Protective film and laminate

Abstract

To provide a protective film excellent in adhesion to an electrode and also excellent in wet heat durability, and a laminate.SOLUTION: A protective film for electrodes, comprising a polymer A having a repeating unit A having an acid group, wherein the protective film has an acid number of 120mgKOH / g or less, the protective film has an absorption maximum in a range of wavelengths of 300 to 400nm, and when the protective film is heated at 140 °C for 30 minutes, a change rate of K (absorption coefficient) / S (scattering coefficient) at the absorption maximum is 10% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a protective film and a laminate. [Background technology]

[0002] In display devices (e.g., organic electroluminescence display devices and liquid crystal display devices) equipped with touch panels such as capacitance-type input devices, electrode patterns such as peripheral wiring portions and wiring of extraction wiring portions corresponding to the sensors of the visible area are provided inside the touch panel.

[0003] In order to protect the electrode pattern, a protective film is often used. As a method for forming a protective film on an electrode pattern, for example, a method for forming a photosensitive layer using a photosensitive material, and a method for using a transfer film having a temporary support and a photosensitive layer formed using a photosensitive material are widely used because the number of steps for obtaining a pattern shape is small. As a method for forming a pattern using a transfer film, a method in which a photosensitive layer transferred from the transfer film to an arbitrary substrate is exposed and developed through a mask having a predetermined pattern shape can be mentioned.

[0004] As a protective film, for example, Patent Document 1 discloses a protective film formed using "a photosensitive resin composition on a substrate, the photosensitive resin composition containing a binder polymer having a carboxyl group with an acid value of 75 mgKOH / g or more, a photopolymerizable compound, and a photopolymerization initiator" and "a photosensitive element including a support film and a photosensitive layer made of the photosensitive resin composition provided on the support film." [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2013 / 084886 Summary of the Invention [Problem to be solved by the invention]

[0006] A protective film for an electrode is required to have both excellent adhesion to the electrode and excellent humidity and heat durability. Excellent humidity and heat durability means that the electrode is less likely to discolor when the protective film is in contact with the electrode and stored under constant temperature and humidity conditions for a certain period of time.

[0007] The present inventors have found that when a protective film is formed on an electrode using a photosensitive material such as that described in Patent Document 1, it is difficult to achieve both adhesion to the electrode and durability against humidity and heat.

[0008] Therefore, an object of the present invention is to provide a protective film that has excellent adhesion to an electrode and excellent durability against humidity and heat, and also to provide a laminate. [Means for solving the problem]

[0009] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0010] (1) A protective film for an electrode, the protective film comprises a polymer A having a repeating unit A having an acid group, The acid value of the protective film is 120 mg KOH / g or less, The protective film has a maximum absorption wavelength in the wavelength range of 300 to 400 nm, A protective film in which the rate of change in K (absorption coefficient) / S (scattering coefficient) at the maximum absorption wavelength is 10% or less when the protective film is heated at 140°C for 30 minutes. (2) The protective film according to (1), wherein the acid value of the protective film is 100 mgKOH / g or less. (3) The protective film according to (1) or (2), wherein the acid value of the protective film is 80 mgKOH / g or less. (4) The protective film according to any one of (1) to (3), in which, after heating the protective film at 140° C. for 30 minutes, K / S at the maximum absorption wavelength is 4.0 or less. (5) The protective film according to any one of (1) to (4), in which after heating the protective film at 140° C. for 30 minutes, K / S at the maximum absorption wavelength is 0.01 or more. (6) Polymer A has a group formed by removing one hydrogen atom from a nitrogen-containing aromatic compound, The protective film according to any one of (1) to (5), wherein the nitrogen-containing aromatic compound has a maximum absorption wavelength in the wavelength range of 300 to 400 nm. (7) The protective film according to any one of (1) to (6), wherein the polymer A has a group represented by the formula (Zb2) described below. (8) The protective film according to any one of (1) to (7), wherein the repeating unit A has a repeating unit represented by the formula (a1) described below or a repeating unit represented by the formula (a2) described below. (9) The protective film according to any one of (1) to (8), wherein the acid value of the protective film is 5 mgKOH / g or more. (10) A laminate comprising, in this order, a substrate, an electrode, and the protective film according to any one of (1) to (9). [Effects of the Invention]

[0011] According to the present invention, a protective film having excellent adhesion to an electrode and excellent durability against humidity and heat can be provided, and a laminate can also be provided. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 2 is a schematic diagram illustrating an example of a layer structure of a transfer film according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below. In this specification, the following notations have the following meanings. A numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In numerical ranges described in stages, the upper or lower limit described in a certain numerical range may be replaced by the upper or lower limit of another numerical range described in stages, or may be replaced by a value shown in an example.

[0014] The term "process" includes an independent process and a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0015] Unless otherwise specified, the temperature condition may be 25° C. For example, unless otherwise specified, the temperature when performing each of the above steps may be 25° C.

[0016] "Transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. For example, a "transparent resin layer" means a resin layer having an average transmittance of visible light having a wavelength of 400 to 700 nm of 80% or more. The average transmittance of visible light can be measured using a spectrophotometer, for example, the spectrophotometer U-3310 (manufactured by Hitachi, Ltd.).

[0017] "Actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, such as g-rays, h-rays, and i-rays, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB), etc. Also, "light" refers to actinic rays or radiation.

[0018] Unless otherwise specified, "exposure" includes exposure using mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, EUV light, etc., as well as drawing using particle beams such as electron beams and ion beams.

[0019] When the molecular weight has a molecular weight distribution, the molecular weight is the weight average molecular weight unless otherwise specified. The weight average molecular weight of a resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0020] The term "(meth)acrylic acid" encompasses both acrylic acid and methacrylic acid, and the term "(meth)acryloyl group" encompasses both acryloyl and methacryloyl groups.

[0021] "Alkali-soluble" means that the dissolution rate determined by the following method is 0.01 μm / second or more. A propylene glycol monomethyl ether acetate solution containing a 25% by mass concentration of the target substance (e.g., resin) is applied to a glass substrate, and then heated in an oven at 100°C for 3 minutes to form a coating film (2.0 μm thick) of the target substance.The coating film is then immersed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 30°C) to determine the dissolution rate (μm / sec) of the coating film. If the target substance does not dissolve in propylene glycol monomethyl ether acetate, the target substance is dissolved in an organic solvent other than propylene glycol monomethyl ether acetate that has a boiling point of less than 200° C. (for example, tetrahydrofuran, toluene, ethanol, etc.).

[0022] "Water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22° C. and a pH of 7.0 is 0.1 g or more. For example, "water-soluble resin" means a resin that satisfies the above-mentioned solubility conditions.

[0023] The "solid content" of a photosensitive material refers to the components that form the photosensitive layer formed using the photosensitive material, and when the photosensitive material contains a solvent (e.g., organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form the photosensitive layer are also considered to be solid content.

[0024] Unless otherwise specified, the thickness of each layer is the average thickness measured using a scanning electron microscope (SEM) if the thickness is 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) if the thickness is less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0025] Unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0026] Unless otherwise specified, the boiling point refers to the boiling point at 1 atmosphere (standard boiling point).

[0027] [Protective film] The protective film of the present invention is a protective film for an electrode, the protective film comprises a polymer A having a repeating unit A having an acid group, The acid value of the protective film is 120 mg KOH / g or less, The protective film has a maximum absorption wavelength in the wavelength range of 300 to 400 nm, When the protective film is heated at 140°C for 30 minutes, the rate of change in K (absorption coefficient) / S (scattering coefficient) at the maximum absorption wavelength is 10% or less.

[0028] In the case of the protective film of the present invention, the mechanism by which the desired effects of the present invention are obtained is not clear, but the present inventors speculate as follows. Characteristics of the protective film of the present invention include, for example, that it contains polymer A, that the acid value of the protective film is a predetermined value or less, that the protective film has a specific maximum absorption wavelength described below, and that the rate of change of K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength is 10% or less. By including polymer A having a repeating unit A with an acid group, the protective film can interact with the electrode and the acid group in polymer A, thereby improving adhesion to the electrode. Furthermore, by setting the acid value of the protective film to a predetermined value or less, deterioration of moist heat durability can be suppressed while maintaining adhesion. On the other hand, when the protective film has a specific maximum absorption wavelength, this suggests the presence of a specific structure in the protective film (e.g., a group formed by removing one hydrogen atom from compound B described below, and a repeating unit derived from compound B described below). This structure can interact with the electrode and improve the packing of polymer A molecules in the protective film, thereby improving moist heat durability. Furthermore, because the rate of change in K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength is low, it is presumed that the fixation of the specific structure in polymer A further facilitates improvement of moist heat durability. Hereinafter, superiority in at least one of the effects of adhesion to the electrode and durability against humidity and heat will also be referred to as "superiority in the effect of the present invention." The various components that the protective film may contain will be described in detail below.

[0029] [Polymer A] The protective film contains polymer A. Polymer A has repeating units A having an acid group.

[0030] Some or all of the acid groups in polymer A may be anionized or not in the protective film. In this specification, the term "acid group" is used to refer to both anionized and non-anionized acid groups. Specifically, some or all of the carboxy groups that the polymer A may have may or may not be anionized in the protective film. In this specification, the term "carboxy group" refers to an anionized carboxy group (-COO - This concept includes both anionized carboxyl groups (-COOH) and non-anionized carboxyl groups (-COOH).

[0031] <Repeating unit A> The repeating unit A is a repeating unit having an acid group. The content of repeating unit A is not particularly limited and is adjusted so that the acid value of the protective film described below falls within a predetermined range. The content of repeating unit A is preferably 15% by mass or less, more preferably 12% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less, relative to the total mass of the protective film. The lower limit is often greater than 0% by mass, and is preferably 1% by mass or more, relative to the total mass of the protective film.

[0032] The acid group in the repeating unit A is preferably a proton dissociating group having a pKa of not more than 12. Specific examples include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxy group, and a sulfonylimide group, with a carboxy group being preferred.

[0033] (Repeating unit having a carboxy group) The repeating unit A is preferably a repeating unit having a carboxy group. The repeating unit having a carboxy group preferably has at least one selected from the group consisting of repeating units represented by formula (a1) and repeating units represented by formula (a2).

[0034] [ka]

[0035] In formula (a1), R a represents a hydrogen atom or a substituent, and X represents a single bond or a divalent linking group having one or more carbon atoms.

[0036] In formula (a2), Y represents a cyclic group having two or more carbon atoms, and Z represents a single bond or a divalent linking group.

[0037] R a represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxycarbonyl group, and a hydroxyalkyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. The alkyl groups constituting the alkoxycarbonyl group and the hydroxyalkyl group are preferably the alkyl groups mentioned above.

[0038] X represents a single bond or a divalent linking group having one or more carbon atoms. Examples of the divalent linking group having one or more carbon atoms include -CO-, -COO-, and -NR NA -(R NA represents an alkyl group having 1 to 5 carbon atoms.), a divalent linking group X1 selected from divalent hydrocarbon groups and groups combining these, and a divalent linking group X2 formed from the above divalent linking group X1 and a divalent linking group selected from -O-, -S-, -NH- and groups combining these. The divalent linking group having one or more carbon atoms is preferably a divalent linking group Y1 selected from an alkylene group, an arylene group, -COO-, an amide linking group, a carbonate linking group, a urethane linking group, a urea linking group, or a combination thereof, or a divalent linking group Y2 formed from the above divalent linking group Y1 and a divalent linking group selected from -O-, -S-, -NH-, or a combination thereof, and more preferably an alkylene group, a cycloalkylene group, an arylene group, -COO-, or a divalent linking group formed from a combination thereof. The divalent linking group having one or more carbon atoms may further have a substituent, for example, a hydroxy group, an alkyl group, or a halogen atom.

[0039] The divalent linking group having 1 or more carbon atoms has 1 or more carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms.

[0040] The divalent hydrocarbon group as the divalent linking group having one or more carbon atoms may be linear, branched, or cyclic. The divalent hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms. Examples of the divalent hydrocarbon group include alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups such as phenylene groups, with alkylene groups, cycloalkylene groups, and arylene groups being preferred.

[0041] As the divalent linking group having one or more carbon atoms, an alkylene group A is preferred. The alkylene group A is a linear alkylene group having 1 to 7 carbon atoms which may have a substituent, and "-CH2-CH2-" in the alkylene group may be replaced with "-CO-O-" or "-CH=CH-". When the alkylene group A has multiple substituents, the two or more substituents may be bonded to each other to form a ring. Examples of the substituent include an alkyl group, an alkenylene group, an alkoxy group, an aryl group, a halogen atom, and a hydroxy group. Specifically, when the alkylene group A is "-CH-CH-CH-CH-CH-COOH", it may be "-CO-O-CH-CH-CH-COOH" or "-CH=CH-CH-CH-CH-COOH". In addition, as shown below, the substituent R in the alkylene group A may be 1 and substituent R 2 may be bonded to each other to form a ring.

[0042] [ka]

[0043] The alkylene group A is also preferably a group represented by formula (a3).

[0044] *-L 1 -L 3 -L 2 -COOH (a3)

[0045] In formula (A3), L 1 represents a single bond or -CH2-. 2 is -(CR a1 R a2 ) nR represents -, an optionally substituted phenylene group, an optionally substituted norbornane ring, or an optionally substituted cyclohexane ring. a1 and R a2 each independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 3. 3 represents a single bond, an optionally substituted phenylene group, *1-COO-*2, or *1-OCO-*2. 1 *2 indicates the bonding position with L 2 * indicates the bonding position. Multiple R a1 and R a2 If there is R a1 Comrades and R a2 They may be the same or different.

[0046] In formula (a2), Y represents a ring group having two or more carbon atoms. The ring may be either a monocyclic ring or a polycyclic ring. The cyclic group is preferably an alicyclic group. The alicyclic group preferably has 1 or more carbon atoms, more preferably 1 to 30 carbon atoms, further preferably 3 to 20 carbon atoms, and particularly preferably 3 to 15 carbon atoms.

[0047] Examples of rings constituting the alicyclic group include a cyclopentane ring, a cyclohexane ring, a dicyclopentane ring, an isobornane ring, an adamantane ring, a tricyclodecane ring, a tricyclodecene ring, a norbornane ring, an isoborone ring, and rings formed by combining these. The alicyclic group may further have a substituent, which is preferably an alkyl group or an alkenyl group.

[0048] The alicyclic group may contain a heteroatom. The heteroatom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The position at which the heteroatom is introduced may be any of a ring atom and a non-ring atom. Specifically, when the carbon atom in the methylene constituting the ring of the alicyclic ring is -O-, -CO-, -NR N -(R Nrepresents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) or a group combining these. In addition, the heteroatom may be introduced into a position other than a ring atom, for example, into a substituent of the alicyclic ring. Examples of the alicyclic ring having a hetero atom include an imide ring such as a succinimide ring.

[0049] Z represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent linking group having one or more carbon atoms represented by X in formula (a1), -O-, -S-, -NH-, and divalent linking groups formed by combining these, and a divalent linking group having one or more carbon atoms represented by X is preferred.

[0050] Examples of the repeating unit A include the following repeating units. In the formula, R 1 and R 2 each independently represents a hydrogen atom or a methyl group.

[0051] [ka]

[0052] Examples of monomers from which the repeating unit having a carboxy group is derived include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid, and (meth)acrylic acid is preferred in terms of excellent pattern-forming ability. That is, the repeating unit having a carboxy group is preferably a repeating unit derived from (meth)acrylic acid.

[0053] The content of repeating units having an acid group (preferably repeating units having a carboxy group) in polymer A is preferably 1 mol % or more, and more preferably 5 mol % or more, based on all repeating units of polymer A. The upper limit is often 100 mol % or less, preferably 65 mol % or less, and more preferably 45 mol % or less, based on all repeating units of polymer A. The content of repeating units having an acid group (preferably repeating units having a carboxy group) in polymer A is preferably 1% by mass or more, and more preferably 5% by mass or more, based on all repeating units of polymer A. The upper limit is often less than 100% by mass, and is preferably 70% by mass or less, and more preferably 50% by mass or less, based on all repeating units of polymer A.

[0054] <Repeating unit B derived from compound B> The polymer A preferably has a repeating unit B derived from the compound B in addition to the repeating units described above. Compound B is as described below.

[0055] Polymer A preferably has a structure derived from compound B, and is preferably a group formed by removing one or more hydrogen atoms from compound B, and more preferably a group formed by removing one hydrogen atom from compound B. The structure derived from compound B may be present in the main chain of polymer A or in a side chain of polymer A, and is preferably present in the side chain of polymer A. When the structure derived from compound B is present in a side chain, the structure derived from compound B is bonded to the main chain of polymer A via a single bond or a linking group. The compound B is preferably a nitrogen-containing aromatic compound (a compound having a nitrogen atom as a heteroatom in a heteroaromatic ring). The compound B from which the repeating unit B is derived preferably has a specific maximum absorption wavelength. In particular, polymer A preferably has a group represented by formula (Zb1) described below, and more preferably has a group represented by formula (Zb2) described below.

[0056] More specifically, the repeating unit B is preferably a repeating unit represented by formula (b1), and more preferably a repeating unit represented by formula (b2).

[0057] [ka]

[0058] In formula (b1), L b represents a single bond or a divalent linking group. b1 represents a group represented by formula (Zb1). b4 represents a hydrogen atom or an alkyl group. In formula (Zb1), nb represents 0 or 1. When nb represents 0, X b1 ~X b3 are each independently a nitrogen atom or CR b5 represents X b1 ~X b3 At least one of nb represents a nitrogen atom. When nb represents 1, X b1 and X b2 represents a carbon atom, and X b3 represents a nitrogen atom. b1 and R b2 each independently represents a substituent; b1 and b2 each independently represents an integer of 0 to 4; * represents a bonding position; CR b5 represents a hydrogen atom or a substituent.

[0059] L b represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -S-, -CO-, -COO-, and -CONR N -, alkylene group, cycloalkylene group, alkenylene group, arylene group, and divalent linking groups combining these groups. N represents a hydrogen atom or a substituent. L b is preferably a single bond.

[0060] Z b1 represents a group represented by formula (Zb1). nb represents 0 or 1. If nb represents 0, then X b1 ~X b3 are each independently a nitrogen atom or CR b5 represents X b1 ~X b3 At least one of the X represents a nitrogen atom. b1 ~X b3One of them represents a nitrogen atom, and the rest are CR b5 It is preferred that If nb represents 1, then X b1 and X b2 represents a carbon atom, and X b3 represents a nitrogen atom.

[0061] R b1 and R b2 each independently represents a substituent. The substituent is preferably an alkyl group, an aryl group, or a group combining these, and more preferably an alkyl group. The alkyl group may be linear, branched, or cyclic, and preferably has 1 to 5 carbon atoms. The aryl group may be either monocyclic or polycyclic, and preferably has 6 to 12 carbon atoms. R b1 If there are multiple b1 R may be the same or different. b2 If there are multiple b2 They may be the same or different.

[0062] R b4 represents a hydrogen atom or an alkyl group. The alkyl group may be linear, branched, or cyclic, and preferably has 1 to 5 carbon atoms.

[0063] R b5 represents a hydrogen atom or a substituent. R b5 Examples of the substituent represented by R b1 and R b2 Examples of the substituent include groups (for example, alkyl groups) represented by the following formula:

[0064] b1 and b2 each independently represent an integer of 0 to 4. b1 and b2 are preferably integers of 0 to 2, and more preferably 0 or 1.

[0065] [ka]

[0066] In formula (b2), L b represents a single bond or a divalent linking group. b2 represents a group represented by formula (Zb2). b4 represents a hydrogen atom or an alkyl group. In formula (Zb2), X b4 ~X b6 are each independently, CR b6 or a nitrogen atom. X b4 ~X b6 At least one of R represents a nitrogen atom. b3 represents an alkyl group. b6 represents a hydrogen atom or an alkyl group. b3 represents an integer of 0 to 4. * represents a bonding position.

[0067] In formula (b2), R b4 and L b is R in formula (b1). b4 and L b The same definition and preferred embodiments are also the same.

[0068] Z b2 represents a group represented by formula (Zb2). b4 ~X b6 are each independently, CR b6 or a nitrogen atom. X b4 ~X b6 At least one of represents a nitrogen atom. X b4 ~X b6 One of them represents a nitrogen atom, and the rest are CR b6 It is preferred that

[0069] R b3 represents an alkyl group. The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 5 carbon atoms. R b3 If there are multipleb3 They may be the same or different.

[0070] R b6 represents a hydrogen atom or an alkyl group. The alkyl group may be linear, branched, or cyclic, and preferably has 1 to 5 carbon atoms.

[0071] b3 represents an integer of 0 to 4. b3 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0072] Z in formula (b1) b1 , and Z in formula (b2) b2 is preferably a group represented by any one of formulae (Zba) to (Zbd).

[0073] [ka]

[0074] In formula (Zba) ~ formula (Zbd), R Zb represents a hydrogen atom or an alkyl group. * represents a bonding position. The alkyl group includes R in formula (Zb2). b3 The meaning and preferred embodiments are also the same as those of the alkyl group represented by the following formula: Multiple Rs Zb may be the same or different. In the formula (Zba), R Zb Preferably, at least one of R represents a hydrogen atom, Zb More preferably, at least four of R represent hydrogen atoms, Zb It is more preferred that all of represent a hydrogen atom. In the formula (Zbb), R Zb Preferably, at least one of R represents a hydrogen atom, Zb More preferably, at least four of R represent hydrogen atoms, Zb It is more preferred that all of represent a hydrogen atom. In the formula (Zbc), RZb Preferably, at least one of R represents a hydrogen atom, Zb More preferably, at least four of R represent hydrogen atoms, Zb It is more preferred that all of represent a hydrogen atom. In the formula (Zbd), R Zb Preferably, at least one of R represents a hydrogen atom, Zb More preferably, at least four of R represent hydrogen atoms, Zb It is more preferred that all of represent a hydrogen atom.

[0075] Examples of the repeating unit B include the following repeating units. In the formula, R b represents a substituent. b represents an integer of 0 to 8. R b If there are multiple b They may be the same or different.

[0076] [ka]

[0077] The content of the repeating unit B is preferably from 3 to 75 mol %, more preferably from 5 to 60 mol %, and even more preferably from 10 to 50 mol %, based on the total repeating units of the polymer A. The content of the repeating unit B is preferably from 1 to 75 mass %, more preferably from 3 to 60 mass %, and even more preferably from 5 to 30 mass %, based on the total repeating units of the polymer A.

[0078] Known synthesis methods can be used to synthesize polymer A having repeating unit B. Specific examples include a synthesis method in which a monomer from which repeating unit A is derived and a monomer from which repeating unit B is derived are polymerized, and a synthesis method in which a photosensitive layer is formed using a photosensitive material containing polymer P and compound B, which will be described later, and the photosensitive layer is exposed to light, thereby causing a reaction in the protective film system. The synthesis method using the photosensitive material will be described in detail in the method for producing a laminate, which will be described later.

[0079] <Repeating units having aromatic rings> In addition to the above repeating units, polymer A preferably contains a repeating unit having an aromatic ring. The aromatic ring is preferably an aromatic hydrocarbon ring. Examples of repeating units having an aromatic ring include repeating units derived from (meth)acrylates having an aromatic ring, and repeating units derived from styrene and polymerizable styrene derivatives. Examples of the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Styrene and polymerizable styrene derivatives include, for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer. The repeating unit having an aromatic ring is preferably a repeating unit represented by formula (C).

[0080] [ka]

[0081] In formula (C), R C1 represents a hydrogen atom, a halogen atom or an alkyl group. C represents a phenyl group or a naphthyl group.

[0082] R C1 represents a hydrogen atom, a halogen atom or an alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 carbon atom.

[0083] Ar C represents a phenyl group or a naphthyl group. The phenyl group and naphthyl group may further have a substituent, such as an alkyl group, an alkoxy group, an aryl group, a halogen atom, or a hydroxy group. Ar C As the alkyl group, a phenyl group is preferred.

[0084] Examples of repeating units having an aromatic ring include the following repeating units.

[0085] [ka]

[0086] The content of repeating units having an aromatic ring in polymer A is preferably from 5 to 80 mol %, more preferably from 15 to 75 mol %, and even more preferably from 30 to 70 mol %, based on all repeating units in polymer A. The content of repeating units having an aromatic ring in polymer A is preferably from 5 to 90 mass %, more preferably from 10 to 80 mass %, and even more preferably from 30 to 70 mass %, based on all repeating units in polymer A.

[0087] <Repeating units having an alicyclic structure> In addition to the above repeating units, polymer A preferably contains a repeating unit having an alicyclic structure. The alicyclic structure may be either a monocyclic or polycyclic structure, and examples of the alicyclic structure include a dicyclopentanyl ring structure, a dicyclopentenyl ring structure, an isobornyl ring structure, an adamantane ring structure, and a cyclohexyl ring structure. Examples of monomers from which repeating units having an alicyclic structure are derived include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0088] The content of repeating units having an alicyclic structure in polymer A is preferably from 3 to 70 mol %, more preferably from 5 to 60 mol %, and even more preferably from 10 to 55 mol %, based on all repeating units of polymer A. The content of repeating units having an alicyclic structure in polymer A is preferably from 3 to 90 mass %, more preferably from 5 to 70 mass %, and even more preferably from 20 to 60 mass %, based on all repeating units of polymer A.

[0089] <Other repeating units> The polymer A may have other repeating units in addition to the repeating units described above. Examples of other repeating units include repeating units derived from alkyl (meth)acrylates such as methyl (meth)acrylate, and repeating units derived from alkylene compounds such as ethylene. The alkyl group in the (meth)acrylic acid alkyl ester may be linear, branched, or cyclic. The alkyl group may further have a substituent. The substituent is preferably a hydroxy group. The number of carbon atoms in the alkyl group is preferably 1 to 50, more preferably 1 to 10. The alkylene group in the alkylene compound such as ethylene may be linear, branched, or cyclic. The alkylene group may further have a substituent. The substituent is preferably a hydroxy group. The number of carbon atoms in the alkylene group is preferably 2 to 10, more preferably 2 to 3.

[0090] The content of other repeating units in polymer A is preferably from 1 to 70 mol %, more preferably from 2 to 50 mol %, and even more preferably from 3 to 20 mol %, based on the total repeating units of polymer A. The content of other repeating units in polymer A is preferably from 1 to 70 mass %, more preferably from 1 to 50 mass %, and even more preferably from 1 to 35 mass %, based on the total repeating units of polymer A.

[0091] The weight average molecular weight of the polymer A is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more, and the upper limit is preferably 50,000 or less.

[0092] The polymer A may be used alone or in combination of two or more. The content of polymer A is preferably from 10 to 100% by mass, more preferably from 30 to 100% by mass, and more preferably from 50 to 100% by mass, relative to the total mass of the protective film.

[0093] [Other ingredients] The protective film may contain other components in addition to the polymer A. Examples of other components include various components contained in the photosensitive material described below (e.g., compound B, etc.).Specific examples of the reaction product include a cured product of polymerizable compounds described below.

[0094] [Properties of protective film] <Acid value> The acid value of the protective film is 120 mgKOH / g or less, and from the viewpoint of providing the protective film with better wet heat durability, it is preferably 100 mgKOH / g or less, more preferably 80 mgKOH / g or less, and even more preferably 50 mgKOH / g or less. There is no particular lower limit, but it is often more than 0 mgKOH / g and more often 5 mgKOH / g or more. The acid value of the protective film can be measured by the following method. First, a predetermined amount (approximately 20 mg) of sample was scraped from the protective film. The resulting sample was freeze-pulverized, and then NMP (N-methyl-2-pyrrolidone) (150 μL) was added. The sample was then stirred for 6 days in a lithium carbonate (Li2CO3) aqueous solution (1.2 g / 100 mL, prepared by dissolving lithium carbonate in ultrapure water and filtering). After stirring, the particles were sedimented by ultracentrifugation (140,000 rpm for 30 minutes). The resulting sediment was then purged with ultrapure water five times and dried to obtain the analytical sample. The amount of Li (lithium) per gram of the resulting analytical sample was analyzed using an ICP-OES (PerkinElmer Optima 7300DV). Because the above procedure replaces the hydrogen atoms in the acid groups with lithium, the amount of Li corresponds to the number of acid groups. The resulting value is divided by the number of Li atoms (6.941 g / mol) to calculate the amount of acid groups (mol / g) in the protective film, and the resulting value is further multiplied by the molecular weight of KOH to calculate the acid value (mgKOH / g) of the protective film. The acid value of this protective film is measured five times, the maximum and minimum values ​​of the five measurements are removed, and the remaining three measurements are arithmetically averaged. The resulting arithmetic mean is the acid value (mgKOH / g) of the protective film of the present invention. In other words, in the present invention, it is sufficient that the arithmetic mean acid value of the protective film is 120 mgKOH / g or less. The Li content is analyzed using the following procedure: Approximately 1.5 to 2 mg of the sample is weighed, and 5 mL of a 60% by mass HNO3 aqueous solution is added. The sample is then incinerated using MW Teflon (registered trademark) (UltraWAVE microwave sample decomposition device, max: 260°C). Ultrapure water is added to the incinerated sample to make a 50 mL volume, and the Li content is quantified using the absolute calibration curve method with ICP-OES.

[0095] <Maximum absorption wavelength> The protective film has a maximum absorption wavelength (specific maximum absorption wavelength) in the wavelength range of 300 to 400 nm. The protective film only needs to have a specific maximum absorption wavelength, and it may also have a maximum absorption wavelength in other wavelength ranges. The specific maximum absorption wavelength is preferably in the range of 300 to 380 nm, more preferably in the range of 310 to 360 nm, and even more preferably in the range of 310 to 330 nm. The protective film may have a plurality of specific maximum absorption wavelengths in the range of 300 to 400 nm. When the protective film has a plurality of maximum absorption wavelengths, it is preferable that any of the specific maximum absorption wavelengths is within the above range. The fact that the protective film has a specific maximum absorption wavelength suggests that the protective film has a predetermined structure. As the above-mentioned predetermined structure, a structure derived from the repeating unit B or the compound B is preferable, and a structure derived from the repeating unit B or a nitrogen-containing aromatic compound is more preferable. The specific maximum absorption wavelength is determined according to the procedure of the measurement method of the change rate of K (absorption coefficient) / S (scattering coefficient) described later.

[0096] <Change rate of K (absorption coefficient) / S (scattering coefficient)> When the protective film is heated at 140 °C for 30 minutes, the change rate of K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength is 10% or less, preferably 8.0% or less, more preferably 6.5% or less, and even more preferably 5.0% or less. The lower limit is often 1.5% or more. The above change rate of K (absorption coefficient) / S (scattering coefficient) is a value obtained by comparing the K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength before and after the heat treatment of the protective film at 140 °C for 30 minutes [100×(|K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength before the heat treatment - K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength after the heat treatment|) / K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength before the heat treatment)]. When the protective film has a plurality of specific maximum absorption wavelengths in the range of 300 to 400 nm, it is preferable that any of the specific maximum absorption wavelengths is within the range of the above change rate of K (absorption coefficient) / S (scattering coefficient). Examples of the above method for measuring K (absorption coefficient) / S (scattering coefficient) include the following methods. First, shave off a total of 30 mg of the protective film, mix it with barium sulfate (270 mg), and use an agate mortar to grind it so that the particle size of the solid powder becomes 2 μm or less to obtain a measurement sample. Set the measurement sample (about 100 mg) on the sample stage and flatten it so that there are no gaps in the measurement range. Next, using a measuring instrument: V-7200 (manufactured by JASCO Corporation), measure the diffuse reflectance of barium sulfate (standard sample) and the measurement sample at wavelengths from 300 to 700 nm to measure the relative reflectance R of the measurement sample. Next, convert the relative reflectance R (%) obtained by measurement into K (absorption coefficient) / S (scattering coefficient) based on the following formula. K / S = (1 - R) 2 / 2R Note that the above formula is called the Kubelka-Munk function. By the above conversion, a graph with the horizontal axis: wavelength and the vertical axis: K (absorption coefficient) / S (scattering coefficient) is obtained, and the peak top in the wavelength range of 300 to 400 nm in the graph is defined as the specific maximum absorption wavelength. Determine K (absorption coefficient) / S (scattering coefficient) at this specific maximum absorption wavelength. The obtained K / S corresponds to K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength before the heat treatment. Next, after heating the protective film at 140 °C for 30 minutes, follow the same procedure as above to determine K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength in the wavelength range of 300 to 400 nm. The obtained K / S corresponds to K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength after the heat treatment.

[0097] <K (absorption coefficient) / S (scattering coefficient)> The K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength after heating the protective film at 140 °C for 30 minutes is preferably 4.0 or less. The lower limit is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.1 or more. When the protective film has a plurality of specific maximum absorption wavelengths in the wavelength range of 300 to 400 nm, it is preferable that K (absorption coefficient) / S (scattering coefficient) at any of the specific maximum absorption wavelengths is within the above range.

[0098] <Other physical properties> As will be described later, the protective film has a reduced content of acid groups, and therefore has low polarity, moisture permeability, and dielectric constant. The acid group content in the protective film is preferably reduced by 5 mol % or more, more preferably 10 mol % or more, even more preferably 20 mol % or more, even more preferably 31 mol % or more, particularly preferably 40 mol % or more, particularly more preferably 51 mol % or more, and most preferably 71 mol % or more, relative to the acid group content in the photosensitive layer (e.g., the photosensitive layer formed in step X1 or step Y1 described later). The upper limit is, for example, less than 100 mol %. The reduction rate of the acid group content can be calculated, for example, by measuring the amount of acid groups in the photosensitive layer before exposure and in the protective film after exposure. The amount of acid groups in the photosensitive layer before exposure can be measured by analytical quantification, for example, by potentiometric titration. The amount of acid groups in the protective film after exposure can be calculated by substituting the hydrogen atoms of the acid groups with metal ions such as lithium and then analytically quantifying the amount of these metal ions using an ICP-OES (Inductivity Coupled Plasma Optical Emission Spectrometer). The reduction rate of the acid group content can be calculated by measuring the IR (Infrared) spectrum of the photosensitive layer before and after exposure and calculating the reduction rate of the peak derived from the acid group.

[0099] The moisture permeability of the protective film is preferably reduced by 5% or more, more preferably by 10% or more, and even more preferably by 20% or more, relative to the moisture permeability of the photosensitive layer (for example, the photosensitive layer formed in step X1 or step Y1 described later). The upper limit is, for example, less than 100%.

[0100] The dielectric constant of the protective film is preferably reduced by 5% or more, more preferably by 10% or more, and even more preferably by 15% or more, relative to the dielectric constant of the photosensitive layer (such as the photosensitive layer formed in step X1 or step Y1 described later). The upper limit is, for example, less than 100%.

[0101] The protective film is preferably achromatic. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) is CIE1976 (L * a * b * ) color space, the above L * is preferably 10 to 90, and * is preferably -1.0 to 1.0, and the above b * is preferably -1.0 to 1.0.

[0102] The thickness of the protective film is preferably 0.5 to 20 μm, more preferably 0.8 to 15 μm, and even more preferably 1.0 to 10 μm.

[0103] [Uses of protective film] The protective film can be used as a variety of protective films. It can also be used as various insulating films. Specifically, it can be used as a protective film for protecting a conductive pattern, as an interlayer insulating film between conductive patterns, and as an etching resist film in the manufacture of circuit wiring. The above pattern is preferably used as a protective film (permanent film) for protecting a conductive pattern or as an interlayer insulating film between conductive patterns because of its excellent low moisture permeability. The protective film can be used, for example, as a protective film (permanent film) for protecting conductive patterns such as an electrode pattern corresponding to a sensor of a visual recognition section provided inside a touch panel, wiring of a peripheral wiring section and an extraction wiring section, or as an interlayer insulating film between conductive patterns. It can also be used as a protective film (permanent film) for protecting conductive patterns such as wiring of a display device, a printed wiring board, or a semiconductor package, or as an interlayer insulating film between conductive patterns.

[0104] [Method of manufacturing the protective film] The protective film can be produced by, for example, a known production method. For example, a composition containing the above-mentioned polymer A may be applied to form a protective layer on a substrate. The protective layer may also be formed by a method involving exposure treatment. Specifically, examples include a method in which a photosensitive layer is formed on a substrate using a photosensitive material described below, and the photosensitive layer is exposed and developed, and a method in which a transfer film described below having a temporary support and a photosensitive layer formed using a photosensitive material is used, and the photosensitive layer transferred onto an arbitrary substrate is exposed and developed through a mask having a predetermined pattern shape. The photosensitive material and the transfer film will be described later.

[0105] The photosensitive material and photosensitive layer preferably comprise a polymer P having a repeating unit A and a compound B, or a polymer P having a repeating unit A and a repeating unit B. In the above structure, the photosensitive layer has a function of reducing the content of acid groups in the polymer P by exposure to light. The estimated mechanism will be described in detail below using the compound B as an example. In the following, the compound B may be read as the repeating unit B. When exposed to light, compound B's electron acceptance increases, and electrons are transferred from the acid group of polymer P. When the acid group transfers electrons to compound B, the acid group becomes unstable and is released as carbon dioxide. When the acid group is released as carbon dioxide, the polarity of that area decreases. In other words, due to the above-mentioned mechanism, the photosensitive layer experiences a change in polarity due to the release of the acid group of polymer P in the exposed area, and its solubility in the developer changes (the solubility of the exposed area in an alkaline developer decreases, and the solubility in an organic solvent-based developer increases). On the other hand, the solubility of the unexposed area in the developer remains largely unchanged. As a result, the photosensitive layer can form a pattern. When the developer is an alkaline developer, the content of acid groups in the polymer P is reduced, making it possible to form a pattern with an excellent dielectric constant. When the developer is an organic solvent-based developer, the content of acid groups in the polymer P is further reduced by exposing the developed pattern to light, making it possible to form a pattern with an excellent dielectric constant. In the above procedure, the content of acid groups in the polymer P is reduced, and the above-mentioned polymer A is formed, resulting in the formation of a protective layer exhibiting a predetermined acid value.

[0106] The photosensitive material preferably contains a polymerizable compound. As described above, when the acid group transfers electrons to compound B, the acid group becomes unstable and is released as carbon dioxide. At this time, radicals are generated at the sites where the acid group of polymer P has been released as carbon dioxide, and the radicals cause a radical polymerization reaction of the polymerizable compound. As a result, the photosensitive layer has superior pattern-forming ability, particularly in alkaline developers, and the formed patterns also have excellent film strength.

[0107] The photosensitive material preferably contains a polymerizable compound and a photopolymerization initiator. When the photosensitive material contains a photopolymerization initiator, the elimination reaction of the acid groups of the polymer P and the polymerization reaction can occur at different times. For example, the photosensitive layer may first be subjected to a first exposure using a wavelength or exposure amount that causes almost no elimination reaction of the acid groups, and then the polymerization reaction of the polymerizable compound based on the photopolymerization initiator may proceed and the layer may be hardened. The hardened photosensitive layer may then be subjected to a second exposure to eliminate the acid groups.

[0108] An example of an embodiment of the photosensitive material will be described below. Photosensitive material of embodiment X-1-a1 The photosensitive layer of the photosensitive material and transfer film is a photosensitive material that contains a polymer P having a repeating unit A and a compound B, or a polymer P having a repeating unit A and a repeating unit B, and is substantially free of a polymerizable compound and a photopolymerization initiator. Photosensitive material of embodiment X-1-a2 The photosensitive layer of the photosensitive material and transfer film is a photosensitive material that contains a polymer P having a repeating unit A and a compound B, or a polymer P having a repeating unit A and a repeating unit B, and is substantially free of a photopolymerization initiator. Photosensitive material of embodiment X-1-a3 The photosensitive layer of the photosensitive material and transfer film is a photosensitive material that contains a polymer P having a repeating unit A and a compound B, or a polymer P having a repeating unit A and a repeating unit B, a polymerizable compound, and a photopolymerization initiator.

[0109] In the photosensitive material of embodiment X-1-a1, "the photosensitive material is substantially free of polymerizable compounds" means that the content of the polymerizable compounds is less than 3 mass %, preferably 0 to 1 mass %, and more preferably 0 to 0.1 mass %, based on the total solid content of the photosensitive material. In the photosensitive materials of Embodiment X-1-a1 and Embodiment X-1-a2, "the photosensitive material is substantially free of a photopolymerization initiator" means that the content of the photopolymerization initiator is less than 0.1 mass %, preferably 0 to 0.05 mass %, and more preferably 0 to 0.01 mass %, based on the total solid content of the photosensitive material.

[0110] [Photosensitive material] [Polymer P] The photosensitive material preferably comprises a polymer P. The polymer P has the repeating unit A having the above-mentioned acid group. The repeating unit A having an acid group has been described above. The content of repeating units having an acid group (preferably repeating units having a carboxy group) in polymer P is preferably 1 mol % or more, and more preferably 5 mol % or more, based on all repeating units of polymer P. The upper limit is often 100 mol % or less, and is preferably 65 mol % or less, and more preferably 45 mol % or less, based on all repeating units of polymer P. The content of repeating units having an acid group (preferably repeating units having a carboxy group) in polymer P is preferably 1% by mass or more, and more preferably 5% by mass or more, based on all repeating units of polymer P. The upper limit is often less than 100% by mass, and is preferably 70% by mass or less, and more preferably 50% by mass or less, based on all repeating units of polymer P.

[0111] The polymer P may contain the repeating unit B described above. The content of the repeating unit B is preferably from 3 to 75 mol %, more preferably from 5 to 60 mol %, and even more preferably from 10 to 50 mol %, based on the total repeating units of the polymer P. The content of the repeating unit B is preferably from 1 to 75 mass %, more preferably from 3 to 60 mass %, and even more preferably from 5 to 30 mass %, based on the total repeating units of the polymer P.

[0112] The polymer P may contain the repeating unit having the aromatic ring described above. The content of repeating units having an aromatic ring in polymer P is preferably from 5 to 80 mol %, more preferably from 15 to 75 mol %, and even more preferably from 30 to 70 mol %, based on all repeating units in polymer P. The content of repeating units having an aromatic ring in polymer P is preferably from 5 to 90 mass %, more preferably from 10 to 80 mass %, and even more preferably from 30 to 70 mass %, based on all repeating units in polymer P.

[0113] The polymer P may contain a repeating unit having the above-mentioned alicyclic structure. The content of repeating units having an alicyclic structure in polymer P is preferably from 3 to 70 mol %, more preferably from 5 to 60 mol %, and even more preferably from 10 to 55 mol %, based on all repeating units in polymer P. The content of repeating units having an alicyclic structure in polymer P is preferably from 3 to 90 mass %, more preferably from 5 to 70 mass %, and even more preferably from 20 to 60 mass %, based on all repeating units in polymer P.

[0114] The weight-average molecular weight of the polymer P is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more, from the viewpoint of excellent photosensitive layer formability. The upper limit is preferably 50,000 or less, from the viewpoint of excellent adhesion (lamination adhesion) when attached to any substrate (during transfer).

[0115] The polymer P may contain other repeating units as described above. The content of other repeating units in polymer P is preferably from 1 to 70 mol %, more preferably from 2 to 50 mol %, and even more preferably from 3 to 20 mol %, based on the total repeating units of polymer P. The content of other repeating units in polymer P is preferably from 1 to 70 mass %, more preferably from 1 to 50 mass %, and even more preferably from 1 to 35 mass %, based on the total repeating units of polymer P.

[0116] <Repeating Unit Having a Polymerizable Group> The polymer P may contain a repeating unit having a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated groups (e.g., (meth)acryloyl group, vinyl group, styryl group, etc.) and cyclic ether groups (e.g., epoxy group, oxetanyl group, etc.), with ethylenically unsaturated groups being preferred and (meth)acryloyl groups being more preferred. An example of a repeating unit having a polymerizable group is a repeating unit represented by formula (B).

[0117] [ka]

[0118] In formula (B), X B1 and X B2 are each independently -O- or -NR N - represents R N represents a hydrogen atom or an alkyl group. L represents an alkylene group or an arylene group. R B1 and R B2 each independently represents a hydrogen atom or an alkyl group.

[0119] X B1 and X B2 are each independently -O- or -NR N - represents R N represents a hydrogen atom or an alkyl group. The alkyl group may be either linear or branched, and preferably has 1 to 5 carbon atoms.

[0120] L represents an alkylene group or an arylene group. The alkylene group may be either linear or branched, and preferably has 1 to 5 carbon atoms. The arylene group may be either a monocyclic or polycyclic group, and preferably has 6 to 15 carbon atoms. The alkylene group and the arylene group may further have a substituent, and the substituent is preferably a hydroxy group.

[0121] R B1 and R B2 each independently represents a hydrogen atom or an alkyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 carbon atom.

[0122] The content of repeating units having a polymerizable group in the polymer P is preferably from 3 to 60 mol %, more preferably from 5 to 40 mol %, and even more preferably from 10 to 30 mol %, based on all repeating units in the polymer P. The content of repeating units having a polymerizable group in the polymer P is preferably from 1 to 70 mass %, more preferably from 5 to 50 mass %, and even more preferably from 12 to 45 mass %, based on all repeating units in the polymer P.

[0123] [Compound B] The photosensitive material preferably contains compound B. Compound B is a compound that has the function of reducing, upon exposure to light, the amount of acid groups in polymer P. The function is as described above.

[0124] Compound B is preferably an aromatic compound, as this reduces the moisture permeability of the protective film. An aromatic compound is a compound that has one or more aromatic rings. The compound B may have only one aromatic ring or may have a plurality of aromatic rings. The aromatic ring may be the entire structure constituting the entire compound B, or may be a partial structure constituting a part of the compound B. The aromatic ring may be monocyclic or polycyclic, and is preferably polycyclic. The polycyclic aromatic ring is, for example, an aromatic ring formed by condensing a plurality of (e.g., 2 to 5) aromatic ring structures, and it is preferred that at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. The aromatic ring may be a heteroaromatic ring, which preferably has one or more (e.g., 1 to 4) heteroatoms (e.g., nitrogen atoms, oxygen atoms, sulfur atoms, etc.) as ring member atoms, and more preferably has one or more (e.g., 1 to 4) nitrogen atoms as ring member atoms. The aromatic ring preferably has 5 to 15 ring atoms.

[0125] Examples of the aromatic ring include monocyclic aromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; aromatic rings fused with two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and aromatic rings fused with three rings such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenazine ring.

[0126] The aromatic ring may have one or more (for example, 1 to 5) substituents. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, an amino group, and a nitro group. When the aromatic ring has two or more substituents, the substituents may be bonded to each other to form a non-aromatic ring. It is also preferred that the aromatic ring is directly bonded to a carbonyl group to form an aromatic carbonyl group in compound B. It is also preferred that a plurality of aromatic rings are bonded via carbonyl groups. It is also preferred that the aromatic ring is bonded to an imide group to form an aromatic imide group in compound B. The imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring. A series of aromatic ring structures may be formed by a plurality of aromatic rings (e.g., 2 to 5 aromatic rings) bonded together via a structure selected from the group consisting of a single bond, a carbonyl group, and a multiple bond (e.g., a vinylene group which may have a substituent, -C≡C-, -N=N-, etc.). Preferably, one or more of the aromatic rings constituting the series of aromatic ring structures is the heteroaromatic ring.

[0127] In order to further reduce the moisture permeability of the protective film, it is preferable that compound B is a compound that satisfies one or more (e.g., 1 to 4) of requirements (1) to (4). Compound B preferably satisfies requirement (2), and preferably has a nitrogen atom as the heteroatom in the heteroaromatic ring. In other words, a nitrogen-containing aromatic compound is preferred. (1) It has polycyclic aromatic rings. (2) It has a heteroaromatic ring. (3) Contains an aromatic carbonyl group. (4) Contains an aromatic imide group.

[0128] Examples of compound B include monocyclic aromatic compounds such as pyridine and pyridine derivatives, pyrazine and pyrazine derivatives, pyrimidine and pyrimidine derivatives, and triazine and triazine derivatives; compounds in which two rings are fused to form an aromatic ring, such as quinoline and quinoline derivatives, isoquinoline and isoquinoline derivatives, quinoxaline and quinoxaline derivatives, and quinazoline and quinazoline derivatives; and compounds in which three or more rings are fused to form an aromatic ring, such as acridine and acridine derivatives, phenanthridine and phenanthridine derivatives, phenanthroline and phenanthroline derivatives, and phenazine and phenazine derivatives. Compound B is preferably one or more selected from the group consisting of pyridine and pyridine derivatives, quinoline and quinoline derivatives, isoquinoline and isoquinoline derivatives, and acridine and acridine derivatives, more preferably one or more selected from the group consisting of quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives, and even more preferably one or more selected from the group consisting of isoquinoline and isoquinoline derivatives. These compounds and derivatives thereof may further have a substituent. The above-mentioned substituent is preferably an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, an amino group, or a nitro group, more preferably an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group, still more preferably an alkyl group, an aryl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group, and particularly preferably an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms).

[0129] In addition, in order to further reduce the moisture permeability of the protective film, compound B is preferably an aromatic compound having a substituent (a compound having a substituent on a constituent atom of the aromatic ring contained in compound B), and more preferably a compound that satisfies one or more (e.g., 1 to 4) of the above-mentioned requirements (1) to (4) and further has a substituent. Regarding the position of the substituent, for example, when compound B is quinoline or a quinoline derivative, it is preferable that the substituent be at least at the 2nd and 4th positions on the quinoline ring, since this will result in a lower moisture permeability of the protective film. Also, for example, when compound B is isoquinoline or an isoquinoline derivative, it is preferable that the substituent be at least at the 1st position on the isoquinoline ring, since this will result in a lower moisture permeability of the protective film. The substituent is preferably an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms).

[0130] Compound B is preferably a compound represented by any one of formulas (B1) to (B4).

[0131] [ka]

[0132] In formulae (B1) to (B4), each R independently represents a hydrogen atom or a substituent. The substituent is preferably an alkyl group. The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 5 carbon atoms. A plurality of R's may be the same or different. In formula (B1), it is preferable that at least one of R represents a hydrogen atom, it is more preferable that at least four of R represent hydrogen atoms, and it is even more preferable that all of R represent hydrogen atoms. In formula (B2), it is preferable that at least one of R represents a hydrogen atom, more preferable that at least four of R represent hydrogen atoms, and even more preferable that all of R represent hydrogen atoms. In formula (B3), it is preferable that at least one of R represents a hydrogen atom, it is more preferable that at least four of R represent hydrogen atoms, and it is even more preferable that all of R represent hydrogen atoms. In formula (B4), it is preferable that at least one of R represents a hydrogen atom, it is more preferable that at least four of R represent hydrogen atoms, and it is even more preferable that all of R represent hydrogen atoms.

[0133] Examples of 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, and 2-chloropyridine.

[0134] Compound B preferably has a specific maximum absorption wavelength. That is, Compound B preferably has a maximum absorption wavelength in the wavelength range of 300 to 400 nm. Compound B may also have a maximum absorption wavelength other than the specific maximum absorption wavelength. The specific maximum absorption wavelength is preferably in the wavelength range of 300 to 380 nm, more preferably in the wavelength range of 310 to 360 nm, and even more preferably in the wavelength range of 310 to 330 nm. Compound B may have a plurality of specific maximum absorption wavelengths in the wavelength range of 300 to 400 nm. The specific maximum absorption wavelength may be measured, for example, by measuring the specific maximum absorption wavelength of a protective film.

[0135] The point at which the moisture permeability of the protective film becomes lower is the molar absorption coefficient (ε 365 ) is, for example, 20,000 (cm mol / L) -1 Less than 18,000 (cm mol / L) -1Preferably less than 15,000 (cm mol / L) -1 Less than 10,000 (cm mol / L) is preferable. -1 The lower limit of the molar extinction coefficient ε is, for example, 0 (cm mol / L) -1 and above 1000 (cm mol / L) -1 Ultra is preferred. ε of compound B 365 When the value is within the above range, it is suitable for an embodiment in which the photosensitive layer is exposed through a temporary support (preferably a PET film). That is, when the acid group of the polymer P is a carboxyl group, the molar absorption coefficient ε 365 Since the viscosity is appropriately low, the generation of bubbles due to decarbonation can be controlled even when the exposure is performed through a temporary support, and deterioration of the pattern shape can be prevented. In addition, ε of compound B 365 By setting the content within the above range, coloration of the protective film can be suppressed. Such an ε 365 The compound B having the formula (I) is preferably the above-mentioned monocyclic aromatic compound or an aromatic compound in which two rings are fused to form an aromatic ring, more preferably pyridine or a pyridine derivative, quinoline or a quinoline derivative, or isoquinoline or an isoquinoline derivative, and even more preferably isoquinoline or an isoquinoline derivative.

[0136] In addition, the moisture permeability of the protective film becomes lower, and the molar absorption coefficient (ε 313 ) is, for example, 20,000 (cm mol / L) -1 Less than 18,000 (cm mol / L) -1 Preferably less than 15,000 (cm mol / L) -1 Less than 10,000 (cm mol / L) is preferable. -1 The lower limit of the molar extinction coefficient ε is, for example, 0 (cm mol / L) -1 and above 1000 (cm mol / L) -1 Ultra is preferred.

[0137] ε of compound B 365 and ε313 is the molar absorption coefficient measured by dissolving compound B in acetonitrile. If compound B is not soluble in acetonitrile, the solvent used to dissolve compound B may be changed as appropriate.

[0138] The lower limit of the pKa of compound B in the ground state is preferably 0.50 or more, and more preferably 2.00 or more, from the viewpoint of more excellent pattern forming ability and / or lower moisture permeability of the formed pattern. The upper limit of the pKa of compound B in the ground state is preferably 10.00 or less, more preferably 9.00 or less, even more preferably 8.00 or less, and particularly preferably 7.00 or less. The pKa of compound B in the ground state refers to the pKa of compound B in an unexcited state, and can be determined by acid titration. When compound B is a nitrogen-containing aromatic compound, the pKa of compound B in the ground state refers to the pKa of the conjugate acid of compound B in the ground state.

[0139] The molecular weight of compound B is preferably less than 5,000, more preferably less than 1,000, further preferably 65 to 300, and particularly preferably 75 to 250.

[0140] Furthermore, in the case where the photosensitive layer is formed by coating, the compound B is less likely to volatilize during the coating process and has a better remaining rate in the photosensitive layer (better pattern-forming ability and / or lower moisture permeability of the pattern formed), so the molecular weight of compound B is preferably 120 or more, more preferably 130 or more, and even more preferably 150 or more. The upper limit of the molecular weight of compound B is preferably less than 5,000, and more preferably 1,000 or less.

[0141] When compound B is a compound exhibiting a cationic state (for example, a nitrogen-containing aromatic compound), the energy level of the HOMO (highest occupied molecular orbital) of compound B in the cationic state is preferably −7.50 eV or less, and more preferably −7.80 eV or less, in terms of achieving better pattern forming ability and / or lower moisture permeability of the formed pattern. The lower limit is preferably −13.60 eV or more. In the case of the HOMO(1-stranded conjugation cycle) of the B-protein complex, the HOM O)'s wavelengths are the high-density waveguide Gaussian09(Gaussian 09, Revision A.02, MJ Frisch, GW Trucks, HB Schlegel, GE Scuseria, MA Robb, JR Cheeseman, G Scalmani, V Barone, B Mennucci, Petersson GA, Nakatsuji H, Caricato M, Li, Hratchian AF, Izmaylov J, Bloino, G Zheng, JL Sonnenberg, 09, Revision A.02; Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery, Jr., Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN. Kobayashi, J, Normand, K, Raghavachari, A, Rendell, JC, Burant, SS, Iyengar, J, Tomasi, M, Cossi, N, Rega, JM, Millam, M, Klene, J, Knox, JB, Cross, V, Bakken, C, Adamo, J, Jaramillo, Gomperts, R, Pomelli C , Ochterski JW , Martin RL , Morokuma K , Zakrzewski VG , Voth GA , Salvador P , Dannenberg JJ , Dapprich S S , Daniels AD Daniels , O .Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, and D.J. Fox, Gaussian, Inc., Wallingford CT, 2009. The calculation method used was the time-dependent density functional method using B3LYP as the functional and 6-31+G(d,p) as the basis set. In addition, to incorporate the solvent effect, the PCM method based on the chloroform parameters set in Gaussian09 was also used. Using this method, a geometry optimization calculation of the first electronic excited state was performed to determine the structure with the lowest energy, and the HOMO energy of that structure was calculated.

[0142] Below, the HOMO energy level (eV) of the cationic state of a representative example of compound B is shown, along with its molecular weight.

[0143] [Table 1]

[0144] The compound B may be used alone or in combination of two or more. The content of compound B is preferably 0.1 to 50% by mass based on the total solid content of the photosensitive material. In the photosensitive material of embodiment X-1-a1, the content of compound B is preferably 2 to 40 mass %, more preferably 4 to 35 mass %, and even more preferably 8 to 30 mass %, based on the total solid content of the photosensitive material. In the photosensitive layer of embodiment X-1-a2, the content of compound B is preferably from 0.5 to 20% by mass, more preferably from 1 to 10% by mass, based on the total solid content of the photosensitive material. In the photosensitive layer of Embodiment X-1-a3, the content of Compound B is preferably from 0.3 to 20% by mass, more preferably from 0.5 to 8% by mass, based on the total solid content of the photosensitive material.

[0145] The total number of moles of compound B is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, particularly preferably 10 mol% or more, and most preferably 20 mol% or more, relative to the total number of moles of acid groups in polymer P. From the viewpoint of the film quality of the resulting protective film, the upper limit is preferably 200 mol% or less, more preferably 100 mol% or less, and even more preferably 80 mol% or less, relative to the total number of moles of acid groups in polymer P.

[0146] [Polymerizable compound] The photosensitive material may contain a polymerizable compound. The polymerizable compound is a component different from the polymer P and does not contain an acid group.

[0147] The polymerizable compound is a polymerizable compound having one or more (for example, 1 to 15) ethylenically unsaturated groups in one molecule. The polymerizable compound preferably contains a difunctional or higher functional polymerizable compound. Here, the term "difunctional or higher functional polymerizable compound" refers to a polymerizable compound having two or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule. Examples of the ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred. As the polymerizable compound, (meth)acrylate is also preferred.

[0148] The photosensitive material preferably contains a difunctional polymerizable compound (preferably a difunctional (meth)acrylate) and a trifunctional or higher functional polymerizable compound (preferably a trifunctional or higher functional (meth)acrylate).

[0149] Examples of bifunctional polymerizable compounds include tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Examples of bifunctional polymerizable compounds include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0150] Examples of the tri- or higher functional polymerizable compound include 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 glycerin tri(meth)acrylate skeleton.

[0151] The term "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and the term "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0152] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0153] Examples of polymerizable compounds include urethane (meth)acrylates (preferably tri- or higher functional urethane (meth)acrylates). The lower limit of the number of functional groups is preferably 6 or more, more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of trifunctional or higher urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0154] The molecular weight of the polymerizable compound (weight average molecular weight when the polymerizable compound has a molecular weight distribution) is preferably less than 5,000, more preferably from 200 to 3,000, even more preferably from 250 to 2,600, and particularly preferably from 280 to 2,200. The minimum molecular weight of all the polymerizable compounds contained in the photosensitive material is preferably 250 or more, more preferably 280 or more.

[0155] The polymerizable compounds may be used alone or in combination of two or more. When a polymerizable compound is contained, the content of the polymerizable compound is preferably 3 to 70 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 55 mass %, based on the total solid content of the photosensitive material. The mass ratio of the content of the polymerizable compound to the content of the polymer P (content of the polymerizable compound / content of the polymer P) is preferably from 0.2 to 2.0, more preferably from 0.4 to 0.9.

[0156] The content of the bifunctional polymerizable compound is preferably 10 to 90 mass %, more preferably 20 to 85 mass %, and even more preferably 30 to 80 mass %, based on the total mass of all polymerizable compounds contained in the photosensitive material. The content of the tri- or higher functional polymerizable compound is preferably 10 to 90 mass %, more preferably 15 to 80 mass %, and even more preferably 20 to 70 mass %, based on the total mass of all polymerizable compounds contained in the photosensitive material.

[0157] The photosensitive material may also contain a difunctional or higher functional polymerizable compound and a monofunctional polymerizable compound. The polymerizable compound contained in the photosensitive material is preferably a bifunctional or higher functional polymerizable compound as a main component. Specifically, the content of the bifunctional or higher functional polymerizable compound is preferably 60 to 100 mass %, more preferably 80 to 100 mass %, and even more preferably 90 to 100 mass %, based on the total mass of all polymerizable compounds contained in the photosensitive material.

[0158] [Photopolymerization initiator] The photosensitive material may contain a photopolymerization initiator. The photopolymerization initiator may be a photoradical polymerization initiator, a photocationic polymerization initiator, or a photoanionic polymerization initiator, and is preferably a photoradical polymerization initiator.

[0159] The photopolymerization initiator is preferably at least one selected from the group consisting of oxime ester compounds (photopolymerization initiators having an oxime ester structure) and aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), and more preferably contains both of these compounds. When both of these compounds are contained, the content of the oxime ester compound is preferably 5 to 90 mass %, more preferably 15 to 50 mass %, of the total content of both of these compounds. In addition to the above photopolymerization initiator, other photopolymerization initiators may be contained. Other photopolymerization initiators include, for example, hydroxyacetophenone compounds, acylphosphine oxide compounds, and bistriphenylimidazole compounds.

[0160] Further, examples of the photopolymerization initiator include those described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0161] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF, and trade name: Lunar 6, DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Powerful Electronic New Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Powerful Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Powerful Electronic New Materials Co., Ltd.).

[0162] Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, the Omnirad series is a product of IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0163] Other photopolymerization initiators include, 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)-butanone-1 (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-diphenylethan-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).

[0164] The photopolymerization initiators may be used alone or in combination of two or more. When a photopolymerization initiator is contained, the content of the photopolymerization initiator is preferably 0.1 to 15 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 5 mass %, based on the total solid content of the photosensitive material.

[0165] [Surfactant] The photosensitive material may contain a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine-based surfactants.

[0166] As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of WO 2018 / 179640 can also be used. Furthermore, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A No. 2009-237362 can also be used. Commercially available fluorine-based surfactants include, for example, Megafac 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, 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, and F-780. EXP.MFS-330, EXP.MFS-578, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, 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 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Futergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by NEOS Co., Ltd.), and U-120E (Unichem Co., Ltd.). Also suitable for use as fluorosurfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac DS-21. As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Furthermore, a block polymer can also be used as the fluorine-based surfactant. Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound 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 groups, propyleneoxy groups) can also be preferably used. As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0167] From the viewpoint of improving environmental friendliness, it is preferable that the fluorine-based surfactant be a surfactant derived from an alternative material to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, 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 esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), and Solsperse 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0168] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0169] Examples of surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), as well as X-22-4952, X-22-4272, and X-22-626 6, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, K F-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-12 4, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (all manufactured by Shin-Etsu Silicones Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Examples include BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0170] The surfactants may be used alone or in combination of two or more. The content of the surfactant is preferably from 0.0001 to 10% by mass, more preferably from 0.001 to 5% by mass, and even more preferably from 0.005 to 3% by mass, based on the total solid content of the photosensitive material.

[0171] <Solvent> The photosensitive material may contain a solvent. The solvent is preferably an organic solvent. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, 2-propanol, and mixed solvents thereof. The solvent is preferably 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.

[0172] The solvents may be used alone or in combination of two or more. When the photosensitive material contains a solvent, the solid content of the photosensitive material is preferably 5 to 80 mass %, more preferably 8 to 40 mass %, and even more preferably 10 to 30 mass %. That is, when the photosensitive material contains a solvent, the content of the solvent is preferably 20 to 95 mass %, more preferably 60 to 95 mass %, and even more preferably 70 to 95 mass %, based on the total mass of the photosensitive material.

[0173] When the photosensitive material contains a solvent, the viscosity (25° C.) of the photosensitive material is preferably from 1 to 50 mPa·s, more preferably from 2 to 40 mPa·s, and even more preferably from 3 to 30 mPa·s, from the viewpoint of coatability. The viscosity can be measured using, for example, a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO., LTD.). When the photosensitive material contains a solvent, the surface tension of the photosensitive material (25° C.) is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m, from the viewpoint of coatability. The surface tension can be measured using, for example, an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0174] Examples of the solvent include those described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005 / 282073, the contents of which are incorporated herein by reference. Further, examples of the solvent include organic solvents with a boiling point of 180 to 250°C (high boiling point solvents).

[0175] [Other additives] The photosensitive material may contain other additives. Examples of other additives include plasticizers, sensitizers, heterocyclic compounds, and alkoxysilane compounds. Examples of the plasticizer, sensitizer, heterocyclic compound, and alkoxysilane compound include those described in paragraphs 0097 to 0119 of WO 2018 / 179640. The photosensitive material may further contain other additives, such as known additives, including rust inhibitors, metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinkers, and organic or inorganic suspending agents. Preferred embodiments of these components are described in paragraphs 0165 to 0184 of JP 2014-085643 A, the contents of which are incorporated herein by reference. The other additives may be used alone or in combination of two or more.

[0176] The photosensitive material may contain impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so it is preferable to set the contents to the following values.

[0177] The content of impurities in the photosensitive material is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably 2 mass ppm or less, based on the total solid content of the photosensitive material. The lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, based on the total solid content of the photosensitive material. Methods for keeping the impurity content within the above range include, for example, selecting raw materials for the photosensitive material that contain a small amount of impurities, preventing impurities from being mixed in when forming the photosensitive material, and removing them by washing. By using such methods, the amount of impurities can be kept within the above range.

[0178] Methods for measuring the content of impurities include known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0179] [Transfer film] As mentioned above, the transfer film can be used to form a protective layer. The transfer film preferably has a temporary support and a photosensitive layer. FIG. 1 is a cross-sectional view showing an example of an embodiment of the transfer film of the present invention. The transfer film 100 shown in FIG. 1 has a configuration in which a temporary support 12, a photosensitive layer 14, and a cover film 16 are laminated in this order. Although the transfer film 100 shown in FIG. 1 has a cover film 16 arranged thereon, the cover film 16 does not necessarily have to be arranged.

[0180] [Temporary support] The temporary support is a support that supports the photosensitive layer and is peelable from the photosensitive layer. The temporary support preferably has light transparency, since the photosensitive layer can be exposed through the temporary support when the photosensitive layer is subjected to pattern exposure. Here, "having optical transparency" means that the transmittance of the dominant wavelength of light used for exposure (which may be pattern exposure or full-surface exposure) is 50% or more. The transmittance of the dominant wavelength of light used for exposure is preferably 60% or more, and more preferably 70% or more, in terms of better exposure sensitivity. The transmittance can be measured using an MCPD Series manufactured by Otsuka Electronics Co., Ltd. Specifically, the transmittance of the temporary support is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more at wavelengths of 313 nm, 365 nm, 313 nm, 405 nm, and 436 nm. Preferred values ​​of the transmittance at each of the above wavelengths include, for example, 87%, 92%, and 98%.

[0181] Specific examples of the temporary support include a glass substrate, a resin film, and paper. Resin films are preferred because of their superior strength and flexibility. Examples of resin films include polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Biaxially stretched polyethylene terephthalate films are preferred.

[0182] From the viewpoint of the pattern forming ability during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matter, and defects contained in the temporary support is small. The number of particles, foreign matter, and defects with a diameter of 2 μm or more is 50 / 10 mm 2 Preferably, it is 10 pieces / 10 mm or less. 2 It is more preferable that the number of pieces is 3 pieces / 10 mm or less. 2 It is more preferable that the number of particles is 1 particle / 10 mm or less. 2 It can be more than that. In order to further improve the handling property, the temporary support has particles with a diameter of 0.5 to 5 μm at a density of 1 particle / mm on the surface opposite to the side on which the photosensitive layer is formed. 2 It is preferable to have a layer in which there are at least 1 to 50 particles / mm 2 It is more preferable that it exists.

[0183] The thickness of the temporary support is preferably from 5 to 200 μm, more preferably from 10 to 150 μm, in terms of ease of handling and versatility. The thickness of the temporary support can be appropriately selected depending on the material, taking into consideration the strength as a support, the flexibility required for bonding to the circuit wiring formation substrate, the light transmittance required in the initial exposure step, and the like.

[0184] The temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning used films and turning them into chips, and then forming the chips into films. Examples of recycled temporary supports include the Ecouse series manufactured by Toray Industries, Inc.

[0185] Examples of temporary supports include those described in paragraphs 0017 to 0018 of JP 2014-085643 A, paragraphs 0019 to 0026 of JP 2016-027363 A, paragraphs 0041 to 0057 of WO 2012 / 081680 A1, and paragraphs 0029 to 0040 of WO 2018 / 179370 A1, the contents of which are incorporated herein by reference.

[0186] Examples of the temporary support include COSMOSHINE (registered trademark) A4100, COSMOSHINE (registered trademark) A4160, and COSMOSHINE (registered trademark) A4360, all manufactured by Toyobo Co., Ltd., and LUMIRROR (registered trademark) 16FB40, LUMIRROR (registered trademark) 16KS40 (16QS62), LUMIRROR (registered trademark) #38-U48, LUMIRROR (registered trademark) #75-U34, and LUMIRROR (registered trademark) #25-T60, all manufactured by Toray Industries, Inc. The temporary support is preferably a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, or a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm.

[0187] [Photosensitive layer] The various components that can be contained in the photosensitive layer are the same as the various components that can be contained in the above-mentioned photosensitive material, and the preferred ranges are also the same. The preferred ranges for the content of each component in the photosensitive layer are the same as those obtained by replacing the above-mentioned "content (mass%) of each component relative to the total solid content of the photosensitive material" with "content (mass%) of each component relative to the total mass of the photosensitive layer." Specifically, the statement "The content of polymer P in the photosensitive material is preferably 25 to 100 mass% relative to the total solid content of the photosensitive material" should be replaced with "The content of polymer P in the photosensitive layer is preferably 25 to 100 mass% relative to the total mass of the photosensitive layer." Note that, as mentioned above, "solid content" refers to all components of the photosensitive material except the solvent. Furthermore, even if the photosensitive material is in liquid form, components other than the solvent are considered to be solid content.

[0188] When a photosensitive layer is formed from a photosensitive material containing a solvent, the solvent may remain, but it is preferable that the photosensitive layer does not contain any solvent. The content of the solvent in the photosensitive layer is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.1% by mass or less, based on the total mass of the photosensitive layer. The lower limit is often 0% by mass or more based on the total mass of the photosensitive layer.

[0189] In addition, 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 layer is preferably low. The content of each of these compounds in the photosensitive layer is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive layer. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the photosensitive layer. Methods for measuring these compounds include, for example, known measurement methods.

[0190] The content of water in the photosensitive layer is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0.5% by mass, based on the total mass of the photosensitive layer, in that better pattern forming ability is achieved.

[0191] [Physical Properties of Photosensitive Layer] The average thickness of the photosensitive layer is preferably 0.5 to 20 μm. When the average thickness of the photosensitive layer is 20 μm or less, the pattern resolution is superior, and when the average thickness of the photosensitive layer is 0.5 μm or more, it is preferable in terms of pattern linearity. The average thickness of the photosensitive layer is more preferably 0.8 to 15 μm, and even more 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.

[0192] The transmittance of the photosensitive layer at a wavelength of 365 nm is preferably 20% or more, more preferably 65% ​​or more, and even more preferably 90% or more, in terms of achieving better pattern-forming ability and / or lower moisture permeability of the pattern formed. The upper limit is, for example, 100% or less. The ratio of the transmittance of the photosensitive layer at a wavelength of 365 nm to the transmittance of the photosensitive layer at a wavelength of 313 nm (transmittance of the photosensitive layer at a wavelength of 365 nm / transmittance of the photosensitive layer at a wavelength of 313 nm) is preferably 1 or more, more preferably 1.5 or more, in terms of achieving better pattern-forming ability and / or lowering the moisture permeability of the pattern formed. The upper limit is, for example, 1,000 or less.

[0193] The visible light transmittance per 1.0 μm of thickness of the photosensitive layer is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. It is preferable that the average transmittance of light with a wavelength of 400 to 800 nm, the minimum transmittance of light with a wavelength of 400 to 800 nm, and the transmittance of light with a wavelength of 400 nm all satisfy the above. Specific examples of the visible light transmittance per 1.0 μm of photosensitive layer thickness include 87%, 92%, and 98%.

[0194] The dissolution rate of the photosensitive layer in a 1.0% by mass aqueous solution of sodium carbonate is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and even more preferably 0.20 μm / sec or more, from the viewpoint of suppressing residues during development. The upper limit is preferably 5.0 μm / sec or less, from the viewpoint of the edge shape of the pattern. Specific examples of the dissolution rate include 1.8 μm / sec, 1.0 μm / sec, and 0.7 μm / sec. The dissolution rate per unit time of the photosensitive layer in a 1.0 mass % aqueous sodium carbonate solution can be measured by the following measurement method. A photosensitive layer (thickness in the range of 1.0 to 10 μm) formed on a glass substrate and from which the solvent has been thoroughly removed is subjected to shower development at 25°C using a 1.0% by mass aqueous solution of sodium carbonate until the photosensitive layer is completely dissolved. The development is carried out for a maximum of 2 minutes. The thickness of the photosensitive layer is then calculated by dividing it by the time required for the photosensitive layer to completely dissolve. If the photosensitive layer is not completely dissolved within 2 minutes of development, the thickness is calculated in the same manner as above using the amount of change in the photosensitive layer up to that point. For development, a 1 / 4MINJJX030PP shower nozzle manufactured by Ikeuchi Co., Ltd. is used, and the shower spray pressure is 0.08MPa. Under the above conditions, the shower flow rate per unit time is 1,800mL / min.

[0195] From the viewpoint of pattern formation ability, the number of foreign particles with a diameter of 1.0 μm or more in the photosensitive layer should be 10 / mm 2 Preferably less than 5 pieces / mm 2 The following is more preferred: The number of foreign objects can be measured by the following method. Five randomly selected areas (1 mm x 1 mm) on the surface of the photosensitive layer are visually observed using an optical microscope from the normal direction of the surface of the photosensitive layer, and the number of foreign particles with a diameter of 1.0 μm or more in each area is counted and the arithmetic average is calculated as the number of foreign particles. Specifically, the number of foreign particles is calculated as 0 particles / mm 2 , 1 piece / mm 2 , 4 pieces / mm 2 , and 8 pieces / mm 2 Examples include: To prevent the formation of aggregates during development, 1.0 cm of the solution was added to 1.0 L of a 1.0% by weight sodium carbonate solution at 30°C. 3The haze of the solution obtained by dissolving the photosensitive layer is preferably 60% or less, more preferably 30% or less, even more preferably 10% or less, and particularly preferably 1% or less. The lower limit is, for example, 0%. The haze can be measured by the following method. First, a 1.0 mass% aqueous solution of sodium carbonate is prepared, and the liquid temperature is adjusted to 30°C. 1.0 cm3 is added to 1.0 L of the aqueous solution of sodium carbonate. 3 The photosensitive layer is added. The mixture is stirred at 30°C for 4 hours, taking care not to introduce air bubbles. After stirring, the haze of the solution in which the photosensitive layer has dissolved is measured. The haze is measured using a haze meter (product name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) with a liquid measurement unit and a dedicated liquid measurement cell with an optical path length of 20 mm. Specific examples of haze include 0.4%, 1.0%, 9%, and 24%.

[0196] [Others] The transfer film may have other layers in addition to those described above. Examples of other layers include a cover film, a high refractive index layer, and other layers (for example, an intermediate layer and a thermoplastic resin layer). When a high refractive index layer is formed on the temporary support or the cover film, the photosensitive layer may be formed on the high refractive index layer.

[0197] <Cover film> The transfer film may further have a cover film on the side opposite to the temporary support of the photosensitive layer. When the transfer film has a high refractive index layer described below, the cover film is preferably disposed on the opposite side of the high refractive index layer from the temporary support (i.e., the opposite side from the photosensitive layer). In this case, the transfer film is, for example, a laminate in which "temporary support / photosensitive layer / high refractive index layer / cover film" are laminated in this order.

[0198] The number of fisheyes in the cover film with a diameter of 80 μm or more is 5 / m 2The following is preferred: "Fisheyes" are foreign matter, unmelted material, and / or oxidized and deteriorated material of the material that is introduced into the cover film when the material is thermally melted and then kneaded, extruded, and / or biaxially stretched, cast, or other methods are used to produce the film.

[0199] The number of particles with a diameter of 3 μm or more in the cover film is 30 / mm 2 Preferably less than 10 pieces / mm 2 Less than 5 pieces / mm is more preferable. 2 The following is more preferable: In the above case, defects caused by the transfer of unevenness due to particles in the cover film to the photosensitive layer can be suppressed.

[0200] The arithmetic mean roughness Ra of the cover film surface is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. Within the above range, the transfer film can be easily wound up. The upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less, from the viewpoint of suppressing defects during transfer.

[0201] Examples of the cover film include a polyethylene terephthalate film, a polypropylene film, a polystyrene film, and a polycarbonate film. As the cover film, for example, those described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138 may be used.

[0202] Examples of cover films include Alphan (registered trademark) FG-201 manufactured by Oji F-Tex Co., Ltd., Alphan (registered trademark) E-201F manufactured by Oji F-Tex Co., Ltd., Therapeel (registered trademark) 25WZ manufactured by Toray Advanced Film Co., Ltd., and Lumirror (registered trademark) 16QS62 (16KS40) manufactured by Toray Industries, Inc. The cover film may be a recycled product. Examples of recycled products include films made from used films that have been cleaned and chipped. Examples of recycled products include the Ecouse (registered trademark) series manufactured by Toray Industries, Inc.

[0203] <High refractive index layer> The high refractive index layer is preferably disposed adjacent to the photosensitive layer, and is also preferably disposed on the side opposite the temporary support from the photosensitive layer. The high refractive index layer is a layer having a refractive index of 1.50 or more for light with a wavelength of 550 nm. The refractive index of the high refractive index layer is preferably 1.55 or more, more preferably 1.60 or more. The upper limit is preferably 2.10 or less, more preferably 1.85 or less, even more preferably 1.78 or less, and particularly preferably 1.74 or less. The refractive index of the high refractive index layer is preferably higher than the refractive index of the photosensitive layer.

[0204] The high refractive index layer may be either photosensitive or thermosetting. The embodiment in which the high refractive index layer is photosensitive has the advantage that after transfer, the photosensitive layer and the high refractive index layer transferred onto the substrate can be patterned together by a single photolithography process. The high refractive index layer preferably has alkali solubility (for example, solubility in a weak alkaline aqueous solution) and is preferably a transparent layer.

[0205] The thickness of the high refractive index layer is preferably 500 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less. The lower limit is preferably 20 nm or more, more preferably 55 nm or more, even more preferably 60 nm or more, and particularly preferably 70 nm or more.

[0206] After transfer, the high refractive index layer may be sandwiched between a transparent electrode pattern (preferably an ITO pattern) and a photosensitive layer to form a laminate together with the transparent electrode pattern and the photosensitive layer. 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. This further improves the concealing ability of the transparent electrode pattern. For example, when a transparent electrode pattern, a high refractive index layer, and a photosensitive layer are laminated in this order, the transparent electrode pattern becomes difficult to see when viewed from the transparent electrode pattern side.

[0207] The refractive index of the high refractive index layer is preferably adjusted according to the refractive index of the transparent electrode pattern. When the refractive index of the transparent electrode pattern is in the range of 1.8 to 2.0, for example, when formed using an oxide of In and Sn (ITO), the refractive index of the high refractive index layer is preferably 1.60 or more. In this case, the upper limit of the refractive index of the high refractive index layer is preferably 2.1 or less, more preferably 1.85 or less, even more preferably 1.78 or less, and particularly preferably 1.74 or less. When the refractive index of the transparent electrode pattern is greater than 2.0, such as when it is formed using an oxide of In and Zn (IZO; Indium Zinc Oxide), the refractive index of the high refractive index layer is preferably 1.70 to 1.85.

[0208] Methods for controlling the refractive index of the high refractive index layer include, for example, a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, and a method of using a complex of a metal salt and a resin.

[0209] As the type of metal oxide particles or metal particles, for example, known metal oxide particles or metal particles can be used. The metals in the metal oxide particles or metal particles include semimetals such as B, Si, Ge, As, Sb, and Te.

[0210] The average primary particle size of the particles (metal oxide particles or metal particles) is preferably from 1 to 200 nm, more preferably from 3 to 80 nm, from the viewpoint of transparency, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side. Specifically, the metal oxide particles are preferably at least one selected from the group consisting of zirconium oxide particles (ZrO2 particles), Nb2O5 particles, titanium oxide particles (TiO2 particles), silicon dioxide particles (SiO2 particles), and composite particles thereof. As these metal oxide particles, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferred, for example, from the viewpoint that the refractive index of the high refractive index layer can be easily adjusted to 1.60 or more.

[0211] When the high refractive index layer contains metal oxide particles, the high refractive index layer may contain only one type of metal oxide particles, or may contain two or more types of metal oxide particles.

[0212] The content of particles (metal oxide particles or metal particles) is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 40 to 85 mass %, relative to the total mass of the high refractive index layer, in order to improve the concealment of objects to be concealed, such as electrode patterns, and effectively improve the visibility of the objects to be concealed. When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95 mass %, more preferably 20 to 90 mass %, and even more preferably 40 to 85 mass %, based on the total mass of the high refractive index layer.

[0213] Commercially available metal oxide particles include, for example, calcined zirconium oxide particles (manufactured by CIK Nanotech, product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech, product name: ZRPGM15WT%-F74), calcined zirconium oxide particles (manufactured by CIK Nanotech, product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech, product name: ZRPGM15WT%-F76), zirconium oxide particles (Nanouse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.), and zirconium oxide particles (Nanouse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

[0214] The high refractive index layer preferably contains at least one selected from the group consisting of inorganic particles (metal oxide particles or metal particles) having a refractive index of 1.50 or more (more preferably 1.55 or more, even more preferably 1.60 or more), resins having a refractive index of 1.50 or more (more preferably 1.55 or more, even more preferably 1.60 or more), and polymerizable compounds having a refractive index of 1.50 or more (more preferably 1.55 or more, even more preferably 1.60 or more). In this embodiment, the refractive index of the high refractive index layer can be easily adjusted to 1.50 or more (more preferably 1.55 or more, particularly preferably 1.60 or more).

[0215] The high refractive index layer preferably contains a binder polymer, a polymerizable monomer, and particles. Examples of the various components contained in the high refractive index layer include the various components of the curable transparent resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of JP2014-108541A, the various components of the transparent layer described in paragraphs 0024 to 0035 and 0110 to 0112 of JP2014-010814A, and the various components of the composition containing an ammonium salt described in paragraphs 0034 to 0056 of WO2016 / 009980A.

[0216] The high refractive index layer also preferably contains a metal oxidation inhibitor. When the high refractive index layer contains a metal oxidation inhibitor, a surface treatment can be performed on a member (e.g., a conductive member formed on a substrate) that comes into direct contact with the high refractive index layer when the high refractive index layer is transferred onto the substrate. This surface treatment imparts a metal oxidation inhibitor function (protective properties) to the member that comes into direct contact with the high refractive index layer.

[0217] 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. The aromatic ring containing a nitrogen atom is preferably a condensed ring of an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, or a thiadiazole ring with another aromatic ring, and more preferably a condensed ring of an imidazole ring, a triazole ring, or a tetrazole ring with another aromatic ring. The "other aromatic ring" forming the fused ring may be a homocyclic ring or a heterocyclic ring, preferably a homocyclic ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0218] The metal oxidation inhibitor is preferably imidazole, benzimidazole, tetrazole, 5-amino-1H-tetrazole, mercaptothiadiazole or benzotriazole, more preferably imidazole, benzimidazole, 5-amino-1H-tetrazole or benzotriazole. An example of a commercially available metal oxidation inhibitor is BT120 (manufactured by Johoku Chemical Industry Co., Ltd.), which contains benzotriazole.

[0219] When the high refractive index layer contains a metal oxidation inhibitor, the content of the metal oxidation inhibitor is preferably 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 5 mass %, relative to the total mass of the high refractive index layer.

[0220] The high refractive index layer may contain other components in addition to the above-mentioned components. Other components that the high refractive index layer may contain include the same components as those that the photosensitive layer may contain. The high refractive index layer also preferably contains a surfactant.

[0221] The high refractive index layer can be formed by, for example, a known method. A method for forming a high refractive index layer includes, for example, applying a composition for forming a high refractive index layer containing an aqueous solvent onto the above-mentioned photosensitive layer formed on a temporary support, and drying it as necessary.

[0222] The composition for forming the high refractive index layer may contain the various components of the high refractive index layer described above. Furthermore, as the composition for forming a high refractive index layer, a composition containing an ammonium salt described in paragraphs 0034 to 0056 of WO 2016 / 009980 is also preferred.

[0223] The high refractive index layer is preferably achromatic. Specifically, the total reflection (incident angle 8°, light source: D-65 (2° visual field)) is preferably achromatic. * a * b * ) color space, * The above L * is preferably 10 to 90, and * is preferably -1.0 to 1.0, and the above b * is preferably -1.0 to 1.0.

[0224] <Other layers> Examples of other layers include those described in paragraphs 0189 to 0193 and 0194 to 0196 of JP-A-2014-085643, the contents of which are incorporated herein by reference.

[0225] <Transfer film manufacturing method> The transfer film can be produced by a known production method. The method for manufacturing a transfer film preferably includes a step of forming a photosensitive layer by applying and drying a photosensitive material containing a solvent on a temporary support, and more preferably includes a step of placing a cover film on the photosensitive layer after the step of forming the photosensitive layer. Furthermore, the method may further include a step of forming a high refractive index layer by applying and drying a composition for forming a high refractive index layer after the step of forming the photosensitive layer. In this case, it is more preferable to further include a step of placing a cover film on the high refractive index layer after the step of forming the high refractive index layer.

[0226] [Method of forming photosensitive layer] The photosensitive layer can be formed by preparing the above-mentioned photosensitive material containing a solvent, coating the photosensitive material, and drying it. Alternatively, the various components may be dissolved in a solvent beforehand to prepare solutions, and then the resulting solutions may be mixed in a predetermined ratio. Furthermore, the photosensitive material is preferably filtered using a filter with a pore size of 0.2 to 30 μm. The photosensitive layer can be formed by applying a photosensitive material onto a temporary support or a cover film and drying it. Examples of the coating method include known methods such as slit coating, spin coating, curtain coating, and inkjet coating. In addition, when other layers described below are formed on the temporary support or the cover film, the photosensitive layer may be formed on the other layers.

[0227] [Laminate] The laminate of the present invention preferably has a substrate and a protective film. The laminate preferably has a substrate having a conductive layer and a protective film in this order, and more preferably has a substrate, an electrode and a protective film in this order. The protective film is as described above.

[0228] [Base material] Examples of the substrate include a glass substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer. Examples of the substrate having a conductive layer include a glass substrate, a silicon substrate, and a resin substrate. The substrate is preferably transparent. The refractive index of the substrate is preferably 1.50 to 1.52.

[0229] The substrate may be made of a light-transmitting substrate such as a glass substrate. The light-transmitting substrate may be, for example, tempered glass (Gorilla Glass, manufactured by Corning, etc.). As the material constituting the substrate, the materials described in JP-A Nos. 2010-086684, 2010-152809, and 2010-257492 are preferred. The resin substrate is preferably a resin film with small optical distortion and / or high transparency. Materials constituting the resin substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer. The substrate having the conductive layer is preferably a resin substrate, more preferably a resin film, from the viewpoint of production by a roll-to-roll method.

[0230] The conductive layer may be any conductive layer used in general circuit wiring or touch panel wiring, and is preferably an electrode. The conductive layer is preferably a transparent layer and may be patterned. As the conductive layer, from the viewpoints of conductivity and fine line formability, one or more layers selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer are preferred, a metal layer is more preferred, and a copper layer or a silver layer is even more preferred.

[0231] Examples of materials that can form the conductive layer include simple metals and conductive metal oxides. Examples of elemental metals include aluminum, zinc, copper, iron, nickel, chromium, molybdenum, silver, and gold. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO2. Note that "conductive" refers to a material having a volume resistivity of 1×10 6 This means that the volume resistivity is less than 1×10 4 Preferably less than Ωcm. Furthermore, the conductive layer in the substrate having a conductive layer may be one layer or two or more layers. When the substrate having a conductive layer has two or more conductive layers, each conductive layer is preferably made of a different material, and preferably contains a conductive metal oxide. The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition portion used in a capacitance type touch panel or wiring of a peripheral extraction portion.

[0232] [Method of manufacturing laminate] Examples of methods for producing the laminate include known production methods. Specifically, the method preferably includes, in this order, a step of forming a photosensitive layer on a substrate, a step of patternwise exposing the photosensitive layer, and a step of developing the exposed photosensitive layer (by alkali development or organic solvent development). When the development is by organic solvent development, it is preferable to further include a step of exposing the resulting pattern. Hereinafter, an embodiment of the method for producing the laminate will be described in detail.

[0233] [Embodiment 1] The method for producing the laminate of embodiment 1 includes steps X1 to X3. Step X1: Step of forming a photosensitive layer on a substrate Step X2: Step of pattern-exposing the photosensitive layer Step X3: A step of developing the photosensitive layer using a developer (an alkaline developer or an organic solvent-based developer)

[0234] The above-mentioned step X2 corresponds to a step of reducing the content of acid groups contained in c in the photosensitive layer by exposure. When the developer used in the step X3 is an organic solvent-based developer, it is preferable to further include a step X4 after the step X3.

[0235] When an alkaline developer is used as the developer in step X3, the photosensitive layer of the transfer film is preferably formed using the photosensitive material of embodiment X-1-a1 or X-1-a2.When an organic solvent-based developer is used as the developer in step X3, the photosensitive layer of the transfer film is preferably formed using the photosensitive material of embodiment X-1-a1.

[0236] <Process X1> Step X1 is a step of forming a photosensitive layer on a substrate, more specifically, it is preferably a step of forming a photosensitive layer on a substrate using the above-mentioned photosensitive material or the above-mentioned transfer film. Examples of a method for forming a photosensitive layer using a photosensitive material include a method in which the photosensitive material is applied to a substrate and, if necessary, the coating is dried to form a photosensitive layer on the substrate. In addition, in the method of forming a photosensitive layer using a transfer film, step X1 is preferably a step of bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with a substrate, and laminating the transfer film and the substrate together. Such a step is also particularly referred to as step X1b.

[0237] Step X1b is preferably a step of laminating by applying pressure and heat using a roll or the like. Specifically, examples of the laminating step include a laminator such as a laminator, a vacuum laminator, or an auto-cut laminator.

[0238] In the step X1b, a roll-to-roll system is preferably used. When the roll-to-roll system is used, the substrate having a conductive layer is preferably a resin film having a conductive layer.

[0239] The "roll-to-roll method" refers to a method in which a substrate that can be wound and unwound is used as the substrate, and includes a step of unwinding the substrate (hereinafter also referred to as an "unwinding step") before any step in a laminate manufacturing method, and a step of winding the substrate (hereinafter also referred to as a "winding step") after any step, and at least any step (preferably all steps or all steps other than the heating step) is performed while the substrate is being transported. As the unwinding method in the unwinding step and the winding method in the winding step, for example, a known method in a manufacturing method that applies a roll-to-roll system can be used.

[0240] <Process X2> Step X2 is a step of pattern-exposing the photosensitive layer after the above step X1. Step X2 corresponds to a step of reducing the content of acid groups contained in the polymer P in the photosensitive layer by exposure. Specifically, the photosensitive layer is preferably subjected to patternwise exposure using light having a wavelength that excites the compound B in the photosensitive layer and / or the group derived from the compound B contained in the polymer P.

[0241] The arrangement and size of the pattern in step X2 are not particularly limited. For example, when the manufacturing method of the laminate of embodiment 1 is applied to the manufacture of circuit wiring, in order to improve the display quality of a display device (e.g., a touch panel) equipped with an input device having circuit wiring manufactured by the manufacturing method of the laminate of embodiment 1 and to reduce the area occupied by the lead-out wiring, it is preferable that at least a part of the pattern (particularly the part corresponding to the electrode pattern and lead-out wiring of the touch panel) be a thin line of 100 μm or less, and more preferably a thin line of 70 μm or less.

[0242] The light source for the exposure light is not particularly limited as long as it is a light source that can irradiate light in a wavelength range that can reduce the content of acid groups in the polymer P in the photosensitive layer. Specifically, a light source capable of irradiating light with a wavelength (e.g., light with a wavelength of 254 nm, 313 nm, 365 nm, or 405 nm) that excites compound B in the photosensitive layer and / or groups derived from compound B contained in polymer P is preferred. Examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (light emitting diode).

[0243] The exposure dose is 10 to 10,000 mJ / cm 2 is preferred, and 50 to 3000 mJ / cm 2 is more preferred.

[0244] In step X2, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed via the temporary support before peeling the temporary support, and then the temporary support may be peeled off. In order to prevent mask contamination due to 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 preferable to perform pattern exposure without peeling the temporary support. Note that the pattern exposure may be either exposure through a mask or direct exposure using a laser or the like. Before the step X3 described below, the temporary support is peeled off from the photosensitive layer.

[0245] <Process X3> Step X3 includes, after the above-mentioned step X2, a step (step X3) of developing the pattern-exposed photosensitive layer using a developer (an alkaline developer or an organic solvent-based developer). In the pattern-exposed photosensitive layer, the content of acid groups in the exposed areas of the photosensitive layer is reduced, resulting in a difference in solubility in a developer (dissolution contrast) between the exposed and unexposed areas. The formation of dissolution contrast in the photosensitive layer enables the formation of a pattern in step X3. When the developer used in step X3 is an alkaline developer, the unexposed areas are removed by performing step X3, forming a negative pattern. On the other hand, when the developer used in step X3 is an organic solvent-based developer, the exposed areas are removed by performing step X3, forming a positive pattern. The resulting positive pattern must be subjected to a treatment to reduce the content of acid groups in polymer A in step X4, which will be described later.

[0246] (alkaline developer) The alkaline developer is not particularly limited as long as it is an alkaline solution capable of removing the unexposed areas of the photosensitive layer. Examples of the alkaline developer include known developers such as the developer described in JP-A No. 5-072724. The alkaline developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L. The alkaline developer may further contain a water-soluble organic solvent, a surfactant, etc. As the alkaline developer, for example, the developer described in paragraph 0194 of WO 2015 / 093271 is preferred. The content of water in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the alkaline developer. The upper limit is, for example, less than 100% by mass.

[0247] (organic solvent-based developer) The organic solvent-based developer is not particularly limited as long as it is an organic solvent that can remove the exposed areas of the photosensitive layer. Examples of organic solvent-based developers include developers containing organic solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. The organic solvent-based developer may contain one or more organic solvents. The organic solvent-based developer may be a mixture of the above organic solvent with an organic solvent other than those mentioned above and / or water. The content of water in the organic solvent-based developer is preferably less than 10% by mass, more preferably less than 1% by mass, based on the total mass of the organic solvent-based developer, and even more preferably substantially free of water. The content of the organic solvent in the organic solvent-based developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent-based developer. The upper limit is, for example, 100% by mass or less.

[0248] Examples of development methods include puddle development, shower development, spin development, and dip development. The shower development is a development method in which a developer is sprayed onto a pattern-exposed photosensitive layer by showering to remove the target portions. After development, a cleaning agent or the like may be sprayed by showering and the resulting residue may be removed by scrubbing with a brush or the like. The temperature of the developer during development is preferably 20 to 40°C.

[0249] The method for producing a laminate according to the first embodiment may include a post-baking step of heat-treating the pattern formed in the step X2. The environment during post-baking is preferably 8.1 kPa or higher, more preferably 50.66 kPa or higher, and the upper limit is preferably 121.6 kPa or lower, more preferably 111.46 kPa or lower, and even more preferably 101.3 kPa or lower. The post-baking temperature is preferably 80 to 250°C, more preferably 110 to 170°C, and even more preferably 130 to 150°C. The post-baking time is preferably from 1 to 60 minutes, more preferably from 2 to 50 minutes, and even more preferably from 5 to 40 minutes. The post-baking may be carried out in an air environment or in a nitrogen-substituted environment.

[0250] <Process X4> The method for producing the laminate of the first embodiment may include step X4. Step X4: After the development step of Step X3, a step of exposing the pattern formed by development

[0251] When the developer used in the step X3 is an organic solvent-based developer, it is preferable to carry out the step X4 on the resulting positive pattern. Step X4 corresponds to a step of exposing the positive pattern obtained in step X3 to light to reduce the content of acid groups in polymer P. The exposure method, light source of exposure light, and exposure dose in step X4 are respectively the same as the exposure method, light source of exposure light, and exposure dose in step X1, and the preferred embodiments are also the same.

[0252] [Embodiment 2] The method for producing a laminate according to the second embodiment includes a step Y1, a step Y2P, and a step Y3 in this order, and further includes a step Y2Q between the step Y2P and the step Y3 or after the step Y3. Step Y1: Forming a photosensitive layer on a substrate Process Y2P: Process of exposing the photosensitive layer Step Y3: Developing the photosensitive layer using a developer Step Y2Q: A step of further exposing the photosensitive layer exposed in Step Y2P

[0253] In the method for producing a laminate of embodiment 2, the photosensitive layer of the transfer film is preferably that of embodiment X-1-a3.

[0254] The method for producing the laminate of the second embodiment will be described in detail below. Steps Y1 and Y3 have the same meanings as steps X1 and X3, respectively, and preferred embodiments are also the same. Step Y3 may be performed after step Y2P, or may be performed between step Y2P and step Y2Q. After step Y3, a post-bake step may be further included, which may be included in the method for producing a laminate of embodiment 1. When step Y3 is performed between step Y2P and step Y2Q, the post-bake step may be performed after step Y3, or may be performed before step Y2Q or after step Y2Q.

[0255] <Process Y2P, Process Y2Q> In the step Y2P, the photosensitive layer is exposed to light, and in the step Y2Q, the photosensitive layer exposed in the step Y2P is further exposed to light. One of process Y2P and process Y2Q is exposure mainly for reducing the content of acid groups in polymer P, and the other of process Y2P and process Y2Q is exposure mainly for initiating a polymerization reaction of the polymerizable compound based on a photopolymerization initiator. Furthermore, each of process Y2P and process Y2Q may be either a blanket exposure or a patterned exposure, and either process Y2P or process Y2Q is a patterned exposure.

[0256] For example, when step Y2P is patterned exposure for reducing the content of acid groups in polymer P by exposure, the developer used in step Y3 may be either an alkaline developer or an organic solvent-based developer. When an organic solvent-based developer is used as the developer, step Y2Q is performed after step Y3, and in the formed pattern, a polymerization reaction of the polymerizable compound based on the photopolymerization initiator occurs, and the content of acid groups in the polymer P is reduced. Furthermore, for example, when step Y2P is patterned exposure for inducing a polymerization reaction of a polymerizable compound based on a photopolymerization initiator, the developer used in step Y3 is preferably an alkaline developer. In the above case, step Y2Q may be performed either before or after step Y3, and when step Y2Q is performed before step Y3, it is preferable that step Y2Q be patterned exposure.

[0257] The exposure method, light source and exposure dose of exposure light in steps Y2P and Y2Q may be, for example, the same as those in step X1. The exposure dose for reducing the content of acid groups in the polymer P by exposure in the photosensitive layer is 10 to 10,000 mJ / cm 2 is preferred, and 50 to 3000 mJ / cm 2 is more preferred. The exposure dose for inducing a reaction of the polymerizable compound based on the photopolymerization initiator in the photosensitive layer is 5 to 200 mJ / cm. 2 is preferred, and 10 to 150 mJ / cm 2 is more preferred.

[0258] In steps Y2P and Y2Q, similar to step X2, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. Pattern exposure is preferably performed without peeling the temporary support. Pattern exposure may be either exposure through a mask or direct exposure using a laser or the like.

[0259] The layout and size of the patterns in the steps Y2P and Y2Q are not particularly limited. For example, see the description regarding the arrangement and size of the pattern in the above-mentioned step X2.

[0260] Other embodiments A preferred method for manufacturing a laminate is to use a substrate having two or more conductive layers on each surface, and to sequentially or simultaneously form patterns on the conductive layers formed on both surfaces. This configuration allows a first conductive pattern to be formed on one surface of the substrate, and a second conductive pattern to be formed on the other surface. Formation from both surfaces of the substrate using a roll-to-roll process is also preferred.

[0261] [Other processes] The method for producing a laminate may include other steps in addition to the steps described above.

[0262] <Cover film peeling process> When the transfer film has a cover film, it is preferable to have a step of peeling off the cover film of the transfer film. As a method for peeling off the cover film, a known method can be used.

[0263] <Step of reducing visible light reflectance> When the substrate has a conductive layer, the method for producing a laminate may further include a step of treating the conductive layer to reduce the visible light reflectance. When the substrate has two or more conductive layers, the treatment to reduce the visible light reflectance may be performed on some or all of the conductive layers. An example of a treatment for reducing the visible light reflectance is oxidation treatment. Specifically, a treatment for reducing the visible light reflectance of the conductive layer is oxidizing copper to blacken it into copper oxide. Suitable embodiments of the treatment for reducing visible light reflectance are described, for example, in paragraphs 0017 to 0025 of JP 2014-150118 A, and in paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, the contents of which are incorporated herein by reference.

[0264] [Circuit wiring manufacturing method] Examples of the method for manufacturing the circuit wiring include known methods for manufacturing circuit wiring. Specifically, a method for producing circuit wiring that includes a photosensitive layer forming step, a first exposure step, a development step, and an etching step in this order is preferred. Photosensitive layer formation process: A process of forming a photosensitive layer on a substrate having a conductive layer using a photosensitive material or transfer film. First exposure step: a step of pattern-exposing the photosensitive layer Development process: A process in which the exposed photosensitive layer is developed using an alkaline developer to form a patterned etching resist film. Etching step: a step of etching the conductive layer in the area where the etching resist film is not disposed.

[0265] The photosensitive layer forming step, the first exposure step, and the development step can be carried out in the same procedures as steps X1, X2, and X3 in the method for producing the laminate of embodiment 1, respectively. The substrate having a conductive layer has the same meaning as the substrate having a conductive layer used in step X1, and the preferred embodiments are also the same.

[0266] In the method for producing circuit wiring of the present invention, it is also preferable that the steps from the laminating step to the etching step are regarded as one set and are repeated multiple times. The film used as an etching resist film can also be used as a protective film (permanent film) for the formed circuit wiring.

[0267] <Etching process> The etching step is a step of etching the conductive layer in the area where the patterned etching resist film is not disposed. Examples of the etching treatment include the wet etching method described in paragraphs 0048 to 0054 of JP-A No. 2010-152155 and known dry etching methods such as plasma etching.

[0268] The wet etching may be, for example, an etching method in which the substrate is immersed in an etching solution, which may be an acidic or alkaline etching solution. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, as well as aqueous solutions of mixtures of acidic components with salts such as ferric chloride, ammonium fluoride, and potassium permanganate. The acidic components may be used alone or in combination of two or more. Examples of alkaline etching solutions include aqueous solutions of alkaline components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), as well as aqueous solutions of mixed alkaline components and salts such as potassium permanganate. The alkaline components may be used alone or in combination of two or more.

[0269] The temperature of the etching solution is preferably 45° C. or less. The pattern formed in step X3 or step X4 and step Y3 and used as an etching resist film preferably has resistance to acidic and alkaline etching solutions at a temperature of 45° C. or less. The above-described configuration can prevent peeling of the etching resist film during the etching step, and can selectively etch areas where no etching resist film is present. After the etching step, a cleaning step for cleaning the etched substrate and a drying step for drying the cleaned substrate may be carried out as necessary to prevent contamination of the process line.

[0270] [Touch panel manufacturing method] Examples of the method for manufacturing the touch panel include known methods for manufacturing touch panels. Specifically, a method for manufacturing a touch panel that includes, in this order, a photosensitive layer forming step, a first exposure step, and a protective film or insulating film forming step is preferred. Photosensitive layer forming step: A step of forming a photosensitive layer on a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or wiring) in a substrate using a photosensitive material or a transfer film. First exposure step: a step of pattern-exposing the photosensitive layer Protective film or insulating film forming step: A step of developing the exposed photosensitive layer with an alkaline developer to form a patterned protective film or insulating film on the conductive layer.

[0271] The protective film functions as a film that protects the surface of the conductive layer. The insulating film functions as an interlayer insulating film between the conductive layers. When forming an insulating film for the conductive layer, the touch panel manufacturing method of the present invention preferably further includes a step of forming a conductive layer (preferably a patterned conductive layer, specifically a conductive pattern such as a touch panel electrode pattern or wiring) on ​​the formed insulating film. The photosensitive layer forming step, the first exposure step, and the development step can be carried out in the same procedures as steps X1, X2, and X3 in the method for producing the laminate of embodiment 1, respectively. The substrate having a conductive layer has the same meaning as the substrate having a conductive layer used in step X1, and the preferred embodiments are also the same.

[0272] The touch panel manufactured by the above-described method for manufacturing a touch panel preferably has a transparent substrate, an electrode, and a protective layer (protective film). Examples of detection methods for the touch panel include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method, with the capacitance method being preferred. Examples of touch panel types include in-cell types (e.g., Figures 5 to 8 of JP 2012-517051 A), on-cell types (e.g., Figure 19 of JP 2013-168125 A, and Figures 1 and 5 of JP 2012-089102 A), OGS (One Glass Solution) types, TOL (Touch-on-Lens) types (e.g., Figure 2 of JP 2013-054727 A), other configurations (e.g., Figure 6 of JP 2013-164871 A), and various out-cell types (so-called GG, G1 / G2, GFF, GF2, GF1, and G1F). [Example]

[0273] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass. In the following examples, the weight average molecular weight of a resin (polymer) is a weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0274] In the following examples, unless otherwise specified, the high-pressure mercury lamp used was a model H03-L31 manufactured by Eye Graphics Co., Ltd. This high-pressure mercury lamp has a dominant wavelength of 365 nm and strong line spectra at wavelengths of 254 nm, 313 nm, 405 nm, and 436 nm.

[0275] [Creating protective film] The various components and contents shown in the table below were mixed and stirred at 250 rpm for 20 minutes to prepare photosensitive materials 1 to 7. The obtained photosensitive materials 1 to 7 were each spin-coated onto a 10 cm square copper substrate to a dry thickness of 3.0 μm, followed by drying. The resulting coating film was exposed to light using a high-pressure mercury lamp through a mask so that the frame portion (1 cm wide) of the copper substrate was shielded from light. Development was then carried out using a 1% by mass aqueous solution of sodium carbonate at 23°C for 50 seconds, yielding an 8 cm square film on the copper substrate. The cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm during exposure was 1000 mJ / cm 2 Thereafter, the substrate was post-baked in an oven at 145° C. for 25 minutes, thereby producing protective films 1 to 7 formed on the copper substrate.

[0276] [Various components of photosensitive material] <Polymer P1> PGMEA (propylene glycol monomethyl ether acetate) (60 parts) and PGME (propylene glycol monomethyl ether) (240 parts) were placed in a 2 L flask, and the mixture was heated to 90°C while stirring at 250 rpm. Styrene (80 parts) and acrylic acid (20 parts) were mixed and diluted with PGMEA (60 parts) to obtain a dropping liquid (1). V-601 (dimethyl 2,2'-azobis(2-methylpropionate)) (9.637 parts) was dissolved in PGMEA (136.56 parts) to obtain a dropping liquid (2). The dropping liquid (1) and the dropping liquid (2) were simultaneously added dropwise over 3 hours to the above-mentioned 2 L flask (specifically, a 2 L flask containing a liquid heated to 90°C). After the dropwise addition was completed, V-601 (2.401 parts) was added to the flask three times every hour. The mixture was then stirred at 90°C for an additional 3 hours. By the above procedure, a solution containing polymer P1 (solid content 36.3% by mass) was obtained.

[0277] <Polymer P2> PGMEA (60 parts) and PGME (240 parts) were added to a 2 L flask, and the mixture was heated to 90°C while stirring at 250 rpm. Styrene (59 parts), 9-vinylacridine (20 parts), and acrylic acid (21 parts) were mixed and diluted with PGMEA (60 parts) to obtain a dropping liquid (1). V-601 (dimethyl 2,2'-azobis(2-methylpropionate) (9.637 parts) was dissolved in PGMEA (136.56 parts) to obtain a dropping liquid (2). Dropping liquid (1) and dropping liquid (2) were simultaneously added dropwise over 3 hours to the above-mentioned 2 L flask (specifically, a 2 L flask containing a liquid heated to 90°C). After the dropwise addition was completed, V-601 (2.401 parts) was added to the flask three times every hour. The mixture was then stirred at 90°C for an additional 3 hours. This procedure yielded a solution containing polymer P2 (solid content 36.3% by mass).

[0278] <Polymer P3> PGMEA (propylene glycol monomethyl ether acetate) (60 parts) and PGME (propylene glycol monomethyl ether) (240 parts) were placed in a 2 L flask, and the mixture was heated to 90°C while stirring at 250 rpm. Styrene (85 parts) and acrylic acid (15 parts) were mixed and diluted with PGMEA (60 parts) to obtain a dropping liquid (1). V-601 (dimethyl 2,2'-azobis(2-methylpropionate)) (9.637 parts) was dissolved in PGMEA (136.56 parts) to obtain a dropping liquid (2). The dropping liquid (1) and the dropping liquid (2) were simultaneously added dropwise over 3 hours to the above-mentioned 2 L flask (specifically, a 2 L flask containing a liquid heated to 90°C). After the dropwise addition was completed, V-601 (2.401 parts) was added to the flask three times every hour. The mixture was then stirred at 90°C for an additional 3 hours. This procedure yielded a solution containing polymer P3 (solid content 36.3% by mass).

[0279] The structures of polymers P1 and P2 are shown below. The compositions of the repeating units in polymer P1 were 80% by mass and 20% by mass, respectively, from left to right, and the compositions of the repeating units in polymer P2 were 59% by mass, 20% by mass, and 21% by mass, respectively, from left to right. Polymer P3 contained the same types of repeating units as polymer P1 represented by the following structural formula, and the compositions of the repeating units were 85% by mass and 15% by mass, from left to right. The weight average molecular weight of polymer P1 was 12,000, the weight average molecular weight of polymer P2 was 13,000, and the weight average molecular weight of polymer P3 was 7,000.

[0280] [ka]

[0281] The protective film of each of the examples and comparative examples formed by the above-described procedure contained one of the following polymers a1 to a4. The protective films of Examples 1 and 2 contained polymer a1, the protective films of Examples 3 and 4 contained polymer a2, the protective film of Example 5 contained polymer a3, the protective film of Example 6 contained polymer a3, and the protective film of Comparative Example 1 contained polymer a4.

[0282] [ka]

[0283] <Compound B> Isoquinoline Quinoline Acridine

[0284] <Photopolymerization initiator> IRGACURE OXE01 (BASF)

[0285] <Polymerizable compound> ·BPE-500 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0286] <Solvent> MEK: Methyl ethyl ketone

[0287] [measurement] [Acid value of protective film] Approximately 20 mg of each of the protective films 1 to 7 on the copper substrate was scraped off and freeze-pulverized. After adding 150 μL of NMP (N-methyl-2-pyrrolidone), the resulting solution was stirred for 6 days in a lithium carbonate (Li2CO3) aqueous solution (1.2 g / 100 mL, prepared by dissolving lithium carbonate in ultrapure water and filtering). After stirring, the particles were sedimented by ultracentrifugation (140,000 rpm for 30 minutes). The resulting sediment was then substituted with ultrapure water five times and dried to obtain the analytical sample. The resulting analytical sample was analyzed for the amount of Li (lithium) using ICP-OES (PerkinElmer Optima 7300DV). The amount of acid groups in the protective film (mol / g) was calculated by dividing the obtained value by the number of Li atoms (6.941 g / mol), and the acid value of the protective film (mg KOH / g) was calculated by multiplying the obtained value by the molecular weight of KOH. The acid value of the protective film was measured five times, the maximum and minimum values ​​were removed from the five measured values, and the remaining three measured values ​​were arithmetically averaged. The arithmetic mean values ​​obtained were shown in the tables below as the acid value (mgKOH / g) of the protective film of each Example and Comparative Example. The Li content was analyzed using the following procedure. Approximately 1.5 to 2 mg of the sample was weighed, and 5 mL of a 60% by mass HNO3 aqueous solution was added. The sample was then incinerated using MW Teflon (registered trademark) (UltraWAVE microwave sample decomposition device, max: 260°C). Ultrapure water was added to the incinerated sample to make a 50 mL volume, and the Li content was quantified using the absolute calibration curve method with ICP-OES.

[0288] [Specific maximum absorption wavelength] A total of 30 mg of each of the protective films 1 to 7 on the copper substrate was scraped off, mixed with barium sulfate (270 mg), and pulverized in an agate mortar to a solid powder particle size of 2 μm or less to obtain a measurement sample. The measurement sample (approximately 100 mg) was placed on the sample stage and smoothed to eliminate gaps within the measurement area. Next, the relative reflectance R of the measurement sample was measured by measuring the diffuse reflectance of the barium sulfate (standard sample) and the measurement sample at wavelengths of 300 to 700 nm using a measuring instrument: V-7200 (manufactured by JASCO Corporation). The relative reflectance R (%) obtained by the measurement was then converted to K (absorption coefficient) / S (scattering coefficient) using the following formula: K / S=(1-R) 2 / 2R The above formula is called the Kubelka-Munk function. By the above conversion, a graph was obtained with the horizontal axis: wavelength and the vertical axis: K (absorption coefficient) / S (scattering coefficient), and the peak top in the wavelength range of 300 to 400 nm on the graph was determined as the specific maximum absorption wavelength.

[0289] [Rate of change in K (absorption coefficient) / S (scattering coefficient) before and after heat treatment] The specific maximum absorption wavelength was determined according to the same procedure as in the above [Specific maximum absorption wavelength]. The K (absorption coefficient) / S (scattering coefficient) ratio at this specific maximum absorption wavelength was calculated and used as the K (absorption coefficient) / S (scattering coefficient) ratio at the specific maximum absorption wavelength before heat treatment. Next, the protective film was heated at 140°C for 30 minutes, and then the K (absorption coefficient) / S (scattering coefficient) ratio at the specific maximum absorption wavelength in the wavelength range of 300 to 400 nm was determined according to the same procedure as above. The obtained K / S corresponds to the K (absorption coefficient) / S (scattering coefficient) ratio at the specific maximum absorption wavelength after heat treatment. Next, the rate of change was calculated according to the following formula: Rate of change (%) = [100 × (|K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength before the heat treatment - K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength after the heat treatment|) / K (absorption coefficient) / S (scattering coefficient) at the specific maximum absorption wavelength before the heat treatment]

[0290] [evaluation] [Adhesion] For each of the protective films 1 to 7 on the copper substrate, a 1 mm square grid pattern was cut using a cutter knife on the surface of each protective film opposite the copper substrate, and transparent adhesive tape #600 (manufactured by 3M) was firmly pressed onto the cut surface. The pressed transparent adhesive tape was peeled off from each protective film in a 180° direction. The state of the grid pattern was observed, and the adhesion of the protective film was evaluated according to the following evaluation criteria. Evaluations A and B are practically acceptable levels. A: The total area of ​​the grid pattern on the copper substrate after peeling is 70% or more of the total area of ​​the grid pattern on the copper substrate before peeling. B: The total area of ​​the grid pattern on the copper substrate after peeling is 35% or more and less than 70% of the total area of ​​the grid pattern on the copper substrate before peeling. C: The total area of ​​the grid pattern on the copper substrate after peeling is less than 35% of the total area of ​​the grid pattern on the copper substrate before peeling.

[0291] [Moist heat durability] The copper substrates having any of the protective films 1 to 7 were left to stand in a thermo-hygrostat set at 65°C and 90% RH for a predetermined time, and the time until the copper substrates were discolored was measured and the wet heat durability was evaluated according to the following evaluation criteria. Note that the discoloration of the copper substrates was visually confirmed through the protective film. A: No discoloration was observed on the copper substrate even after 240 hours. B: No discoloration was observed on the copper substrate after 120 hours, but discoloration was observed on the copper substrate after 240 hours. C: No discoloration was observed on the copper substrate after 60 hours, but discoloration was observed on the copper substrate after 120 hours. D: Discoloration of the copper substrate was confirmed after 60 hours.

[0292] [result] In the table, each description indicates the following. The numbers in parentheses in the columns of "Polymer P," "Compound B," "Polymerizable compound," and "Solvent" indicate the respective contents (parts by mass). The content of Polymer P indicates the amount equivalent to the solid content. In the table, "-" in the "specific maximum absorption wavelength" column indicates that there is no specific maximum absorption wavelength in the wavelength range of 300 to 400 nm. In the table, the column "K / S after heating" indicates the K (absorption coefficient) / S (scattering coefficient) at a specific maximum absorption wavelength after heat treatment, with "A" indicating that K / S is 0.01 or greater and 4.0 or less, "B" indicating that K / S is greater than 4.0, and "C" indicating that K / S is less than 0.01 or that the maximum absorption wavelength is not in the range of 300 to 400 nm. In the table, the "change rate" column indicates the change rate calculated by the above [change rate of K / S before and after heat treatment]. In the table, "<10%" indicates less than 10%.

[0293] [Table 2]

[0294] From the evaluation results in the table, it was confirmed that the protective film of the present invention has excellent adhesion to the electrode and also has excellent durability against humidity and heat. It was confirmed that when the acid value of the protective film is 100 mgKOH / g or less (preferably 80 mgKOH / g or less), the wet heat durability is superior. [Explanation of symbols]

[0295] 12: Temporary support 14: Photosensitive layer 16: Cover film 100: Transfer film

Claims

1. A protective film for an electrode, the protective film contains a polymer A having a repeating unit A having an acid group, The acid value of the protective film is 120 mg KOH / g or less, the protective film has a maximum absorption wavelength in the wavelength range of 300 to 400 nm, A protective film in which, when the protective film is heated at 140° C. for 30 minutes, the rate of change in K (absorption coefficient) / S (scattering coefficient) at the maximum absorption wavelength is 10% or less.

2. The protective film according to claim 1 , wherein the acid value of the protective film is 100 mg KOH / g or less.

3. The protective film according to claim 1 , wherein the acid value of the protective film is 80 mg KOH / g or less.

4. 2. The protective film according to claim 1, wherein after heating the protective film at 140°C for 30 minutes, K / S at the maximum absorption wavelength is 4.0 or less.

5. 2. The protective film according to claim 1, wherein after heating the protective film at 140°C for 30 minutes, K / S at the maximum absorption wavelength is 0.01 or more.

6. the polymer A has a group formed by removing one hydrogen atom from a nitrogen-containing aromatic compound, 2. The protective film according to claim 1, wherein the nitrogen-containing aromatic compound has a maximum absorption wavelength in the wavelength range of 300 to 400 nm.

7. The protective film according to claim 1 , wherein the polymer A has a group represented by formula (Zb2): 【Chemistry 1】 In formula (Zb2), X ｂ４ ~X ｂ６ are each independently CR ｂ６ or a nitrogen atom. ｂ４ ~X ｂ６ At least one of R represents a nitrogen atom. ｂ３ represents an alkyl group. ｂ６ represents a hydrogen atom or an alkyl group. b3 represents an integer of 0 to 4. * represents a bonding position.

8. The protective film according to claim 1 , wherein the repeating unit A has a repeating unit represented by formula (a1) or a repeating unit represented by formula (a2). 【Chemistry 2】 In formula (a1), R ａ represents a hydrogen atom or a substituent. X represents a single bond or a divalent linking group having one or more carbon atoms. In formula (a2), Y represents a cyclic group having two or more carbon atoms, Z represents a single bond or a divalent linking group, and at least one of Y and Z represents a group having one or more carbon atoms.

9. The protective film according to claim 1 , wherein the acid value of the protective film is 5 mg KOH / g or more.

10. A laminate comprising, in this order, a substrate, an electrode, and the protective film according to any one of claims 1 to 9.

Images