polymer A decreases.

[0636] Also, for example, when Step Y2P is a pattern exposure for causing a polymerization reaction of the polymerizable compound based on the photoinitiator, the developer used in Step Y3 is usually an alkaline developer. In this case, Step Y2Q can be implemented before or after Step Y3, and Step Y2Q when implemented before Step Y3 is usually a pattern exposure.

[0637] In step Y2P and step Y2Q, as the light source used for exposure, any light source that irradiates a wavelength range that can reduce the content of carboxyl groups in the polymer A in the photosensitive layer (light of a wavelength that excites the structure b0 (preferably the structure b) in the photosensitive layer. For example, light of a wavelength range such as 254nm, 313nm, 365nm, and 405nm) and a wavelength range that can cause a reaction of a polymerizable compound based on a photopolymerization initiator in the photosensitive layer (light of a wavelength that makes the photopolymerization initiator photosensitize. For example, 254nm, 313nm, 365nm, 405nm, etc.) can be appropriately selected. Specifically, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes) can be mentioned.

[0638] In the exposure for reducing the content of the carboxyl group of the polymer A in the photosensitive layer, the exposure amount is preferably 10 to 10000 mJ / cm 2 , more preferably 50 to 3000 mJ / cm 2 .

[0639] In the exposure for inducing a reaction of the polymerizable compound by the photopolymerization initiator in the photosensitive layer, the exposure amount is preferably 5 to 200 mJ / cm 2 , more preferably 10 to 150 mJ / cm 2 .

[0640] When process Y1 is implemented in the same manner as process X1b, in process Y2P and / or process Y2Q, pattern exposure may be performed after peeling off the temporary support from the photosensitive layer, or pattern exposure may be performed across the temporary support before peeling off the temporary support, and then the temporary support is peeled off. In order to prevent mask contamination caused by contact between the photosensitive layer and the mask, and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferred to perform pattern exposure without peeling off the temporary support. In addition, pattern exposure may be exposure across the mask, or direct exposure using a laser or the like.

[0641] In the exposure process, the detailed arrangement and specific size of the pattern are not particularly limited.

[0642] For example, when the pattern forming method of embodiment 2 is applied to the manufacture of circuit wiring, from the perspective of improving the display quality of a display device (for example, a touch panel) having an input device with circuit wiring manufactured by the pattern forming method of embodiment 2, and from the perspective of minimizing the area occupied by the lead-out wiring, at least a portion of the pattern (especially the portion corresponding to the electrode pattern of the touch panel and the portion of the lead-out wiring) is preferably a thin line of less than 100 μm, and more preferably a thin line of less than 70 μm.

[0643] (Preferred mode)

[0644] As the pattern forming method of Embodiment 2, in which step Y2P is step Y2A, step Y2Q is step Y2B, and preferably has step Y1, step Y2A, step Y3 and step Y2B in sequence. In addition, one of step Y2A and step Y2B corresponds to an exposure step for reducing the carboxyl group content of polymer A by exposure, and the other corresponds to an exposure step for causing the reaction of the photoinitiator and the polymerizable compound.

[0645] Step Y1: A step of forming a photosensitive layer on a substrate using the photosensitive material of the present invention (preferably a step of bringing the surface of the photosensitive layer of the transfer film on the side opposite to the temporary support into contact with the substrate and laminating the transfer film to the substrate).

[0646] Step Y2A: A step of exposing the photosensitive layer in a pattern.

[0647] Step Y3: A step of developing the photosensitive layer with an alkali developer to form a patterned photosensitive layer.

[0648] Step Y2B: A step of exposing the patterned photosensitive layer.

[0649] The above step Y2A is preferably an exposure step for causing the reaction of the photoinitiator and the polymerizable compound, and the above step Y2B is preferably an exposure step for reducing the carboxyl group content from polymer A by exposure.

[0650] (Any step that the pattern forming methods of Embodiment 1 and Embodiment 2 can have)

[0651] The pattern forming methods of Embodiment 1 and Embodiment 2 may include any other steps (other steps) in addition to the above. For example, the following steps can be cited, but are not limited to these steps.

[0652] (Cover film peeling step)

[0653] When a photosensitive layer is formed on a substrate using a transfer film and the transfer film has a cover film, the above pattern forming method preferably includes a step of peeling the cover film of the transfer film (hereinafter, also referred to as "cover film peeling step"). The method of peeling the cover film is not particularly limited, and a known method can be applied.

[0654] (Step of reducing visible light reflectance)

[0655] When the substrate is a substrate having a conductive layer, the above-described pattern forming method may further include a step of performing a treatment for reducing the visible light reflectance of the conductive layer. Further, when the substrate is a substrate having a plurality of conductive layers, the treatment for reducing the visible light reflectance may be performed on a part of the conductive layers or on all of the conductive layers.

[0656] As the treatment for reducing the visible light reflectance, an oxidation treatment can be cited. For example, by subjecting copper to an oxidation treatment to become copper oxide and turn black, the visible light reflectance of the conductive layer can be reduced.

[0657] Regarding the preferred mode of the treatment for reducing the visible light reflectance, it is described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of Japanese Patent Application Laid-Open No. 2013-206315, and the content of this publication is incorporated into this specification.

[0658] (Etching step)

[0659] When the substrate is a substrate having a conductive layer, the above-described pattern forming method preferably includes a step (etching step) of using the pattern formed by step X3 (or step X4) and step Y3 as an etching resist film and etching the conductive layer in a region where the etching resist film is not disposed.

[0660] As a method of the etching treatment, a method based on wet etching described in paragraphs 0048 to 0054 of Japanese Patent Application Laid-Open No. 2010-152155 and a method based on dry etching such as known plasma etching can be applied.

[0661] For example, as a method of the etching treatment, a wet etching method of generally immersing in an etching solution can be cited. As the etching solution used in wet etching, an acidic type or a basic type etching solution may be appropriately selected according to the object to be etched.

[0662] As the acidic type etching solution, aqueous solutions of acidic components alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts such as ferric chloride, ammonium fluoride, or potassium permanganate are exemplified. As the acidic component, a component combining a plurality of acidic components can be used.

[0663] As the basic type etching solution, aqueous solutions of basic components alone such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines such as tetramethylammonium hydroxide, and mixed aqueous solutions of basic components and salts such as potassium permanganate are exemplified. As the basic component, a component combining a plurality of basic components can be used.

[0664] The temperature of the etching solution is not particularly limited, and is preferably 45°C or lower. In the method for manufacturing a circuit wiring of the present invention, the pattern formed by process X3 (or process X4) and process Y3 and used as an etching resist film exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45°C or lower. With the above structure, peeling of the etching resist film during the etching process can be prevented, and the portion without the etching resist film can be selectively etched.

[0665] After the etching process, in order to prevent contamination of the process circuit, a cleaning process for cleaning the etched substrate and a drying process for drying the cleaned substrate can be performed as needed.

[0666] The film used as the etching resist film can be removed, or it can be left as a protective film (permanent film) for the conductive layer of the circuit wiring.

[0667] (Other embodiments)

[0668] Regarding the above pattern formation method, it is also preferable to use substrates having a plurality of conductive layers on both surfaces, and to form patterns on the conductive layers formed on the two surfaces sequentially or simultaneously.

[0669] With this structure, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface. It is also preferable to form from both sides of the base material in a roll-to-roll manner.

[0670] <Pattern>

[0671] Due to the decrease in the carboxyl group content, the pattern formed by the pattern formation methods of the above Embodiment 1 and Embodiment 2 has a reduced polarity and a reduced relative dielectric constant.

[0672] The content of the carboxyl group in the above pattern is preferably reduced by 5 mol% or more, more preferably reduced by 10 mol% or more, still more preferably reduced by 20 mol% or more, further preferably reduced by 31 mol% or more, particularly preferably reduced by 40 mol% or more, particularly preferably reduced by 51 mol% or more, and most preferably reduced by 71 mol% or more, relative to the content of the carboxyl group in the photosensitive layer formed in process X1 or process Y1. In addition, there is no particular limitation as the upper limit value, for example, it is 100 mol% or less.

[0673] The moisture permeability of the above pattern is preferably reduced by 5% or more, more preferably reduced by 10% or more, and further preferably reduced by 20% or more, relative to the moisture permeability of the photosensitive layer formed in process X1 or process Y1. In addition, there is no particular limitation as the upper limit value, for example, it is 100% or less.

[0674] The relative dielectric constant of the above-mentioned pattern is preferably reduced by 5% or more, more preferably by 10% or more, and further preferably by 15% or more, relative to the relative dielectric constant of the photosensitive layer formed in Process X1 or Process Y1. Additionally, there is no particular limitation on the upper limit value, for example, it is 100% or less.

[0675] The average thickness of the pattern formed by the above-mentioned pattern forming method is preferably 0.5 - 20 μm. As the average thickness of the pattern, it is more preferably 0.8 - 15 μm, and further preferably 1.0 - 10 μm.

[0676] The pattern formed by the above-mentioned pattern forming method is preferably colorless. Specifically, for total reflection (incident angle 8°, light source: D - 65 (2° field of view)) in the CIE1976 (L * , a * , b * ) color space, the L * value of the pattern is preferably 10 - 90, the a * value of the pattern is preferably - 1.0 - 1.0, and the b * value of the pattern is preferably - 1.0 - 1.0.

[0677] There is no particular limitation on the use of the pattern formed by the above-mentioned pattern forming method, and it can be used as various protective films or insulating films.

[0678] Specifically, examples include uses as a protective film (permanent film) for protecting conductive patterns, as an interlayer insulating film between conductive patterns, and as an etching resist film when manufacturing circuit wirings, etc. Since the relative dielectric constant of the above-mentioned pattern is reduced, among them, it is preferably used as a protective film (permanent film) for protecting conductive patterns or an interlayer insulating film between conductive patterns. And after using the pattern as an etching resist film, it can be directly used as a protective film (permanent film).

[0679] In addition, the above-mentioned pattern can be used, for example, as follows, that is, as a protective film (permanent film) for protecting conductive patterns such as electrode patterns, peripheral wiring parts, and lead - out wiring parts of the sensor equivalent to the visual recognition part provided inside the touch panel, or as an interlayer insulating film between conductive patterns.

[0680] [Manufacturing method of circuit wiring]

[0681] The present invention also relates to a manufacturing method of circuit wiring.

[0682] The manufacturing method of the circuit wiring involved in the present invention (also referred to as "the manufacturing method of the circuit wiring of the present invention") is not particularly limited as long as it is a manufacturing method of circuit wiring using the above photosensitive material, and preferably includes, in sequence, a step of forming a photosensitive layer on the conductive layer in a substrate having a conductive layer using a photosensitive material (preferably the photosensitive material of Method 3) (photosensitive layer forming step), a step of exposing the photosensitive layer into a pattern (first exposure step), a step of developing the exposed photosensitive layer using an alkali developer to form a patterned photosensitive layer (alkali development step), a step of exposing the patterned photosensitive layer to form an etching resist film (second exposure step), and a step of etching the conductive layer in the area where the etching resist film is not disposed (etching step).

[0683] The above photosensitive layer forming step is also preferably a step of bringing the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support side into contact with the conductive layer in the substrate having a conductive layer and bonding the transfer film to the substrate having a conductive layer (bonding step).

[0684] In the manufacturing method of the circuit wiring of the present invention, the photosensitive layer forming step, the first exposure step, the alkali development step, and the second exposure step can all be carried out in the same order as the steps Y1, Y2A, Y3, and Y2B of the pattern forming method of the above Embodiment 2. And, the substrate having a conductive layer used in the manufacturing method of the circuit wiring of the present invention is the same as the substrate having a conductive layer used in the above step X1. And, the manufacturing method of the circuit wiring of the present invention may have other steps in addition to the above steps. As other steps, steps that are the same as any steps that the pattern forming methods of the first embodiment and the second embodiment may have can be cited.

[0685] The manufacturing method of the circuit wiring of the present invention also preferably groups the above four steps of the bonding step, the first exposure step, the development step, the second exposure step, and the etching step as one set and repeats them multiple times.

[0686] The film used as the etching resist film can also be used as a protective film (permanent film) for the formed circuit wiring.

[0687] [Manufacturing method of touch panel]

[0688] The present invention also relates to a manufacturing method of a touch panel.

[0689] The manufacturing method of the touch panel according to the present invention (also referred to as "the manufacturing method of the touch panel of the present invention") is not particularly limited as long as it is a manufacturing method of a touch panel using the above-described photosensitive material, and preferably sequentially includes a step of forming a photosensitive layer on a conductive layer in a substrate having a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring pattern) using a photosensitive material (preferably the photosensitive material of Method 3) (photosensitive layer forming step), a step of exposing the photosensitive layer into a pattern shape (first exposure step), a step of developing the exposed photosensitive layer using an alkaline developer to form a patterned photosensitive layer (alkaline development step), and a step of exposing the patterned photosensitive layer to form a protective film or an insulating film for the conductive layer (second exposure step).

[0690] The protective film formed by the second exposure step has a function of protecting the surface of the conductive layer. Also, the insulating film has a function of an interlayer insulating film between the conductive layers. Further, when the second exposure step is a step of forming an insulating film for the conductive layer, the manufacturing method of the touch panel of the present invention preferably further has a step of forming a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring) on the insulating film formed by the second exposure step.

[0691] The above-described photosensitive layer forming step is also preferably a step of bringing the surface of the photosensitive layer on the transfer film opposite to the temporary support side into contact with the conductive layer in the substrate having the conductive layer and bonding the transfer film to the substrate having the conductive layer (bonding step).

[0692] In the manufacturing method of the touch panel of the present invention, the photosensitive layer forming step, the first exposure step, the alkaline development step, and the second exposure step can all be carried out in the same order as the steps Y1, Y2A, Y3, and Y2B of the pattern forming method of the above-described Embodiment 2. Also, the substrate having the conductive layer used in the manufacturing method of the touch panel of the present invention is the same as the substrate having the conductive layer used in the above step X1. As other steps, steps that are the same as any steps that the pattern forming methods of the first embodiment and the second embodiment can have can be cited.

[0693] As the manufacturing method of the touch panel of the present invention, structures other than the above-described manner can refer to known manufacturing methods of touch panels.

[0694] The touch panel manufactured by the manufacturing method of the touch panel of the present invention preferably has a transparent substrate, electrodes, and a protective layer (protective film).

[0695] As the detection method in the above touch panel, it can be any of the known methods such as the resistive film method, the capacitive method, the ultrasonic method, the electromagnetic induction method, and the optical method. Among them, the capacitive method is preferred.

[0696] As the touch panel type, there can be mentioned the so-called in-cell type (for example, as described in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517051), the so-called on-cell type (for example, as described in FIG. 19 of Japanese Patent Application Laid-Open No. 2013-168125, and Figure 1 as described in FIG. 5 of Japanese Patent Application Laid-Open No. 2012-089102), the OGS (One Glass Solution) type, the TOL (Touch-on-Lens) type (for example, as described in FIG. 2 of Japanese Patent Application Laid-Open No. 2013-054727), other structures (for example, as described in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), and various out-cell types (the so-called GG, G1 / G2, GFF, GF2, GF1, G1F, etc.).

[0697] Examples

[0698] Hereinafter, examples are given to further illustrate the present invention in detail. The materials, amounts used, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[0699] In the following examples, as the high-pressure mercury lamp, unless otherwise specified, the H03-L31 manufactured by EYE GRAPHICS CO., LTD. was used. The above high-pressure mercury lamp has a main wavelength of 365 nm and strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0700] As the ultra-high-pressure mercury lamp, unless otherwise specified, the USH-2004MB manufactured by USHIO INC. was used. The above ultra-high-pressure mercury lamp has strong line spectra at 313 nm, 365 nm, 405 nm, and 436 nm.

[0701] [Example 1 System]

[0702] [Preparation of Photosensitive Material]

[0703] As polymer A having a carboxyl group, a styrene / acrylic acid copolymer (acid value: 200, Mw: 8500, manufactured by TOAGOSEI CO., LTD., ARUFON UC3910 (trade name)) and compound β shown in Table 2 were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) to satisfy the compounding amounts described in Table 2 shown in the latter part, and the solid content concentration of the finally obtained photosensitive material was made 25% by mass, thereby obtaining a mixed solution. In the above mixed solution, MEGAFACE F551 (a fluorine-containing nonionic surfactant manufactured by DIC Corporation) was added as a surfactant so that the concentration with respect to the total solid content of the photosensitive material became 100 mass ppm, thereby preparing the photosensitive materials of each example or comparative example.

[0704] In addition, the compounding amounts (parts by mass) shown in the table are the solid component amounts of each component.

[0705] <Physical Property Evaluation of Compound β>

[0706] (Measurement of pKa of Compound β in the Ground State)

[0707] The pKa of compound β in the ground state was measured by the following method using an automatic titrator manufactured by HIRANUMA Co., Ltd. In addition, when compound β is a nitrogen-containing aromatic compound, the pKa of compound β in the ground state represents the pKa of the conjugate acid of compound β.

[0708] 0.1 g of compound β was dissolved in 20 ml of methanol, and 20 ml of ultrapure water was added thereto. It was titrated with a 0.1N-HCL aqueous solution, and the pH at the 1 / 2 time point of the titration amount required until the equivalence point was set as pKa (pKa of compound β in the ground state).

[0709] (Measurement and Evaluation of ε365 and ε365 / ε313)

[0710] The molar extinction coefficient of compound β at 365 nm ((cm·mol / L) -1 , "ε365") and the molar extinction coefficient at 313 nm ((cm·mol / L) -1 , "ε313") were determined, and the value obtained by dividing ε365 by ε313 (ε365 / ε313) was determined.

[0711] ε365 and ε313 of compound β are the molar extinction coefficients measured by dissolving compound β in acetonitrile. When compound β is not soluble in acetonitrile, the solvent in which compound β is dissolved can be appropriately changed. Among them, it is preferably 1 or less.

[0712] <Evaluation of photosensitive material>

[0713] (Fabrication of photosensitive layer)

[0714] The photosensitive materials of each example or comparative example were spin-coated on a silicon wafer, and then, at 80 °C, the obtained coating film was dried using a hot plate to obtain a photosensitive layer with a film thickness of 5 μm.

[0715] The obtained photosensitive layer was evaluated in the following manner.

[0716] (Evaluation of carboxyl consumption rate (IR measurement))

[0717] The obtained photosensitive layer was exposed over the entire surface using a high-pressure mercury lamp. The cumulative exposure dose measured with a 365 nm illuminometer was 1000 mJ / cm 2 . In addition, the light emitted from the above high-pressure mercury lamp has a main wavelength of 365 nm and strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0718] The IR (infrared) spectra of the photosensitive layer were measured before and after exposure, and the carboxyl consumption rate (mol%) was calculated based on the reduction rate of the peak (1710 cm -1 of the peak) of the C=O stretching of the carboxyl group.

[0719] The higher the carboxyl consumption rate, the more the decarboxylation reaction proceeds.

[0720] The results are shown in Table 2 (refer to the column of "Carboxyl consumption rate (mol%) [IR measurement]").

[0721] (Evaluation of carboxyl consumption rate (ashing measurement))

[0722] The carboxyl consumption rate was measured in the following sequence.

[0723] · Measurement of the carboxyl group amount of the photosensitive layer after exposure (Measurement of the carboxyl group amount after exposure)

[0724] The photosensitive layer obtained in the upper section was exposed under the following exposure conditions.

[0725] <Exposure conditions>

[0726] The obtained photosensitive layer was exposed over the entire surface using a high-pressure mercury lamp. The cumulative exposure dose measured with a 365 nm illuminometer was 1000 mJ / cm 2 . In addition, the light emitted from the above high-pressure mercury lamp has a main wavelength of 365 nm and strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0727] Next, about 20 mg of the exposed photosensitive layer was scraped off, cryo-ground, and then 150 μL of NMP (N-methyl-2-pyrrolidone) was added. Then, it was stirred in an aqueous solution of lithium carbonate (Li2CO3) (1.2 g / 100 mL. An aqueous solution of lithium carbonate obtained by dissolving lithium carbonate in ultrapure water and then filtering it through a filter.) for 6 days.

[0728] After the stirring was completed, the particles were sedimented by ultracentrifugation (140,000 rpm × 30 min), the supernatant was replaced with ultrapure water (the replacement was repeated 5 times), and then the obtained precipitate was dried and solidified as an analysis sample (samples were prepared with n = 2). The analysis sample was analyzed by ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.).

[0729] In addition, the above ICP-OES measurement was carried out in the following order.

[0730] About 1.5 mg to 2 mg (n = 3) of the above analysis sample was weighed, 5 mL of 60% HNO3 aqueous solution was added, and then MW Teflon ashing (microwave sample decomposition device Ultra WAVE max: 260 °C) was carried out.

[0731] After ashing, ultrapure water was added to make 50 mL, ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.) was used, and the Li amount was quantified by the absolute calibration curve method.

[0732] · Determination of the carboxyl group amount of the photosensitive material before exposure (Determination of the carboxyl group amount before exposure)

[0733] The carboxyl group amount of the photosensitive materials of each example and comparative example used in forming the above photosensitive layer was measured in the following order.

[0734] 1 g of the photosensitive material was dissolved in 63 ml of tetrahydrofuran, and 12 ml of ultrapure water was added thereto. Then, an automatic titrator manufactured by HIRANUMA Co., Ltd. was used, and the obtained solution was titrated with 0.1N-NaOH aqueous solution. The carboxyl group amount obtained by titration was converted based on the solid component concentration, and thus the carboxyl group amount in the photosensitive material was calculated.

[0735] · Calculation of the decarboxylation rate

[0736] Based on the measurement results of the carboxyl group amounts before and after the above exposure, the decarboxylation rate was calculated by the following formula.

[0737] Decarboxylation rate (%) : { (Carboxyl group amount before exposure - Carboxyl group amount after exposure) / Carboxyl group amount before exposure} × 100 (%)

[0738] Based on the obtained numerical values, evaluation was carried out according to the following evaluation criteria.

[0739] In the case of the above method, there is a detection limit. When the carboxyl content is 1.05 mmol / g or less, more than 90% of Li can be substituted. In other regions, a calibration curve was made using a crosslinked polymer with a known acid value and calculations were performed.

[0740] · Evaluation criteria

[0741] A: The decarboxylation rate is 71 mol% or more

[0742] B: The decarboxylation rate is 50 mol% or more and less than 71 mol%

[0743] C: The decarboxylation rate is 31 mol% or more and less than 50 mol%

[0744] D: The decarboxylation rate is 5 mol% or more and less than 31 mol%

[0745] E: The decarboxylation rate is less than 5 mol%

[0746] The results are shown in Table 2 (refer to the column of "carboxyl consumption rate [determined by ashing]").

[0747] (Pattern formation evaluation 1)

[0748] The obtained photosensitive layer was exposed through any one of the following masks (1) to (3) using a high-pressure mercury lamp. The cumulative exposure measured with a 365 nm illuminometer was 1000 mJ / cm 2 .

[0749] (1) Mask with line size = 25 μm and line:space = 1:1

[0750] (2) Mask with line size = 50 μm and line:space = 1:1

[0751] (3) Mask with line size = 250 μm and line:space = 1:1

[0752] After the exposed photosensitive layer was dip-coated and developed in a 1 mass% aqueous sodium carbonate solution for 30 seconds, it was rinsed with pure water for 20 seconds and dried to obtain a pattern (line and space pattern).

[0753] The line and space patterns with line widths and space widths of 25 μm, 50 μm, or 250 μm produced in this way were observed and evaluated as follows.

[0754] A: The line and space pattern has been resolved (the photosensitive layer in the space part has been removed) and the film of the pattern has not decreased.

[0755] B: The lines and space pattern have been resolved, but the film of the pattern is slightly reduced.

[0756] C: The lines and space pattern have been resolved, but the film of the pattern is significantly reduced.

[0757] D: The lines and space pattern has not been resolved (the photosensitive layer in the space part remains or the entire pattern is dissolved and disappears).

[0758] (Relative dielectric constant evaluation 1)

[0759] A photosensitive material was spin-coated on an aluminum substrate with a thickness of 0.1 mm, and then the obtained coating film was dried with a hot plate at 80 °C to fabricate a photosensitive layer with a thickness of 8 μm.

[0760] The obtained photosensitive layer was exposed uniformly using a high-pressure mercury lamp. The cumulative exposure dose measured with a 365-nm illuminometer was 1000 mJ / cm 2 .

[0761] Regarding the exposed photosensitive layer, using an LCR meter 4284A and a Dielectric test fixture 16451B manufactured by Agilent Technologies, Inc., and in an environment of 23 °C and 50% RH, the relative dielectric constant at 1 kHz was measured.

[0762] Taking the relative dielectric constant of the photosensitive layer formed using the photosensitive material of Comparative Example 1A after exposure as 100%, in comparison, the reduction rate of how much the relative dielectric constant of the photosensitive layer formed using the photosensitive material of each Example decreased after exposure was calculated, and the evaluation was made according to the following criteria.

[0763] The larger the value of the reduction rate, the lower the relative dielectric constant compared with Comparative Example 1A, and it is effective as an insulating film.

[0764] A: The reduction rate is 15% or more

[0765] B: The reduction rate is 10% or more and less than 15%

[0766] C: The reduction rate is 5% or more and less than 10%

[0767] D: The reduction rate is less than 5%

[0768] (Relative dielectric constant evaluation before and after exposure 1)

[0769] The photosensitive layer after exposure was fabricated in the same manner as above (Relative dielectric constant evaluation 1). At this time, before and after exposure, the relative dielectric constant of each photosensitive layer was measured in the same manner as above (Relative dielectric constant evaluation 1).

[0770] The relative dielectric constant of each photosensitive layer before exposure was set to 100%, and it was calculated how much the dielectric constant of each photosensitive layer decreased by exposure, and evaluation was performed according to the following criteria.

[0771] It can be judged that the larger the reduction rate, the more the reduction of the dielectric constant based on the decarboxylation reaction caused by exposure proceeds.

[0772] A: The reduction rate is 15% or more

[0773] B: The reduction rate is 10% or more and less than 15%

[0774] C: The reduction rate is 5% or more and less than 10%

[0775] D: The reduction rate is less than 5%

[0776] <Evaluation of Transfer Film (Photosensitive Transfer Material)>

[0777] (Production of Transfer Film)

[0778] On a polyethylene terephthalate film with a thickness of 16 μm (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) (temporary support), using a slit-shaped nozzle, the photosensitive material of each example or comparative example was adjusted and coated to a thickness of 5 μm after drying, and dried at 100 °C for 2 minutes to form a photosensitive layer.

[0779] On the obtained photosensitive layer, a polyethylene terephthalate film with a thickness of 16 μm (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) (cover film) was pressure-bonded to produce a transfer film of Example 1 series.

[0780] (Evaluation of Carboxyl Consumption Rate (IR Measurement))

[0781] By peeling the cover film from the transfer film produced above and laminating it onto a silicon wafer, the photosensitive layer of the transfer film was transferred onto the surface of the silicon wafer. The lamination conditions were set to a temperature of 40 °C for the touch panel substrate, a rubber roller temperature (i.e., lamination temperature) of 110 °C, a line pressure of 3 N / cm, and a conveying speed of 2 m / minute.

[0782] The photosensitive layer after transfer was exposed under the following exposure conditions.

[0783] <Exposure Conditions>

[0784] After removing the temporary support, using a high-pressure mercury lamp, the photosensitive layer was exposed over the entire surface. The cumulative exposure amount measured with a 365 nm illuminometer was 1000 mJ / cm 2In addition, the light emitted from the above high-pressure mercury lamp has a main wavelength of 365 nm and strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0785] Before and after exposure, the IR spectra of the photosensitive layer were measured, and the carboxyl consumption rate (mol%) was calculated based on the reduction rate of the peak (1710 cm -1 of the peak) of the C=O stretching of the carboxyl group.

[0786] The higher the carboxyl consumption rate, the more the decarboxylation reaction proceeds.

[0787] The results are shown in Table 1 (refer to the column of "Carboxyl consumption rate (mol%) [IR measurement]").

[0788] (Carboxyl consumption rate evaluation (ashing measurement))

[0789] By peeling off the cover film from the transfer film produced above and laminating it onto glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) of 10×10 cm 2 , the photosensitive layer of the transfer film was transferred onto the surface of the glass. The lamination conditions were set to a temperature of 40 °C for the touch panel substrate, a temperature of the rubber roller (i.e., the lamination temperature) of 110 °C, a line pressure of 3 N / cm, and a conveying speed of 2 m / min.

[0790] ·Measurement of the carboxyl group amount in the photosensitive layer after exposure (Measurement of the carboxyl group amount after exposure)

[0791] The photosensitive layer after transfer was exposed under the following exposure conditions.

[0792] 《Exposure conditions》

[0793] After removing the temporary support, the photosensitive layer was exposed over the entire surface using a high-pressure mercury lamp. The cumulative exposure amount measured with a 365-nm illuminometer was 1000 mJ / cm 2 In addition, the light emitted from the above high-pressure mercury lamp has a main wavelength of 365 nm and strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.

[0794] Next, about 20 mg of the photosensitive layer after exposure was scraped off, cryogenically pulverized, then 150 μL of NMP (N-methyl-2-pyrrolidone) was added, and then it was stirred in an aqueous solution of lithium carbonate (Li2CO3) (1.2 g / 100 mL. An aqueous solution of lithium carbonate (Li2CO3) obtained by dissolving lithium carbonate in ultrapure water and then filtering it through a filter.) for 6 days.

[0795] After stirring was completed, the particles were sedimented by ultracentrifugation (140,000 rpm × 30 min). After replacing the supernatant with ultrapure water (the replacement was repeated 5 times), the obtained precipitate was dried and solidified to obtain an analytical sample (samples were prepared with n = 2). The analytical sample was analyzed by ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.).

[0796] In addition, the above ICP-OES measurement was carried out in the following order.

[0797] Approximately 1.5 mg to 2 mg (n = 3) of the above analytical sample was weighed, and after adding 5 mL of 60% HNO₃ aqueous solution, MW Teflon ashing (microwave sample decomposition device Ultra WAVE max: 260 °C) was carried out.

[0798] After ashing, ultrapure water was added to make 50 mL, and using ICP-OES (Optima 7300DV manufactured by Perkin Elmer Co., Ltd.), the amount of Li was quantified by the absolute calibration curve method.

[0799] · Determination of the amount of carboxyl groups in the photosensitive layer before exposure (Determination of the amount of carboxyl groups before exposure)

[0800] The amount of carboxyl groups in the photosensitive layers of each example and comparative example was measured in the following order.

[0801] 1 g of the photosensitive layer before exposure was scraped off, dissolved in 63 ml of tetrahydrofuran, and 12 ml of ultrapure water was added thereto. Then, using an automatic titrator manufactured by HIRANUMA Co., Ltd., the obtained solution was titrated with 0.1N-NaOH aqueous solution. The amount of carboxyl groups obtained by titration was converted based on the solid component concentration, and thus the amount of carboxyl groups in the photosensitive layer was calculated.

[0802] · Calculation of the decarboxylation rate

[0803] Based on the measurement results of the amount of carboxyl groups before and after the above exposure, the decarboxylation rate was calculated by the following formula.

[0804] Decarboxylation rate (%) : { (Amount of carboxyl groups before exposure - Amount of carboxyl groups after exposure) / Amount of carboxyl groups before exposure} × 100 (%)

[0805] Based on the obtained values, evaluation was carried out according to the following evaluation criteria.

[0806] Among them, in the case of the above method, there is a detection limit. When the carboxyl group content is 1.05 mmol / g or less, more than 90% of Li can be substituted. In other regions, a calibration curve was made using a crosslinked polymer with a known acid value and calculations were performed.

[0807] · Evaluation criteria

[0808] A The decarboxylation rate is 71 mol% or more

[0809] B The decarboxylation rate is 50 mol% or more and less than 71 mol%

[0810] C The decarboxylation rate is 31 mol% or more and less than 50 mol%

[0811] D The decarboxylation rate is 5 mol% or more and less than 31 mol%

[0812] E The decarboxylation rate is less than 5 mol%

[0813] The results are shown in Table 1 (refer to the column of "carboxyl group consumption rate [ash determination]").

[0814] (365 nm transmittance)

[0815] Using the UV-visible spectrophotometer UV1800 manufactured by SHIMADZU CORPORATION, the 365 nm transmittance of the photosensitive layer was measured, and evaluation was carried out based on the following evaluation criteria.

[0816] A The transmittance is 90% or more

[0817] B The transmittance is 65% or more and less than 90%

[0818] C The transmittance is 20% or more and less than 65%

[0819] D The transmittance is less than 20%

[0820] (365 nm transmittance / 313 nm transmittance)

[0821] Using the UV-visible spectrophotometer UV1800 manufactured by SHIMADZU CORPORATION, the transmittance of the photosensitive layer at 365 nm and the transmittance at 313 nm were measured, and the value calculated by dividing the 365 nm transmittance by the 313 nm transmittance was evaluated as follows.

[0822] A 1.5 or more

[0823] B 1 or more and less than 1.5

[0824] C Less than 1

[0825] (Lamination suitability evaluation)

[0826] By peeling off the cover film from the transfer film prepared above and laminating it onto the PET film (substrate for touch panel) with a copper foil laminated thereon by GEOMATEC Co., Ltd., the photosensitive layer of the transfer film was transferred onto the surface of the copper foil, and a laminate having a laminated structure of "temporary support / photosensitive layer / copper foil / substrate (PET film)" was obtained. The lamination conditions were set to a temperature of 40 °C for the substrate for touch panel, a temperature of the rubber roller (i.e., lamination temperature) of 110 °C, a line pressure of 3 N / cm, and a conveying speed of 2 m / min. In addition, the copper foil is a film assuming the wiring of the touch panel.

[0827] Visually evaluate the area where the photosensitive layer adheres to the copper foil without bubbles and floating, calculate the proportion (%) of the adhered area based on the following formula, and evaluate according to the following criteria. It can be considered that the larger the adhered area (%), the more excellent the lamination suitability.

[0828] Proportion (%) of the adhered area = Area where the photosensitive layer adheres ÷ Area of the transferred film laminated × 100

[0829] A: Proportion (%) of the adhered area is 95% or more

[0830] B: Proportion (%) of the adhered area is less than 95%

[0831] (Pattern formation evaluation 2)

[0832] Next, the temporary support was peeled off from the above laminate, and the exposed photosensitive layer was exposed using a high-pressure mercury lamp. During exposure, exposure was performed through any one of the following masks (1) to (3). The cumulative exposure dose measured with an illuminometer of 365 nm was 1000 mJ / cm 2 .

[0833] (1) Mask with a line size of 25 μm and a line:space ratio of 1:1

[0834] (2) Mask with a line size of 50 μm and a line:space ratio of 1:1

[0835] (3) Mask with a line size of 250 μm and a line:space ratio of 1:1

[0836] Next, the exposed photosensitive layer was developed for 40 seconds using an aqueous solution of 1 mass% sodium carbonate (liquid temperature: 32 °C) as the developer. After development, it was rinsed with pure water for 20 seconds, and air was further blown to remove moisture, obtaining a pattern (line and space pattern).

[0837] The line and space patterns with line widths and space widths of 25 μm, 50 μm, or 250 μm produced in this manner were evaluated in the same way as in the above (pattern formation evaluation 1).

[0838] (Relative permittivity evaluation 2)

[0839] The cover film was peeled off from the transfer film produced above and laminated onto an aluminum substrate with a thickness of 0.1 mm under the same conditions as in the above (lamination suitability evaluation) to obtain a laminate having a laminated structure of "temporary support / photosensitive layer / aluminum substrate". Subsequently, the temporary support was peeled off from the laminate. The exposed photosensitive layer was exposed uniformly using a high-pressure mercury lamp. The cumulative exposure dose measured with an illuminometer at 365 nm was 1000 mJ / cm 2 .

[0840] Regarding the exposed photosensitive layer, the relative permittivity at 1 kHz was measured using an LCR meter 4284A and a Dielectric test fixture 16451B manufactured by Agilent Technologies, Inc. in an environment of 23°C and 50% RH.

[0841] Taking the relative permittivity of the photosensitive layer formed using the photosensitive material of Comparative Example 1A after exposure as 100%, the reduction rate of how much the relative permittivity of the photosensitive layer formed using the photosensitive material of each Example decreased after exposure was calculated and evaluated according to the following criteria.

[0842] The larger the value of the reduction rate, the lower the relative permittivity compared to Comparative Example 1A, and it is effective as an insulating film.

[0843] A: The reduction rate is 15% or more

[0844] B: The reduction rate is 10% or more and less than 15%

[0845] C: The reduction rate is 5% or more and less than 10%

[0846] D: The reduction rate is less than 5%

[0847] (Relative permittivity evaluation before and after exposure 2)

[0848] The photosensitive layer after exposure was produced in the same way as in the above (relative permittivity evaluation 2). At this time, the relative permittivity of each photosensitive layer was measured in the same way as in the above (relative permittivity evaluation 2) before and after exposure.

[0849] The relative permittivity before exposure of each photosensitive layer was set to 100%, and it was calculated how much the permittivity of each photosensitive layer decreased by exposure, and evaluation was performed according to the following criteria.

[0850] It can be judged that the larger the reduction rate, the more the reduction of the permittivity based on the decarboxylation reaction caused by exposure progresses.

[0851] A: The reduction rate is 15% or more

[0852] B: The reduction rate is 10% or more and less than 15%

[0853] C: The reduction rate is 5% or more and less than 10%

[0854] D: The reduction rate is less than 5%

[0855] (Evaluation of water vapor transmission rate (WVTR))

[0856] · Preparation of specimen for water vapor transmission rate measurement

[0857] On a polyethylene terephthalate (PET) film (temporary support) with a thickness of 75 μm, the photosensitive material of each example or comparative example was coated using a slit-shaped nozzle, and then dried to form a photosensitive layer with a thickness of 8 μm, obtaining a transfer film for specimen production.

[0858] Next, the transfer film for specimen production was laminated onto a PTFE (tetrafluoroethylene resin) Membrane filter FP-100-100 manufactured by Sumitomo Flectric Industries, Ltd., to form a laminate A having a layer structure of "temporary support / photosensitive layer with a thickness of 8 μm / membrane filter". The lamination conditions were set to a membrane filter temperature of 40°C, a laminating roll temperature of 110°C, a line pressure of 3 N / cm, and a conveying speed of 2 m / minute.

[0859] Next, the temporary support was peeled off from the laminate A.

[0860] On the photosensitive layer of the laminate A that was exposed, the transfer film for specimen production was further laminated in the same manner, and the temporary support was peeled off from the obtained laminate 4 times, forming a laminate B having a layer structure of "photosensitive layer with a total film thickness of 40 μm / membrane filter".

[0861] The photosensitive layer of the obtained laminate B was exposed over the entire surface using a high-pressure mercury lamp. The cumulative exposure amount measured with a 365 nm illuminometer was 1000 mJ / cm 2 。

[0862] In the above manner, a specimen for measuring moisture permeability with a laminated structure of "exposed photosensitive layer / membrane filter with a total film thickness of 40 μm" was obtained.

[0863] ·Measurement of moisture permeability (WVTR)

[0864] Using the specimen for measuring moisture permeability, with reference to JIS-Z-0208 (1976), the moisture permeability measurement based on the cup method was carried out. Details will be described below.

[0865] First, a circular specimen with a diameter of 70 mm was cut out from the specimen for measuring moisture permeability. Then, 20 g of dried calcium chloride was placed in the measuring cup, and then covered with the above circular specimen to prepare a measuring cup with a lid.

[0866] Under the conditions of 65 °C and 90% RH, the measuring cup with a lid was placed in a thermo-hygrostat for 24 hours. Based on the mass change of the measuring cup with a lid before and after the above placement, the moisture permeability (WVTR) of the circular specimen (unit: g / (m 2 ·day)) was calculated.

[0867] The above measurement was carried out 3 times, and the average value of WVTR in the 3 measurements was calculated.

[0868] Based on the reduction rate (%) of WVTR of each example when the WVTR of Comparative Example 1A was set to 100%, the moisture permeability was evaluated. In addition, the larger the value of the reduction rate, the lower the moisture permeability compared to Comparative Example 1A, and it is preferably used as a protective film. In the following evaluation criteria, A or B is preferred, and A is more preferred.

[0869] In addition, in the above measurement, the WVTR of the circular specimen with a laminated structure of "exposed photosensitive layer / membrane filter with a total film thickness of 40 μm" was measured in the above manner. However, since the WVTR of the membrane filter is extremely high compared to the WVTR of the exposed photosensitive layer, in the above measurement, it essentially means measuring the WVTR of the exposed photosensitive layer itself.

[0870] A: The reduction rate of WVTR is 20% or more

[0871] B: The reduction rate of WVTR is 10% or more and less than 20%

[0872] C: The reduction rate of WVTR is 7.5% or more and less than 10%

[0873] D: The reduction rate of WVTR is 5% or more and less than 7.5%

[0874] E: The reduction rate of WVTR is less than 5%

[0875] <Result>

[0876] In Table 2 below, the types and amounts of Polymer A and Compound β in the photosensitive materials of each example or comparative example in Example 1 and the test results are shown.

[0877] In the "Amount" column in the table, the amounts (parts by mass) of Polymer A and Compound β added to the photosensitive material are shown. In addition, the above amounts (parts by mass) are the amounts of Polymer A and Compound β themselves (solid components) incorporated into the photosensitive material.

[0878] In the column of "Molar ratio of carboxyl groups of Compound β to Polymer A (mol%)" in the table, the ratio (mol%) of the total number of structures (Structure b0) in Compound β that reduce the amount of carboxyl groups of Polymer A (preferably a structure (Structure b) that can accept electrons from the carboxyl groups of Polymer A in the photoexcited state) to the total number of carboxyl groups of Polymer A in the photosensitive material is shown.

[0879] The "ε365" column represents the molar extinction coefficient of Compound β with respect to light of wavelength 365 nm in acetonitrile ((cm·mol / L) -1 ).

[0880] The "ε365 / ε313" column represents the value obtained by dividing the molar extinction coefficient of Compound β with respect to light of wavelength 365 nm ((cm·mol / L) -1 ) by the molar extinction coefficient of Compound β with respect to light of wavelength 313 nm ((cm·mol / L) -1 ). In addition, the molar extinction coefficients are all values in acetonitrile.

[0881] The "365 nm transmittance" column represents the transmittance of the photosensitive layer with respect to light of wavelength 365 nm.

[0882] The "365 nm transmittance / 313 nm transmittance" column represents the value obtained by dividing the transmittance of the photosensitive layer with respect to light of wavelength 365 nm by the transmittance of the photosensitive layer with respect to light of wavelength 313 nm.

[0883] [Table 2]

[0884]

[0885] [Table 3]

[0886]

[0887] It was confirmed from the results shown in the above table that the problems of the present invention can be solved as long as the photosensitive material of the present invention is used.

[0888] Further, it was confirmed that, from the viewpoint of more excellent effects of the present invention, in the photosensitive material, the total number of the structure b0 (preferably the structure b) possessed by the compound β is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, relative to the total number of carboxyl groups possessed by the polymer A (refer to the comparison of the results of Examples 1-4, 1-8, 1-9, 1-10, and 1-11, etc.).

[0889] Further, it was confirmed that, in the photosensitive layer of the transfer film of the present invention, the compound β has a molar extinction coefficient of 1×10 3 (cm·mol / L) -1 for light with a wavelength of 365 nm in the case of the following compound (preferably having a molar extinction coefficient of 1×10 2 (cm·mol / L) -1 for light with a wavelength of 365 nm in the case of the following compound), and the pattern formability is more excellent (refer to the comparison of the results of Examples 1-1 to 1-7, etc.).

[0890] Further, it was confirmed that, in the photosensitive layer of the transfer film of the present invention, when the compound β is a compound having a ratio represented by the molar extinction coefficient ((cm·mol / L) -1 ) with respect to light with a wavelength of 365 nm / the molar extinction coefficient ((cm·mol / L) -1 ) with respect to light with a wavelength of 313 nm of 3 or less, the pattern formability is more excellent (refer to the comparison of the results of Examples 1-1 to 1-7, etc.).

[0891] [Example 2 Series]

[0892] [Preparation and Evaluation of Photosensitive Material]

[0893] The materials described in Table 3 shown in the latter stage were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the mixing ratio described in Table 3, and the solid content concentration of the finally obtained photosensitive material was made 25% by mass, thereby preparing a photosensitive material.

[0894] Regarding the obtained photosensitive materials of the Example 2 series (the photosensitive materials of Examples 2-1 to 2-8), the results of the carboxyl group consumption rate (mol%) were confirmed by IR measurement in the same manner as shown in the Example 1 series, and it was found that the carboxyl group consumption rates were all 20 mol% or more.

[0895] Further, regarding the photosensitive materials of each example or comparative example in Example 2 series, the carboxyl consumption rate, pattern formability of the photosensitive material, relative dielectric constant, change in relative dielectric constant before and after exposure, and lamination suitability, pattern formability, relative dielectric constant, change in relative dielectric constant before and after exposure, and moisture permeability of the transfer film were evaluated in the same manner as shown in Example 1 series. Also, in the same manner as shown in Example 1 series, regarding the photosensitive layer in the transfer film, the carboxyl consumption rate, transmittance with respect to light of 365 nm, and the ratio of the transmittance with respect to light of 365 nm to the transmittance with respect to light of 313 nm were also evaluated. Further, in the same manner as shown in Example 1 series, the physical property of ε365 / ε313 of Compound β contained in the photosensitive material and the photosensitive layer was evaluated.

[0896] Among them, the reference for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film was set to the relative dielectric constant or moisture permeability of Comparative Example 2A.

[0897] The following Table 3 shows the composition of the solid components of the photosensitive materials of each example or comparative example in Example 2 series and the test results.

[0898] In the table, the values described in the "Solid Component Composition" column represent the content (parts by mass) of each solid component contained in the photosensitive material of each example or comparative example. In addition, the value in parentheses in Compound β indicates the following: the total number of structures (Structure b0) in the photosensitive material that reduce the amount of carboxyl groups of Polymer A in Compound β (preferably a structure (Structure b) that can accept electrons from the carboxyl groups of Polymer A in the photoexcited state) relative to the total number of carboxyl groups of Polymer A (mol%).

[0899] Further, the value (ε365) in angle brackets described together with the component name of Compound β represents the molar extinction coefficient of Compound β with respect to light of wavelength 365 nm in acetonitrile ((cm·mol / L) -1 )

[0900] Also, the value (pKa in the ground state) in angle brackets described together with the component name of Compound β represents the pKa of Compound β in the ground state. The measurement method is as described above.

[0901] Further, the "ε365 / ε313" column in the evaluation of the photosensitive material and the evaluation of the transfer film represents the molar extinction coefficient of Compound β with respect to light of wavelength 365 nm ((cm·mol / L) -1 ) divided by the molar extinction coefficient of Compound β with respect to light of wavelength 313 nm ((cm·mol / L) -1The values obtained thereby. In addition, all the molar extinction coefficients are the values in acetonitrile.

[0902] In addition, in the "365 nm transmittance" column in the evaluation of the transfer film, it represents the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[0903] In addition, in the "365 nm transmittance / 313 nm transmittance" column in the evaluation of the transfer film, it represents the value obtained by dividing the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm by the transmittance of the photosensitive layer with respect to light having a wavelength of 313 nm.

[0904] [Table 4]

[0905]

[0906] UC3910: ARUFON UC3910 (manufactured by TOAGOSEI CO., LTD.)

[0907] DPHA: Dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0908] A-NOD-N: 1,9-Nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0909] DTMPT: Di-trimethylolpropane tetraacrylate (KAYARAD T-1420 (T) manufactured by Nippon Kayaku Co., Ltd)

[0910] A-DCP: Dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0911] TMPT: Trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0912] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[0913] From the results of the above table, it was confirmed that: Even when the photosensitive material contains a polymerizable compound, the problems of the present invention can be solved by the photosensitive material of the present invention.

[0914] Moreover, it was confirmed that the conditions for even more excellent effects of the present invention were the same as the trends confirmed for Example 1 series.

[0915] [Example 3 series]

[0916] <Preparation and Evaluation of Photosensitive Material>

[0917] In a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio), the materials described in Table 4 shown in the latter part were mixed and dissolved so as to satisfy the compounding amounts described in Table 4, and the solid content concentration of the finally obtained photosensitive material was made 25% by mass, thereby preparing a photosensitive material.

[0918] In addition, when preparing the photosensitive material, as the "synthesis method of Resin A" and "synthesis method of Resin B", a solution of Resin A or a solution of Resin B obtained by the method described later was used, and Resin A or Resin B was introduced into the photosensitive material.

[0919] Regarding the obtained photosensitive materials of Example 3 series (photosensitive materials of Examples 3-1 to 3-12), in the same manner as shown in Example 1 series (carboxyl consumption rate evaluation (IR measurement)), the results of the carboxyl consumption rate (molar ratio) were confirmed by IR measurement, and it was found that the carboxyl consumption rates were all 20 mol% or more.

[0920] In addition, the following test was also carried out: before the exposure of 1000 mJ / cm 2 using the high-pressure mercury lamp shown in Example 1 series (carboxyl consumption rate evaluation (IR measurement)), exposure of 100 mJ / cm 2 using an ultra-high-pressure mercury lamp was carried out, and then, exposure of 1000 mJ / cm 2 using the high-pressure mercury lamp was carried out. Even when the exposure of 100 mJ / cm 2 was carried out in this way in advance, when using any of the photosensitive materials of Example 3 series (photosensitive materials of Examples 3-1 to 3-12), the carboxyl consumption rates before and after the exposure of 1000 mJ / cm 2 also became 20 mol% or more.

[0921] Furthermore, with respect to the photosensitive materials of each example or comparative example in Example Series 3, in the same manner as shown in Example Series 1, the carboxyl consumption rate, the relative dielectric constant of the photosensitive material, the change in the relative dielectric constant before and after exposure, and the lamination suitability, relative dielectric constant, change in the relative dielectric constant before and after exposure, and moisture permeability of the transfer film were evaluated. Also, in the same manner as shown in Example Series 1, with respect to the photosensitive layer in the transfer film, the carboxyl consumption rate, the transmittance with respect to light of 365 nm, and the ratio of the transmittance with respect to light of 365 nm to the transmittance with respect to light of 313 nm were also evaluated. Further, in the same manner as shown in Example Series 1, the physical property of ε365 / ε313 of Compound β contained in the photosensitive material and the photosensitive layer was evaluated.

[0922] Among them, the reference for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film was set to the relative dielectric constant or moisture permeability of Comparative Example 3A.

[0923] Moreover, with respect to the photosensitive materials of each example or comparative example in Example Series 3, the pattern formability was evaluated. As the specific procedure for the evaluation of the pattern formability, the evaluation was carried out in the same order as the above (Pattern Formability Evaluation 1) of Example Series 1, except that the pattern forming method was changed as follows.

[0924] The photosensitive material of each example or comparative example was spin-coated on a silicon wafer, and then the obtained coating film was dried on a hot plate at 80 °C to obtain a photosensitive layer with a film thickness of 5 μm.

[0925] The obtained photosensitive layer was exposed using an ultra-high pressure mercury lamp through the same mask as in Example Series 1. The cumulative exposure dose measured with a 365 nm illuminometer was 100 mJ / cm 2 。

[0926] Subsequently, a 1 mass% aqueous solution of sodium carbonate (liquid temperature: 32 °C) was used as the developer to develop the pattern-exposed photosensitive layer for 40 seconds. After development, it was rinsed with pure water for 20 seconds, and air was further blown to remove moisture to obtain a pattern.

[0927] The obtained pattern was exposed over the entire surface using a high pressure mercury lamp. The cumulative exposure dose measured with a 365 nm illuminometer was 1000 mJ / cm 2 。

[0928] For the line and space patterns with a line width and space width of 25 μm, 50 μm, or 250 μm produced in this way, the evaluation was carried out based on the evaluation criteria described in the above (Pattern Formability Evaluation 1) of Example Series 1.

[0929] Furthermore, with respect to the transfer films of the respective examples or comparative examples in Example 3, the pattern formability was evaluated. As the specific procedure for evaluating the pattern formability, the evaluation was carried out in the same procedure as the above (Pattern Formability Evaluation 2) of Example 1, except that the pattern forming method was changed as follows.

[0930] By peeling off the cover film from the produced transfer film and laminating it onto a COP film (substrate for touch panel) laminated with a copper foil, the photosensitive layer of the transfer film was transferred onto the surface of the copper foil, and a laminate having a laminated structure of "temporary support / photosensitive layer / copper foil / substrate (COP film)" was obtained. The lamination conditions were set as follows: the temperature of the substrate for touch panel was 40°C, the temperature of the rubber roller (i.e., the lamination temperature) was 110°C, the line pressure was 3 N / cm, and the conveyance speed was 2 m / min. Herein, the copper foil was a film assuming the wiring of the touch panel.

[0931] As a result, the lamination property was good.

[0932] Next, using a proximity exposure machine (Hitachi High-Tech Corporation.) having an ultra-high pressure mercury lamp, and setting the distance between the exposure mask surface and the surface of the temporary support to 125 μm, the photosensitive layer of the above laminate was pattern-exposed through the temporary support under the condition of using the ultra-high pressure mercury lamp with an exposure amount of 100 mJ / cm 2 (i-ray).

[0933] The mask was the same mask as the line-and-space pattern in Example 1. After the exposure, the temporary support was peeled off from the laminate.

[0934] Next, using a 1 mass% aqueous solution of sodium carbonate (liquid temperature: 32°C) as the developer, the photosensitive layer of the laminate from which the temporary support had been peeled off was developed for 40 seconds. After the development, it was washed with pure water for 20 seconds, and air was blown to remove the moisture, thereby obtaining a pattern.

[0935] The obtained pattern was subjected to overall exposure using a high-pressure mercury lamp. The cumulative exposure amount measured with a 365 nm illuminometer was 1000 mJ / cm 2 .

[0936] With respect to the line-and-space patterns having a line width and a space width of 25 μm, 50 μm, or 250 μm produced in this manner, the evaluation was carried out based on the evaluation criteria described in the above (Pattern Formability Evaluation 1) of Example 1.

[0937] <Evaluation of Relative Dielectric Constant under Double Exposure Conditions>

[0938] In Example 3 series, the relative permittivity was also evaluated under two exposure conditions. In addition, the evaluation of the relative permittivity under one exposure condition refers to the evaluation of the relative permittivity evaluated under the same conditions as those shown in the above (Relative Permittivity Evaluation 2) in Example 1 series.

[0939] Regarding the photosensitive material of Example 3 series, a transfer film was manufactured in the same manner as that shown in (Manufacture of Transfer Film) in Example 1 series. The cover film was peeled off from the obtained transfer film, and the transfer film was laminated on an aluminum substrate with a thickness of 0.1 mm under the same conditions as those of the above (Lamination Suitability Evaluation) to obtain a laminate having a laminated structure of "temporary support / photosensitive layer / aluminum substrate".

[0940] On the above laminate, as the first exposure, an ultra-high pressure mercury lamp was used, and the photosensitive layer was exposed over the entire surface through the temporary support. In the first exposure, the cumulative exposure measured with a 365 nm illuminometer was 100 mJ / cm 2 . In addition, since the first exposure was through the temporary support (polyethylene terephthalate), most of the light with wavelengths of 320 nm or less was blocked. Therefore, it is considered that substances with a large molar extinction coefficient with respect to light of wavelength 365 nm (for example, 1×10 3 (cm·mol / L) -1 or more) preferentially participate in the reaction.

[0941] Then, the temporary support was peeled off from the above laminate, and as the second exposure, a high pressure mercury lamp was used to expose the photosensitive layer over the entire surface. In the second exposure, the cumulative exposure measured with a 365 nm illuminometer was 1000 mJ / cm 2 .

[0942] Regarding the photosensitive layer exposed in this way, the relative permittivity was measured in the same manner as that shown in the above (Relative Permittivity Evaluation 2) in Example 1 series.

[0943] Among them, as the reference of the relative permittivity, the relative permittivity of Comparative Example 3A under two exposure conditions was set.

[0944] The following Table 4 shows the composition of the solid components of the photosensitive materials of each example or comparative example in Example 3 series and the test results.

[0945] The same notations in Table 4 as those in Table 3 have the same meanings as those described with respect to Table 3.

[0946] [Table 5]

[0947]

[0948] Resin A: A resin with the following structure (acid value: 94.5 mg KOH / g)

[0949] [Chemical formula 8]

[0950]

[0951] Synthesis method of Resin A

[0952] 200 g of propylene glycol monomethyl ether and 50 g of propylene glycol monomethyl ether acetate were added to a flask and heated to 90 °C under a nitrogen stream. In this liquid, a solution in which 192.9 g of cyclohexyl methacrylate, 4.6 g of methyl methacrylate, and 89.3 g of methacrylic acid were dissolved in 60 g of propylene glycol monomethyl ether acetate and a solution in which 9.2 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was dissolved in 114.8 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After completion of the dropwise addition, a solution obtained by dissolving 2 g of V-601 in 10 g of propylene glycol monomethyl ether acetate was added 3 times at 1-hour intervals. Then, the reaction was further continued for 3 hours. It was diluted with 168.7 g of propylene glycol monomethyl ether acetate. Under an air stream, the reaction solution was heated to 100 °C, and 1.5 g of tetraethylammonium bromide and 0.67 g of p-methoxyphenol were added. 63.4 g of glycidyl methacrylate (BLEMMER GH manufactured by NOF CORPORATION) was added dropwise thereto over 20 minutes. The reaction was carried out at 100 °C for 6 hours to obtain a solution of Resin A. The solid content concentration of the obtained solution was 36.2%. The weight-average molecular weight in terms of standard polystyrene in GPC was 27,000, the dispersity was 2.9, and the acid value of the polymer was 94.5 mg KOH / g. The residual monomer amount measured using a gas chromatograph was less than 0.1 mass% with respect to the polymer solid content for any monomer.

[0953] Resin B: A resin with the following structure (acid value: 94.5 mg KOH / g)

[0954] [Chemical formula 9]

[0955]

[0956] Synthesis method of Resin B

[0957] 82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90 °C under a nitrogen stream. In this liquid, a solution in which 38.4 g of styrene, 30.1 g of dicyclopentanyl methacrylate, and 34.0 g of methacrylic acid were dissolved in 20 g of propylene glycol monomethyl ether and a solution in which 5.4 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was dissolved in 43.6 g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After completion of the dropwise addition, 0.75 g of V-601 was added 3 times at 1-hour intervals. Then, the reaction was further continued for 3 hours. Then, it was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. Under an air stream, the reaction solution was heated to 100 °C, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. 25.5 g of glycidyl methacrylate (BLEMMER GH manufactured by NOF CORPORATION) was added dropwise thereto over 20 minutes. The reaction was carried out at 100 °C for 7 hours to obtain a solution of resin B. The solid content concentration of the obtained solution was 36.2%. The weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersion was 2.4, and the acid value of the polymer was 94.5 mgKOH / g. The residual monomer amount measured using a gas chromatograph was less than 0.1 mass% with respect to the polymer solid content in any monomer.

[0958] DPHA: Dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0959] A-NOD-N: 1,9-Nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0960] DTMPT: Di-trimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd)

[0961] A-DCP: Dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0962] TMPT: Trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[0963] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[0964] OXE-02: Irgacure OXE02 (manufactured by BASF Corporation, oxime ester compound), molar extinction coefficient with respect to light of wavelength 365 nm in acetonitrile: 2700 (cm·mol / L) -1

[0965] Omn907: Omnirad 907 (manufactured by IGM Resins B.V., aminophenylethanone compound), molar extinction coefficient with respect to light of wavelength 365 nm in acetonitrile: 120 (cm·mol / L) -1

[0966] As shown in the table, it was confirmed that: even when the photosensitive material contains a photopolymerization initiator, the photosensitive material according to the present invention can solve the problems of the present invention.

[0967] Moreover, it was confirmed that: regarding the conditions where the effects of the present invention are more excellent, the trend is the same as that confirmed for Example 1 series.

[0968] [Evaluation under the conditions of double exposure of the layer having a photosensitive layer and a second resin layer formed using the photosensitive material of Example 3 series]

[0969] <Manufacture of transfer film>

[0970] (Formation of photosensitive layer)

[0971] On a polyethylene terephthalate film with a thickness of 16 μm (Toray Industries, Inc. manufacture, 16KS40) (temporary support), using a slit-shaped nozzle, the photosensitive material liquid of each example shown in Example 3 series was adjusted and coated so that the dried thickness became 5 μm, and it was dried at 100 °C for 2 minutes to form a photosensitive layer.

[0972] (Formation of second resin layer)

[0973] Next, on the photosensitive layer, a coating liquid for the second resin layer composed of the following Formulation 201 was adjusted and coated so that the dried thickness became 70 nm, and after drying at 80 °C for 1 minute, it was further dried at 110 °C for 1 minute to form a second resin layer disposed in direct contact with the photosensitive layer. The film thickness of the second resin layer was 70 nm and the refractive index was 1.68.

[0974] In addition, Formulation 201 was prepared using a resin having an acid group and an aqueous ammonia solution, and the resin having an acid group was neutralized with the aqueous ammonia solution. That is, the coating liquid for the second resin layer is an aqueous resin composition containing an ammonium salt of a resin having an acid group.

[0975] · Coating liquid for the second resin layer: Formulation 201 (aqueous resin composition)

[0976] · Acrylic resin (resin having an acid group, copolymer resin of methacrylic acid / methacrylic acid allyl ester, weight average molecular weight 25,000, composition ratio (molar ratio) = 40 / 60, solid content 99.8%): 0.29 parts

[0977] · ARONIX TO-2349 (monomer having a carboxyl group, manufactured by TOAGOSEI CO., LTD.): 0.04 parts

[0978] · Nanouse OZ-S30M (ZrO2 particles, solid content 30.5%, methanol 69.5%, refractive index 2.2, average particle size: about 12 nm, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.): 4.80 parts

[0979] · BT120 (benzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.): 0.03 parts

[0980] · MEGAFACE F444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.01 part

[0981] · Ammonia water solution (2.5 mass%): 7.80 parts

[0982] · Distilled water: 24.80 parts

[0983] · Methanol: 76.10 parts

[0984] (Formation of pattern)

[0985] For the laminate in which a photosensitive layer is sequentially provided on a temporary support and a second resin layer is disposed in direct contact on the photosensitive layer obtained in the above-described manner, a polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16KS40) having a thickness of 16 μm (cover film) was pressure-bonded onto the second resin layer thereof. Thus, a transfer film (photosensitive transfer material) having a photosensitive layer and a second resin layer formed using the photosensitive materials of the respective examples of Example 3 was produced.

[0986] By peeling off the covering film from the transfer film produced as described above and laminating it onto a PET film (substrate for touch panel) on which a copper foil of GEOMATEC Co., Ltd. is laminated, the photosensitive layer of the transfer film was transferred onto the surface of the copper foil, and a laminate having a laminated structure of "temporary support / photosensitive layer / second resin layer / copper foil / substrate (PET film)" was obtained. The lamination conditions were set as follows: the temperature of the substrate for touch panel was 40 °C, the temperature of the rubber roller (i.e., the lamination temperature) was 110 °C, the line pressure was 3 N / cm, and the conveyance speed was 2 m / min. Herein, the copper foil is a film assuming the wiring of the touch panel.

[0987] The laminating property is equivalent to and good as that of each transfer film of Example 3 series without the second resin layer.

[0988] Next, using a proximity exposure machine (Hitachi High-Tech Corporation.) equipped with an ultra-high pressure mercury lamp, and setting the distance between the surface of the exposure mask (quartz exposure mask having a pattern for forming a protective layer) and the surface of the temporary support to 125 μm, the photosensitive layer of the above laminate was pattern-exposed through the temporary support under the condition of an exposure amount of 100 mJ / cm 2 (i-ray).

[0989] During the exposure, the exposure was performed through a mask with a line size = 50 μm and a line:space = 1:1, or a mask with a line size = 250 μm and a line:space = 1:1.

[0990] After the exposure, the temporary support was peeled off from the laminate.

[0991] Next, using a 1 mass% aqueous solution of sodium carbonate (liquid temperature: 32 °C) as the developer, the photosensitive layer of the laminate from which the temporary support was peeled off was developed for 40 seconds. After the development, it was washed with pure water for 20 seconds, and air was blown to remove the moisture, obtaining a pattern. The obtained pattern was subjected to overall exposure using a high-pressure mercury lamp. The cumulative exposure amount measured with an illuminometer of 365 nm was 1000 mJ / cm 2 .

[0992] Evaluating the results of the line-and-space pattern with a line width and a space width of 50 μm or 250 μm produced in this way in the same manner as above (pattern formation evaluation 1), it was found that the evaluation results were equally good when the pattern was formed and evaluated in the same manner as each transfer film of Example 3 series without the second resin layer.

[0993] That is, the photosensitive material of the present invention containing a polymerizable compound and a photoinitiator also has good pattern formability under two-stage exposure conditions.

[0994] A PET film with an ITO film assumed to be a transparent electrode of a touch panel was used instead of a PET film laminated with a copper foil, and the same evaluation as that under the conditions of two exposures of a layer having a photosensitive layer and a second resin layer formed of the photosensitive material of Example 3 was performed. The results showed good laminability and pattern formability as in the case of using a PET film laminated with a copper foil.

[0995] [Example 4 Series]

[0996] The structure of Polymer A used in Example 4 series is shown in Table 5 below. In addition, Polymer A was a polymer synthesized by a known method.

[0997] Hereinafter, as a representative example, the synthesis method of the polymer of Compound No. 1 is shown.

[0998] (Synthesis of Polymer of Compound No. 1)

[0999] PGMEA (60 parts) and PGME (240 parts) were introduced into a 2000 mL flask. The obtained liquid was stirred at a stirring speed of 250 rpm (round per minute; the same hereinafter), and at the same time, it was heated to 90°C.

[1000] As the preparation of dropping solution (1), styrene (47.7 parts), methyl methacrylate (1.3 parts) and methacrylic acid (51 parts) were mixed and diluted with PGMEA (60 parts) to obtain dropping solution (1).

[1001] As the preparation of dropping solution (2), V-601 (dimethyl 2,2'-azobis(2-methylpropionate) (9.637 parts) was dissolved in PGMEA (136.56 g) to obtain dropping solution (2).

[1002] Dropping solution (1) and dropping solution (2) were simultaneously dropped into the above-mentioned 2000 mL flask (specifically, a 2000 mL flask filled with liquid heated to 90°C) over 3 hours. After the dropping was completed, V-601 (2.401 g) was added to the above flask 3 times at intervals of 1 hour. Then, it was further stirred at 90°C for 3 hours.

[1003] Then, the solution (reaction solution) obtained in the above flask was diluted with PGMEA (178 parts). Next, tetraethylammonium bromide (1.8 parts) and hydroquinone monomethyl ether (0.8 parts) were added to the reaction solution. Then, the temperature of the reaction solution was raised to 100°C.

[1004] Next, glycidyl methacrylate in an amount corresponding to the composition of Compound No. 1 in Table 5 was added dropwise to the reaction solution over 1 hour. The reaction solution was reacted at 100 °C for 6 hours to obtain a polymer solution (solid content concentration: 36.3 mass%).

[1005] As shown in Table 5, the weight-average molecular weight of Polymer A is in the range of 10,000 to 50,000.

[1006] Moreover, the numerical values of the respective structural units in Table 5 represent mass ratios.

[1007] In the column of Polymer A in Table 5, the abbreviations of the respective monomers forming the polymer are as follows. In addition, GMA-MAA represents a structural unit obtained by adding glycidyl methacrylate to the structural unit derived from methacrylic acid, and GMA-AA represents a structural unit obtained by adding glycidyl methacrylate to the structural unit derived from acrylic acid.

[1008] St: Styrene

[1009] CHMA: Cyclohexyl methacrylate

[1010] CHA: Cyclohexyl acrylate

[1011] MMA: Methyl methacrylate

[1012] FA: Ethyl acrylate

[1013] BzMA: Benzyl methacrylate

[1014] BzA: Benzyl acrylate

[1015] HEMA: 2-Hydroxyethyl methacrylate

[1016] HEA: 2-Hydroxyethyl acrylate

[1017] MAA: Methacrylic acid

[1018] AA: Acrylic acid

[1019] [Table 6]

[1020]

[1021] [Preparation and Evaluation of Photosensitive Material]

[1022] The materials described in Table 6 shown in the latter stage were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the blending amounts described in Table 6, and the solid content concentration of the finally obtained photosensitive material was made 25 mass% to prepare a photosensitive material.

[1023] In addition, in Table 6 below, the numbers of the examples and comparative examples are represented by a head number + a serial number. That is, Example 4-1-1 corresponds to an example with a head number of 4-1 and a serial number of 1. Also, Comparative Example 4A-1 corresponds to an example with a head number of 4A and a serial number of 1.

[1024] Furthermore, regarding the photosensitive materials of each example or comparative example in the Example 4 series, in the same manner as shown in the Example 1 series, the carboxyl consumption rate, the pattern formability of the photosensitive material, the relative dielectric constant, the change in the relative dielectric constant before and after exposure, and the lamination suitability, pattern formability, relative dielectric constant, change in the relative dielectric constant before and after exposure, and moisture permeability of the transfer film were evaluated. Also, in the same manner as shown in the Example 1 series, the carboxyl consumption rate of the photosensitive layer in the transfer film, the transmittance with respect to light of 365 nm, and the ratio of the transmittance with respect to light of 365 nm to the transmittance with respect to light of 313 nm were also evaluated. Also, in the same manner as shown in the Example 1 series, the physical property of ε365 / ε313 of Compound β contained in the photosensitive material and the photosensitive layer was evaluated.

[1025] Among them, the reference for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film was set to the relative dielectric constant or moisture permeability of the comparative example with the same serial number. That is, for example, in the case of Example 4-1-1, since the serial number is 1, Comparative Example 4A-1 with the same serial number meets the reference. Also, for example, in the case of Example 4-27-51, since the serial number is 51, Comparative Example 4A-51 with the same serial number meets the reference.

[1026] Hereinafter, Table 6 shows the composition of the solid components of the photosensitive materials of each example or comparative example in the Example 4 series and the test results.

[1027] In the table, the "Compound Number" in the "Polymer A" column corresponds to the "Compound Number" described in Table 5 above.

[1028] In the table, the values described in the "Parts by Mass" column represent the contents (parts by mass) of the solid components of each component. In addition, the above-mentioned compounding amounts (parts by mass) are the amounts of "Polymer A" and "Compound β" themselves (solid components) added to the photosensitive material.

[1029] Moreover, the value of "molar ratio (mol%) relative to the carboxyl groups of polymer A" in Compound β in the table is represented as follows: the ratio (mol%) of the total number of structures (Structure b0) in photosensitive material that reduce the amount of carboxyl groups of polymer A in Compound β (preferably a structure (Structure b) capable of accepting electrons from the carboxyl groups contained in polymer A in a photoexcited state) to the total number of carboxyl groups of polymer A.

[1030] Moreover, the "ε365 / ε313" column in the evaluation of the photosensitive material and the evaluation of the transfer film represents the value obtained by dividing the molar extinction coefficient ((cm·mol / L) -1 ) of Compound β with respect to light of wavelength 365 nm by the molar extinction coefficient ((cm·mol / L) -1 ) of Compound β with respect to light of wavelength 313 nm. In addition, the molar extinction coefficients are all values in acetonitrile.

[1031] Moreover, the "365 nm transmittance" column in the evaluation of the transfer film represents the transmittance of the photosensitive layer with respect to light of wavelength 365 nm.

[1032] Moreover, the "365 nm transmittance / 313 nm transmittance" column in the evaluation of the transfer film represents the value obtained by dividing the transmittance of the photosensitive layer with respect to light of wavelength 365 nm by the transmittance of the photosensitive layer with respect to light of wavelength 313 nm.

[1033] Moreover, in Table 6, the types of Compound β used in the preparation of the photosensitive material are represented by notations.

[1034] The correspondence between the types of Compound β and the notations is as follows. Hereinafter, the measurement method of "pKa in the ground state" described for each Compound β is as described above. "ε365" represents the molar extinction coefficient ((cm·mol / L) -1 ) of Compound β in acetonitrile with respect to light of wavelength 365 nm.

[1035]

[1036]

[1037]

[1038]

[1039]

[1040]

[1041]

[1042]

[1043]

[1044]

[1045]

[1046]

[1047]

[1048]

[1049]

[1050]

[1051]

[1052]

[1053]

[1054]

[1055]

[1056]

[1057]

[1058]

[1059]

[1060]

[1061]

[1062]

[1063]

[1064]

[1065]

[1066]

[1067] It was confirmed from the results of the above table that the transfer film of the present invention can solve the problems of the present invention.

[1068] Moreover, it was confirmed that the conditions for more excellent effects of the present invention are the same as the trends confirmed for Example 1.

[1069] [Example 5 Series]

[1070] [Preparation and Evaluation of Photosensitive Material]

[1071] The materials described in Table 7 shown in the latter stage were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so that the solid content concentration of the finally obtained photosensitive material became 25% by mass, thereby preparing a photosensitive material.

[1072] Moreover, regarding the photosensitive materials of each example or comparative example in Example 5 series obtained, in the same manner as shown in Example 1 series, the carboxyl consumption rate, pattern formability of the photosensitive material, relative dielectric constant and change in relative dielectric constant before and after exposure, and lamination suitability, pattern formability, relative dielectric constant, change in relative dielectric constant before and after exposure, and moisture permeability of the transfer film were evaluated. Also, in the same manner as shown in Example 1 series, the carboxyl consumption rate, transmittance with respect to light of 365 nm, and the ratio of the transmittance with respect to light of 365 nm to the transmittance with respect to light of 313 nm in the photosensitive layer of the transfer film were evaluated.

[1073] Among them, the reference for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film was set to the relative dielectric constant or moisture permeability of Comparative Example 5A.

[1074] Hereinafter, Table 7 shows the composition of the solid components of the photosensitive materials of each example or comparative example in Example 5 series and the results of the tests.

[1075] In addition, the solid component in the photosensitive material of each example shown in Example 5 series has a composition of 100% by mass of Polymer A. And Polymer A used in each example shown in Example 5 series corresponds to Polymer Ab.

[1076] In the "x / y / z" column in the table represents the mass ratio of each structural unit constituting Polymer A.

[1077] The weight average molecular weight of Polymer A shown in Table 7 is 10,000 to 50,000 as shown in Table 7.

[1078] In addition, the "365 nm transmittance" column in the evaluation of the transfer film represents the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm.

[1079] In addition, the "365 nm transmittance / 313 nm transmittance" column in the evaluation of the transfer film represents the value obtained by dividing the transmittance of the photosensitive layer with respect to light having a wavelength of 365 nm by the transmittance of the photosensitive layer with respect to light having a wavelength of 313 nm.

[1080] In addition, the notation of St / AA in the table represents styrene / acrylic acid copolymer (composition ratio: repeating unit based on styrene / repeating unit based on acrylic acid = 80 / 20 (mass ratio)).

[1081]

[1082] It was confirmed from the results of the above table that the problems of the present invention can be solved by the transfer film of the present invention.

[1083] [Example 6 series]

[1084] [Preparation and Evaluation of Photosensitive Material]

[1085] The materials described in Table 8 shown in the latter stage were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the blending amounts described in Table 8, and the solid content concentration of the finally obtained photosensitive material was made 25% by mass, thereby preparing a photosensitive material.

[1086] In addition, with respect to the photosensitive materials of each example or comparative example in the obtained Example 6 series, in the same manner as shown in Example 1 series, the carboxyl consumption rate, the pattern formability of the photosensitive material, the relative dielectric constant and the change in relative dielectric constant before and after exposure, and the lamination suitability, pattern formability, relative dielectric constant, change in relative dielectric constant before and after exposure, and moisture permeability of the transfer film were evaluated. In addition, in the same manner as shown in Example 1 series, the carboxyl consumption rate of the photosensitive layer in the transfer film, the transmittance with respect to light having a wavelength of 365 nm, and the ratio of the transmittance with respect to light having a wavelength of 365 nm to the transmittance with respect to light having a wavelength of 313 nm were also evaluated. In addition, in the same manner as shown in Example 1 series, the physical properties of ε365 / ε313 of compound β contained in the photosensitive material and the photosensitive layer were evaluated.

[1087] Among them, the reference for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and in the evaluation of the relative dielectric constant and moisture permeability of the transfer film was set to the relative dielectric constant or moisture permeability of Comparative Example 6A.

[1088] The composition of the solid components of the photosensitive materials of each example or comparative example in Example 6 and the test results are shown in Table 8 below.

[1089] In the table, the values described in the "Solid Component Composition" column represent the contents (parts by mass) of the respective solid components contained in the photosensitive materials of each example or comparative example. In addition, the value in parentheses in Compound β indicates the ratio (mol%) of the total number of structures (Structure b0) in the photosensitive material that reduce the amount of carboxyl groups in Polymer A (preferably a structure (Structure b) that can accept electrons from the carboxyl groups contained in Polymer A in the photoexcited state) to the total number of carboxyl groups in Polymer A.

[1090] Also, the method for measuring the "pKa of Compound β in the ground state" in the table is as described above.

[1091] Also, the "ε365 of Compound β" column in the table represents the molar extinction coefficient of Compound β in acetonitrile with respect to light of wavelength 365 nm ((cm·mol / L) -1 ).

[1092] Also, the "ε365 / ε313" column in the evaluation of the photosensitive material and the evaluation of the transfer film represents the molar extinction coefficient of Compound β with respect to light of wavelength 365 nm ((cm·mol / L) -1 ) divided by the molar extinction coefficient of Compound β with respect to light of wavelength 313 nm ((cm·mol / L) -1 ). In addition, all molar extinction coefficients are values in acetonitrile.

[1093] Also, the "365 nm Transmittance" column in the evaluation of the transfer film represents the transmittance of the photosensitive layer with respect to light of wavelength 365 nm.

[1094] Also, the "365 nm Transmittance / 313 nm Transmittance" column in the evaluation of the transfer film represents the value obtained by dividing the transmittance of the photosensitive layer with respect to light of wavelength 365 nm by the transmittance of the photosensitive layer with respect to light of wavelength 313 nm.

[1095]

[1096]

[1097]

[1098]

[1099]

[1100]

[1101]

[1102]

[1103]

[1104]

[1105]

[1106] (Polymer A)

[1107] Polymers 1 to 4 equivalent to Polymer A were synthesized by the same method as in Example 4 above. In addition, the abbreviations of the monomers of the respective structural units forming the polymers are as described above.

[1108] Polymer 1: St / MAA / MMA / gMA-MAA = 47.7 / 19.0 / 1.3 / 32.0 (mass ratio)

[1109] Polymer 2: CHMA / MAA / BzMA = 49 / 19 / 32 (mass ratio)

[1110] Polymer 3: St / AA / AA-GMA = 53.5 / 14.5 / 32 (mass ratio)

[1111] Polymer 4: CHA / AA / HEA = 53.5 / 14.5 / 32 (mass ratio)

[1112] In addition, the weight-average molecular weights of Polymer A shown in Table 8 are all in the range of 10,000 to 50,000 as shown in Table 8.

[1113] (Polymerizable compound)

[1114] DPHA: Dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1115] A-NOD-N: 1,9-Nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1116] DTMPT: Di-trimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd)

[1117] A-DCP: Dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1118] TMPT: Trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1119] SR601: Ethoxylated (4) bisphenol A diacrylate (SR601 manufactured by TOMOE ENGINEERING CO., LTD.)

[1120] KRM8904: 9-functional aliphatic acrylic urethane (KRM8904 manufactured by DAICEL-ALLNEX LTD.)

[1121] KRM8452: 10-functional aliphatic acrylic urethane (KRM8452 manufactured by DAICEL-ALLNEX LTD.)

[1122] (Surfactant)

[1123] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[1124] R41: MEGAFACE R-41 (manufactured by DIC Corporation)

[1125] 710FL: FTERGENT710FL (manufactured by Neos Corporation)

[1126] It was confirmed from the results of the above table that even when the photosensitive material contains a polymerizable compound, the problems of the present invention can be solved by the transfer film of the present invention.

[1127] [Example 7 system]

[1128] [Preparation and evaluation of photosensitive material]

[1129] The materials described in Table 9 shown in the latter stage were mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50 / 50 (mass ratio) so as to satisfy the mixing ratio described in Table 9, and the solid content concentration of the finally obtained photosensitive material was made 25% by mass, thereby preparing a photosensitive material.

[1130] Furthermore, with respect to the photosensitive materials of each example or comparative example in Example Series 7 obtained, in the same manner as shown in Example Series 1, the carboxyl consumption rate, pattern formability of the photosensitive material, relative dielectric constant, change in relative dielectric constant before and after exposure, and laminate suitability, pattern formability, relative dielectric constant, change in relative dielectric constant before and after exposure, moisture permeability, and change in relative dielectric constant after two exposures of the transfer film were evaluated. Also, in the same manner as shown in Example Series 3, the carboxyl consumption rate of the photosensitive layer in the transfer film, transmittance with respect to light of 365 nm, transmittance with respect to light of 313 nm, and the ratio of the transmittance with respect to light of 313 nm to the transmittance with respect to light of 313 nm were also evaluated. Also, in the same manner as shown in Example Series 1, the physical property of ε365 / ε313 of Compound β contained in the photosensitive material and the photosensitive layer was evaluated.

[1131] Among them, the reference for the reduction rate in the evaluation of the relative dielectric constant of the photosensitive material and the evaluation of the relative dielectric constant and moisture permeability of the transfer film was set to the relative dielectric constant or moisture permeability of Comparative Example 7A.

[1132] The results of the composition of the solid components and tests of the photosensitive materials of each example or comparative example in Example Series 7 are shown in Table 9 below.

[1133] In the table, the values described in the "Solid Component Composition" column represent the content (parts by mass) of each solid component contained in the photosensitive material of each example or comparative example. In addition, the value in parentheses in Compound β represents the ratio (mol%) of the total number of structures (Structure b0) in the photosensitive material that reduce the amount of carboxyl groups of Polymer A in Compound β (preferably a structure (Structure b) that can accept electrons from the carboxyl groups contained in Polymer A in the photoexcited state) to the total number of carboxyl groups of Polymer A.

[1134] Also, the measurement method of "pKa of Compound β in the ground state" in the table is as described above.

[1135] Also, the "ε365 of Compound β" column in the table represents the molar extinction coefficient of Compound β with respect to light of wavelength 365 nm in acetonitrile ((cm·mol / L) -1 ).

[1136] Also, the "ε365 / ε313" column in the evaluation of the photosensitive material and the evaluation of the transfer film represents the molar extinction coefficient of Compound β with respect to light of wavelength 365 nm ((cm·mol / L) -1 ) divided by the molar extinction coefficient of Compound β with respect to light of wavelength 313 nm ((cm·mol / L) -1)The values obtained. Additionally, the molar extinction coefficients are all values in acetonitrile.

[1137] Moreover, in the evaluation of the transfer film, the "365 nm transmittance" column indicates the transmittance of the photosensitive layer with respect to light of wavelength 365 nm.

[1138] Moreover, in the evaluation of the transfer film, the "365 nm transmittance / 313 nm transmittance" column indicates the value obtained by dividing the transmittance of the photosensitive layer with respect to light of wavelength 365 nm by the transmittance of the photosensitive layer with respect to light of wavelength 313 nm.

[1139]

[1140]

[1141]

[1142]

[1143]

[1144]

[1145]

[1146]

[1147]

[1148]

[1149]

[1150]

[1151]

[1152]

[1153] (Polymer A)

[1154] Polymers 1 to 4 equivalent to Polymer A were synthesized by the same method as in Example 4 above. Additionally, the abbreviations of the monomers for each structural unit forming the polymers are as described above.

[1155] Polymer 1: St / MAA / MMA / gMA-MAA = 47.7 / 19.0 / 1.3 / 32.0 (mass ratio)

[1156] Polymer 2: CHMA / MAA / BzMA = 49 / 19 / 32 (mass ratio)

[1157] Polymer 3: St / AA / AA-GMA = 53.5 / 14.5 / 32 (by mass)

[1158] Polymer 4: CHA / AA / HEA = 53.5 / 14.5 / 32 (by mass)

[1159] In addition, the weight-average molecular weight of Polymer A shown in Table 9 is in the range of 10,000 to 50,000 as shown in Table 9.

[1160] (Polymerizable compound)

[1161] DPHA: Dipentaerythritol hexaacrylate (A-DPH manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1162] A-NOD-N: 1,9-Nonanediol diacrylate (A-NOD-N manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1163] DTMPT: Di-trimethylolpropane tetraacrylate (KAYARAD T-1420(T) manufactured by Nippon Kayaku Co., Ltd)

[1164] A-DCP: Dicyclopentane dimethanol diacrylate (A-DCP manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1165] TMPT: Trimethylolpropane triacrylate (A-TMPT manufactured by Shin Nakamura Chemical Industry Co., LTD.)

[1166] SR601: Ethoxylated (4) bisphenol A diacrylate (SR601 manufactured by TOMOE ENGINEERING CO., LTD.)

[1167] KRM8904: 9-functional aliphatic acrylic urethane (KRM8904 manufactured by DAICEL-ALLNEX LTD.)

[1168] KRM8452: 10-functional aliphatic acrylic urethane (KRM8452 manufactured by DAICEL-ALLNEX LTD.)

[1169] (Photoinitiator)

[1170] Omn379: Omnirad 379 (manufactured by IGM Resins B.V., an alkylbenzophenone compound)

[1171] Oxe02: Irgacure OXE02 (manufactured by BASF, an oxime ester compound)

[1172] Api307: (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (manufactured by Shenzhen UV-Chem Tech LTD)

[1173] (Surfactant)

[1174] F551: MEGAFACE F551 (manufactured by DIC Corporation)

[1175] R41: MEGAFACE R-41 (manufactured by DIC Corporation)

[1176] 710FL: FTERGENT710FL (manufactured by Neos Corporation)

[1177] [Examples 201 - 218, Comparative Example 201: Physical Property Evaluation of Compound β]

[1178] Regarding Compound β used in the above Examples 1 series - Examples 7 series, the volatility resistance (residual rate in the photosensitive layer after the coating process) in the coating process when forming the photosensitive layer was evaluated in the following order.

[1179] [Preparation of Photosensitive Material]

[1180] In the photosensitive material of Example 1-1 of the above Example 1 series, except that Compound β was changed to the compounds exemplified below, and the compounding amount of Compound β was set to 0.2 equivalents relative to the molar amount of the carboxyl group of Polymer A, the photosensitive materials of Examples 201 - 218 were prepared in the same manner.

[1181] Also, in the photosensitive material of Example 1-1 of the above Example 1 series, except that 5,6,7,8-tetrahydroquinoline was not added, the photosensitive material of Comparative Example 201 was prepared in the same manner.

[1182] [Evaluation of Photosensitive Material]

[1183] (Production of Photosensitive Layer)

[1184] The photosensitive materials of each example and comparative example were spin-coated on glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) measuring 10×10 cm 2 , and then, using a hot plate, the obtained coating film was dried at 80 °C to obtain a photosensitive layer with a film thickness of 5 μm.

[1185] The obtained photosensitive layer was evaluated in the following manner.

[1186] (Determination of the residual ratio of compound β)

[1187] First, the following two kinds of samples were prepared.

[1188] (1) A sample obtained by diluting the photosensitive material 2-fold with deuterated acetone (Sample A)

[1189] (2) A sample obtained by cutting off about 5 mg of the obtained photosensitive layer and dissolving it in deuterated acetone (Sample B)

[1190] Next, using AVANCE III manufactured by Bruker Corporation, the 1 1H-NMR of each sample was measured (locking solvent: deuterated acetone, pulse program: zg30, number of accumulations 32 times). Based on the peak area ratio of styrene to compound β, the residual ratio (%) of compound β was calculated by the following formula (H).

[1191] Formula (H): Residual ratio = (content of compound β in Sample A - content of compound β in Sample B) / content of compound β in Sample A × 100 [%]

[1192] Next, evaluation was carried out based on the following evaluation criteria. The results are shown in Table 10. In addition, in Table 10 shown below, the molecular weight of compound β is also shown together.

[1193] (Evaluation criteria)

[1194] A The residual ratio is 85% or more

[1195] B The residual ratio is 60% or more and less than 85%

[1196] C The residual ratio is 20% or more and less than 60%

[1197] D The residual ratio is less than 20%

[1198] [Table 64]

[1199]

[1200] It was clarified from the results in Table 10 that when the molecular weight of Compound β was 120 or more (preferably 130 or more, more preferably 180 or more), the volatility in the coating process was low (the residual rate of Compound β in the photosensitive layer after the coating process was high).

[1201] <Evaluation of Transfer Film>

[1202] (Production of Transfer Film)

[1203] On a polyethylene terephthalate film with a thickness of 16 μm (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) (temporary support), using a slit nozzle, the photosensitive materials of each example and comparative example were adjusted and coated to a dry thickness of 5 μm, and dried at 100 °C for 2 minutes to form a photosensitive layer.

[1204] A polyethylene terephthalate film with a thickness of 16 μm (manufactured by Toray Industries, Inc., 16KS40 (16QS62)) (cover film) was pressure-bonded onto the obtained photosensitive layer, and transfer films of the examples and comparative examples were produced.

[1205] By peeling off the cover film from the transfer film produced above and laminating it onto a glass (Eagle XG manufactured by Corning Incorporated Co., Ltd.) 10 × 10 cm 2 , the photosensitive layer of the transfer film was transferred onto the surface of the glass. The lamination conditions were set to a temperature of 40 °C for the touch panel substrate, a temperature of the rubber roller (i.e., lamination temperature) of 110 °C, a line pressure of 3 N / cm, and a conveyance speed of 2 m / minute.

[1206] Approximately 5 mg of the photosensitive layer of the obtained glass with a photosensitive layer was cut off to prepare a sample (Sample C) dissolved in deuterated acetone.

[1207] In the above (Determination of Residual Rate of Compound β), except that Sample B was changed to Sample C, the volatility of Compound β in the coating process (residual rate of Compound β in the photosensitive layer after the coating process) was determined in the same manner, and the results were the same as those shown in Table 10 above.

[1208] [Example 1001 (Fabrication and Evaluation of Device)]

[1209] <Fabrication of Transparent Laminate>

[1210] A substrate having an ITO transparent electrode pattern and a meandering wiring of copper formed on a cycloolefin transparent film was prepared.

[1211] Using the transfer film of Example 1-1 of Example 1 with the protective film peeled off, the ITO transparent electrode pattern and the copper detour wiring were laminated to the position covering the transfer film. A vacuum laminator manufactured by MCK was used, and lamination was performed under the conditions of a temperature of the cycloolefin transparent film: 40 °C, a temperature of the rubber roller: 100 °C, a line pressure: 3 N / cm, and a conveying speed: 2 m / minute.

[1212] Then, after peeling off the temporary support, pattern exposure was performed using an exposure mask (quartz exposure mask having a pattern for forming an outer coating) and a high-pressure mercury lamp. As the exposure conditions, the cumulative exposure measured with a 365 nm illuminometer was 1000 mJ / cm 2 .

[1213] After exposure, a 1 mass% aqueous solution of sodium carbonate (liquid temperature: 32 °C) as a developer was used to develop the photosensitive layer of the laminate from which the temporary support had been peeled off for 40 seconds.

[1214] Then, residues were removed by spraying ultrapure water from an ultra-high pressure cleaning nozzle onto the transparent film substrate after the developing treatment. Next, air was blown in to remove the moisture on the transparent film substrate, and a transparent laminate in which an ITO transparent electrode pattern, a copper detour wiring, and a cured film were laminated in sequence was formed on the transparent film substrate.

[1215] Using the produced transparent laminate, a touch panel was manufactured by a known method. The manufactured touch panel was attached to a liquid crystal display element manufactured by the method described in paragraphs 0097 to 0119 of Japanese Patent Application Laid-Open No. 2009-47936, thereby manufacturing a liquid crystal display device having a touch panel.

[1216] It was confirmed that the obtained liquid crystal display device having a touch panel had excellent display characteristics and operated normally.

[1217] [Example 1002 (Fabrication and Evaluation of Device)]

[1218] Except that the above transfer film was changed to any one of the transfer films other than Example 1-1 of the above Example 1 series and the transfer films of the Examples of the above Example 2 series, Example 4 series, Example 5 series, and Example 6 series, a liquid crystal display device having a touch panel was prepared by the same method as in Example 1001.

[1219] It was confirmed that the obtained liquid crystal display device having a touch panel had excellent display characteristics and operated normally.

[1220] [Example 1003 (Fabrication and Evaluation of Device)]

[1221] [Fabrication of Transparent Laminate]

[1222] A substrate was prepared in which an ITO transparent electrode pattern and copper routing wiring were formed on a cycloolefin transparent film.

[1223] Using the transfer film of the embodiment of the embodiment 3 series from which the protective film was peeled off, the ITO transparent electrode pattern and the copper bypass wiring were laminated to the position covering the transfer film. The lamination was performed using a vacuum laminator manufactured by MCK under the conditions of a cycloolefin transparent film temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min.

[1224] Then, the temporary support of the obtained substrate with a photosensitive layer was adhered to an exposure mask (quartz exposure mask having a pattern for forming an outer coating layer), and pattern exposure was performed through the temporary support using a proximity exposure machine (manufactured by Hitachi High-Tech Corporation.) with an ultra-high pressure mercury lamp and a filter that cuts wavelengths below 350nm. As exposure conditions, the cumulative exposure measured by an illuminometer at 365nm was 80mJ / cm 2 .

[1225] After the exposure, the temporary support was peeled off, and then the photosensitive layer of the laminate from which the temporary support was peeled off was developed for 40 seconds using a 1 mass % sodium carbonate aqueous solution (liquid temperature: 32° C.) as a developer.

[1226] Then, ultrapure water was sprayed from an ultrahigh pressure cleaning nozzle onto the transparent film substrate after the development process to remove the residues, and then air was blown in to remove the moisture on the transparent film substrate.

[1227] Next, the formed pattern was subjected to a second exposure using a high pressure mercury lamp. In the second exposure using the high pressure mercury lamp, the cumulative exposure amount measured by a 365 nm illuminometer was 1000 mJ / cm 2 .

[1228] Through the above-mentioned sequence, a transparent laminated body in which an ITO transparent electrode pattern, a copper routing wiring, and a cured film were sequentially laminated on a transparent film substrate was formed.

[1229] A touch panel was manufactured by a known method using the produced transparent laminate, and the produced touch panel was bonded to a liquid crystal display element produced by the method described in paragraphs 0097 to 0119 of Japanese Patent Application Laid-Open No. 2009-47936 to produce a liquid crystal display device including the touch panel.

[1230] It was confirmed that the obtained liquid crystal display devices equipped with a touch panel all had excellent display characteristics and operated normally.

[1231] 〔Example 1004 (Fabrication and Evaluation of Device)〕

[1232] A liquid crystal display device with a touch panel was fabricated by the same method as in Example 1003, except that the transfer film described above was replaced with the transfer film of the Example of the 7-series of the above Examples.

[1233] It was confirmed that the obtained liquid crystal display device with a touch panel had excellent display characteristics and operated normally.

[1234] Symbol Explanation

[1235] 12 - Temporary support, 14 - Photosensitive layer, 16 - Covering film, 100 - Transfer film.

Claims

1. A photosensitive material that satisfies the following requirement V01 and in which the following compound β in the following requirement V01 is one or more selected from quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives, V01: Comprising a polymer A having a carboxyl group and a compound β having a structure b0 that reduces the amount of the carboxyl group by decarboxylating the carboxyl group possessed by the polymer A upon exposure.

2. The photosensitive material according to claim 1, wherein the compound β is an aromatic compound having a substituent.

3. The photosensitive material according to claim 1 or 2, wherein The molar extinction coefficient ε of the compound β at 365 nm is 1×10 3 (cm·mol / L) -1 as follows.

4. The photosensitive material according to claim 1 or 2, wherein the ratio of the molar extinction coefficient ε of the compound β at 365 nm to the molar extinction coefficient ε' of the compound β at 313 nm is 3 or less.

5. The photosensitive material according to claim 1 or 2, wherein the pKa of the compound β in the ground state is 2.0 or more.

6. The photosensitive material according to claim 1 or 2, wherein the pKa of the compound β in the ground state is 9.0 or less.

7. The photosensitive material according to claim 1 or 2, wherein the polymer A has a repeating unit based on (meth)acrylic acid.

8. The photosensitive material according to claim 1 or 2, wherein the polymer A has a repeating unit having a polymerizable group.

9. The photosensitive material according to claim 1 or 2, in the photosensitive material, the total number of the structures b possessed by the compound β is 5 mol% or more relative to the total number of carboxyl groups possessed by the polymer A.

10. The photosensitive material according to claim 9, in the photosensitive material, the total number of the structures b possessed by the compound β is 10 mol% or more and 100 mol% or less relative to the total number of carboxyl groups possessed by the polymer A.

11. The photosensitive material according to claim 1, in the photosensitive material, the content of the compound β is 4 mass% to 35 mass% relative to the total solid content of the photosensitive material.

12. The photosensitive material according to claim 1 or 2, which further comprises a polymerizable compound.

13. The photosensitive material according to claim 1, which further comprises a photoinitiator.

14. The photosensitive material according to claim 13, wherein the photoinitiator is one or more selected from oxime ester compounds and aminobenzophenone compounds.

15. A method for forming a pattern, which sequentially includes: a step of forming a photosensitive layer on a substrate using the photosensitive material according to claim 13 or 14; a step of exposing the photosensitive layer into a pattern shape; a step of developing the exposed photosensitive layer with an alkali developer to form a patterned photosensitive layer; and a step of exposing the patterned photosensitive layer.

16. A method for manufacturing a circuit wiring, which sequentially includes: a step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material according to claim 13 or 14; a step of exposing the photosensitive layer into a pattern shape; A step of developing the exposed photosensitive layer with an alkali developer to form a patterned photosensitive layer; A step of exposing the patterned photosensitive layer to form an etching resist film; and A step of etching the conductive layer in a region where the etching resist film is not disposed.

17. A method of manufacturing a touch panel, which sequentially includes: A step of forming a photosensitive layer on a substrate having a conductive layer using the photosensitive material according to claim 13 or 14; A step of exposing the photosensitive layer in a pattern; A step of developing the exposed photosensitive layer with an alkali developer to form a patterned photosensitive layer; And A step of exposing the patterned photosensitive layer to form a protective film or an insulating film of the conductive layer.

18. A transfer film, which has a temporary support and a photosensitive layer formed using the photosensitive material according to any one of claims 1 to 14.

19. The transfer film according to claim 18, wherein The transmittance of the photosensitive layer at 365 nm is 65% or more.

20. The transfer film according to claim 18 or 19, wherein The ratio of the transmittance of the photosensitive layer at 365 nm to the transmittance of the photosensitive layer at 313 nm is 1.5 or more.

21. The transfer film according to claim 18 or 19, wherein The content of carboxyl groups in the photosensitive layer is reduced at a reduction rate of 5 mol% or more due to irradiation with actinic rays or radiation.

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