Photosensitive resin composition

Abstract

The present invention provides a photosensitive resin composition. A photosensitive resin composition for forming a protective film on a conductor portion, comprising (A) an alkali-soluble resin, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator, wherein the photosensitive resin composition satisfies the following conditions (1) and (2): (1) the minimum storage modulus of the photosensitive resin composition before curing is 40 Pa or less; (2) the moisture permeability of the photosensitive resin composition after curing is 300 g / m 2 Less than 24 hours.

Description

[0001] This application is a divisional application. The international application number of its original application is PCT / JP2017 / 043358, the international application date is December 1, 2017, the Chinese national application number is 201780074657.4, the date of entry into China is May 31, 2019, and the name of the invention is "Photosensitive resin composition, photosensitive resin laminate, method for manufacturing resin pattern and method for manufacturing cured film pattern". Technical Field

[0002] The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, a method for producing a resin pattern using the photosensitive resin laminate, and a method for producing a cured film pattern. More specifically, the present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for producing a resin pattern using the same, which are suitable for forming planarizing films, protective films, and interlayer insulating films in electronic components such as liquid crystal displays, organic EL displays, touch panel displays, integrated circuit devices, solid-state image sensors, and semiconductor devices. Background Art

[0003] In recent years, with the progress of high performance, diversification and miniaturization and lightweighting of electronic devices, the number of devices with transparent touch panels (touch sensors) installed on the entire surface of display elements such as liquid crystals has increased. The use of transparent touch panels to identify and select text, symbols, patterns, etc. displayed on the display element, and the use of transparent touch panels to switch the various functions of the device are also increasing. Touch panels are not only used in large electronic devices such as personal computers and televisions, but also in small electronic devices such as car navigation, mobile phones, electronic dictionaries, and display devices such as OA and FA equipment. Electrodes formed of transparent conductive electrode materials are provided in the touch panels. As transparent conductive electrode materials, ITO (Indium-Tin-Oxide), indium oxide and tin oxide are known. These materials have high visible light transmittance and are therefore mainly used as electrode materials for substrates for liquid crystal display elements.

[0004] As existing touch panel methods, there are resistive film methods, optical methods, pressure methods, electrostatic capacitance methods, electromagnetic wave induction methods, image recognition methods, vibration detection methods, ultrasonic methods, etc. Various methods have been put into practical use. In recent years, the utilization of electrostatic capacitance touch panels has progressed the fastest. In an electrostatic capacitance touch panel, when a fingertip, which is a conductor, contacts the touch input surface, capacitive coupling is generated between the fingertip and the conductive film, forming a capacitor. Therefore, the electrostatic capacitance touch panel detects the coordinates of the contact position by capturing the charge change at the contact position of the fingertip. In particular, the projection type electrostatic capacitance touch panel has good operability that can perform complex instructions because it can perform multi-point detection of the fingertip. Therefore, it is being promoted as an input device on the display surface of a device with a small display device such as a mobile phone and a portable music player. Typically, in a projection type electrostatic capacitance touch panel, in order to represent a two-dimensional coordinate based on the X-axis and the Y-axis, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the plurality of X electrodes form a two-layer structure, and ITO is used as the electrode material.

[0005] Furthermore, since the touch panel's border area is not capable of detecting touch locations, narrowing this border area is a key factor in improving product value. Metal wiring is required to transmit touch location detection signals within the border area, but minimizing the border area requires a narrower width. Because ITO's conductivity is not high enough, copper is typically used for the metal wiring.

[0006] However, when a fingertip touches a touch panel like this, corrosive elements such as moisture and salt can penetrate through the sensing area. If these elements penetrate the touch panel, they can corrode the metal wiring, increase the resistance between the electrodes and the driving circuit, or even cause disconnection. To prevent these problems, a rust-proof protective film is required on the metal wiring.

[0007] Furthermore, the metal wiring used to transmit detection signals must be connected to other components via terminals to ensure continuity, and the protective film must be removed from the terminals. Therefore, the protective film requires excellent developability and good removability even in various patterns such as circular holes.

[0008] For example, Patent Document 1 proposes solutions to these problems. Patent Document 1 describes the use of a protective film to suppress corrosion of copper wiring used to transmit touch position detection signals, and mentions the film's moisture permeability and rust resistance. However, there is no mention of the film's rust resistance after undergoing an alkaline development process, suggesting that its rust resistance remains insufficient.

[0009] In response to the recent surge in demand for flexible display substrates, various film-like photosensitive materials, such as photosensitive solder resists and photosensitive dry film resists, are used as protective films to protect the surfaces of wiring boards or patterned circuits on these substrates, in addition to the aforementioned protective films, depending on their intended use.

[0010] Patent Document 2 describes a protective film used as a solder resist for a printed circuit board, and mentions the protective film's alkali developability, soldering heat resistance, and electroless plating resistance. However, there is no description of its rust prevention effect against corrosion caused by salt or the like.

[0011] Patent Documents 3 and 4 describe protective films used as photosensitive dry film resists for forming patterned circuits on printed circuit boards and touch panels. These protective films exhibit excellent alkali developability, resolution, film strength, and adhesion to substrates. However, they fail to describe the properties required as a permanent material for protecting electrodes or metal wiring (e.g., inhibiting corrosion of copper wiring).

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-121929

[0015] Patent Document 2: Japanese Patent Application Laid-Open No. 2011-59613

[0016] Patent Document 3: International Publication No. 2016 / 017596

[0017] Patent Document 4: International Publication No. 2015 / 175961 Summary of the Invention

[0018] Problems to be solved by the invention

[0019] As described above, the techniques described in Patent Documents 1 to 4 still have room for improvement. Therefore, the present invention aims to provide a photosensitive resin composition and a method for producing the same, which exhibit excellent developability, rust resistance, and moisture permeability of the film after alkali development, making it suitable for protecting conductive parts such as electrodes.

[0020] Means for solving problems

[0021] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator has a minimum storage modulus of 40 Pa or less before curing and a moisture permeability of 300 g / m2 after curing. 224 hours or less, a photosensitive resin composition having excellent developability, rust resistance, and moisture permeability of the film after the alkali development step can be obtained, and a photosensitive resin composition suitable for protecting conductive parts such as wiring and electrodes can be obtained, thereby completing the present invention.

[0022] That is, the present invention is as follows. [1]

[0024] A photosensitive resin composition for forming a protective film on a conductor portion, comprising the following components:

[0025] (A) alkali-soluble resin;

[0026] (B) a compound having an ethylenically unsaturated double bond; and

[0027] (C) a photopolymerization initiator,

[0028] The photosensitive resin composition is characterized in that it satisfies the following conditions (1) and (2):

[0029] (1) The minimum storage modulus of the photosensitive resin composition before curing is 40 Pa or less;

[0030] (2) The moisture permeability of the photosensitive resin composition after curing is 300 g / m 2 Less than 24 hours. [2]

[0032] The photosensitive resin composition as described in [1], wherein the glass transition temperature of the alkali-soluble resin (A) is 70° C. or higher. [3]

[0034] In the photosensitive resin composition described in [1] or [2], the alkali-soluble resin (A) comprises (a1) a structure derived from (meth)acrylic acid and (a2) a structure derived from a styrene derivative. [4]

[0036] The photosensitive resin composition according to any one of [1] to [3], wherein the compound (B) having an ethylenically unsaturated double bond comprises:

[0037] (b1) a compound having three or more polymerizable groups in the molecule and a molecular weight of 430 or less, and

[0038] (b2) A compound having only one polymerizable group in the molecule and a molecular weight of 350 or less. [5]

[0040] The photosensitive resin composition as described in [4], wherein the compound (b2) having only one polymerizable group in the molecule and a molecular weight of 350 or less is a compound composed only of atoms selected from the group consisting of C, H, O, N, S, Si, and F. [6]

[0042] The photosensitive resin composition as described in [4] or [5], wherein the compound (b2) having only one polymerizable group in the molecule and a molecular weight of 350 or less is a compound composed only of atoms selected from the group consisting of C, H, O, N, and S. [7]

[0044] The photosensitive resin composition according to any one of [1] to [6], wherein the (C) photopolymerization initiator is an oxime ester compound. [8]

[0046] The photosensitive resin composition according to any one of [1] to [7], further comprising (D) a thermal crosslinking agent. [9]

[0048] The photosensitive resin composition according to any one of [1] to [8], further comprising (E) a rosin ester compound.

[10]

[0050] The photosensitive resin composition as described in [9], wherein the alkali-soluble resin (A) contains an aromatic structure which may have a substituent.

[11]

[0052] The photosensitive resin composition according to any one of [1] to

[10] , further comprising (F) a compound having a phosphate structure and an ethylenically unsaturated group and having a molecular weight greater than 250.

[12]

[0054] The photosensitive resin composition according to any one of [1] to

[11] , wherein the storage modulus of the photosensitive resin composition before curing has two minimum values, both of which are 40 Pa or less.

[13]

[0056] A photosensitive resin composition comprising the following components:

[0057] (A) alkali-soluble resin;

[0058] (B) a compound having an ethylenically unsaturated double bond; and

[0059] (C) a photopolymerization initiator,

[0060] The photosensitive resin composition is characterized in that:

[0061] The above-mentioned (B) compound having an ethylenically unsaturated double bond includes:

[0062] (b1) a compound having three or more polymerizable groups in the molecule and a molecular weight of 430 or less, and

[0063] (b2) a compound having only one polymerizable group in the molecule and a molecular weight of 350 or less,

[0064] The compound (b2) having only one polymerizable group in the molecule and a molecular weight of 350 or less is a compound composed only of atoms selected from the group consisting of C, H, O, N, S, Si, and F.

[14]

[0066] The photosensitive resin composition as described in

[13] , wherein the compound (b2) having only one polymerizable group in the molecule and a molecular weight of 350 or less is a compound composed only of atoms selected from the group consisting of C, H, O, N, and S.

[15]

[0068] The photosensitive resin composition as described in

[13] or

[14] , wherein the alkali-soluble resin (A) comprises (a1) a structure derived from (meth)acrylic acid and (a2) a structure derived from a styrene derivative.

[16]

[0070] The photosensitive resin composition according to any one of

[13] to

[15] , wherein the alkali-soluble resin (A) contains the structure (a2) derived from a styrene derivative in a ratio of 40% by mass to 80% by mass.

[17]

[0072] The photosensitive resin composition according to any one of

[13] to

[16] , wherein the alkali-soluble resin (A) contains the structure (a2) derived from a styrene derivative in a ratio of 50% by mass to 70% by mass.

[18]

[0074] The photosensitive resin composition according to any one of

[13] to

[17] , wherein the alkali-soluble resin (A) contains (a1) a structure derived from (meth)acrylic acid at a ratio of 0.1% by mass to 25% by mass.

[19]

[0076] The photosensitive resin composition according to any one of

[13] to

[18] , wherein the (C) photopolymerization initiator is an oxime ester compound.

[20]

[0078] The photosensitive resin composition according to any one of

[13] to

[19] , wherein the photopolymerization initiator (C) is a compound represented by the following structural formula (1):

[0079] [Chemistry 1]

[0080]

[0081] {wherein, X1 represents an H group or a monovalent organic group, and Y1 and Y2 each independently represent a monovalent organic group, and at least one of Y1 and Y2 comprises a structure represented by the following formula (2),

[0082] [Chemistry 2]

[0083]

[0084] (wherein R1 represents a monovalent organic group, and R2 represents an alkyl group or an organic group having an aryl group)}. [twenty one]

[0086] The photosensitive resin composition as described in

[20] , wherein each of Y1 and Y2 includes a structure represented by the above formula (2). [twenty two]

[0088] The photosensitive resin composition according to any one of

[13] to

[21] , further comprising (D) a thermal crosslinking agent. [twenty three]

[0090] The photosensitive resin composition as described in

[22] , wherein the thermal crosslinking agent (D) contains a blocked isocyanate compound. [twenty four]

[0092] The photosensitive resin composition as described in

[22] or

[23] , wherein the thermal crosslinking agent (D) contains a diol compound.

[25]

[0094] The photosensitive resin composition according to any one of

[13] to

[24] , further comprising (E) a rosin ester compound.

[26]

[0096] The photosensitive resin composition as described in

[25] , wherein the alkali-soluble resin (A) contains an aromatic structure which may have a substituent.

[27]

[0098] The photosensitive resin composition as described in

[25] or

[26] , wherein the acid value of the rosin ester compound (E) is 20 mgKOH / g or less.

[28]

[0100] The photosensitive resin composition according to any one of

[25] to

[27] , wherein the (E) rosin ester compound has a softening point of 100° C. or higher.

[29]

[0102] The photosensitive resin composition according to any one of

[13] to

[28] , further comprising (F) a compound having a phosphate structure and an ethylenically unsaturated group and having a molecular weight greater than 250.

[30]

[0104] The photosensitive resin composition according to any one of

[13] to

[29] , wherein the contents of the (A) alkali-soluble resin, the (b1) compound, the (b2) compound, and the (C) photopolymerization initiator in the photosensitive resin composition are as follows, based on the total mass of the solid content of the photosensitive resin composition:

[0105] The alkali-soluble resin (A) is present in an amount of 10% by mass or more and 70% by mass or less,

[0106] The above-mentioned compound (b1) is 10% by mass or more and 60% by mass or less,

[0107] The above-mentioned (b2) compound is 1% by mass or more and 30% by mass or less, and

[0108] The amount of the photopolymerization initiator (C) is 0.1% by mass or more and 10% by mass or less.

[31]

[0110] A protective film for a touch panel or a touch sensor or a force sensor, characterized in that:

[0111] In an infrared absorption spectrum obtained by infrared spectroscopy, the peak intensity ratio (I / II) of the peak intensity (I) of the spectrum derived from aromatic groups to the peak intensity (II) of the spectrum derived from aliphatic groups is 1.5 or more, and

[0112] The refractive index at a wavelength of 532 nm is 1.550 or higher.

[32]

[0114] A photosensitive resin laminate comprising a support film and a photosensitive resin layer provided on the support film, wherein the photosensitive resin layer is formed from the photosensitive resin composition for forming a protective film for a conductor portion according to any one of [1] to

[30] .

[33]

[0116] A method for producing a pattern, comprising the steps of laminating the photosensitive resin laminate described in

[32] on a substrate, exposing the laminate to light, and then developing the laminate to produce a pattern.

[34]

[0118] A method for manufacturing a cured film pattern, comprising the following steps:

[0119] A process of laminating the photosensitive resin laminate described in

[32] on a substrate, exposing it to light, and then developing it to form a pattern; and

[0120] This pattern is subjected to a post-exposure treatment and / or a heat treatment step for curing.

[35]

[0122] A method for manufacturing a touch panel display device, a device having a touch sensor, or a device having a force sensor, comprising the method for manufacturing a cured film pattern described in

[34] .

[0123] Effects of the Invention

[0124] According to the present invention, a photosensitive resin composition and a photosensitive resin laminate can be provided, which have excellent developability of the photosensitive resin composition (hereinafter also referred to as developability), rust resistance of the film after undergoing an alkali development step (hereinafter also referred to as rust resistance), and moisture permeability, and are suitable for protecting conductive parts such as electrodes. DETAILED DESCRIPTION

[0125] The specific embodiments of the present invention (hereinafter referred to as "embodiments") are described in detail below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

[0126] [Photosensitive resin composition, photosensitive resin laminate]

[0127] In the embodiment of the present invention, the photosensitive resin laminate includes a support film and a photosensitive resin layer containing a photosensitive resin composition.

[0128] The photosensitive resin composition is a photosensitive resin composition for forming a protective film of a conductor portion, and contains the following components:

[0129] (A) alkali-soluble resin;

[0130] (B) a compound having an ethylenically unsaturated double bond; and

[0131] (C) a photopolymerization initiator,

[0132] The photosensitive resin composition satisfies the following conditions (1) and (2):

[0133] (1) The minimum storage modulus of the photosensitive resin composition before curing is 40 Pa or less;

[0134] (2) The moisture permeability of the photosensitive resin composition after curing is 300 g / m 2 Less than 24 hours.

[0135] The photosensitive resin composition may contain (D) a thermal crosslinking agent, (E) a rosin ester compound, (F) a compound having a phosphate structure and an ethylenically unsaturated group and a molecular weight greater than 500, (G) a rust inhibitor, and other components (H) as desired.

[0136] By setting the minimum storage modulus of the photosensitive resin composition before curing to 40 Pa or less, good developability can be achieved. This indicates that the entanglement density of the molecular chains of the components contained in the photosensitive resin composition is sufficiently low. Therefore, it is believed that the alkaline developer has high permeability into the photosensitive resin composition layer and good developability. It is also believed that a low minimum storage modulus indicates a high degree of freedom of molecular motion at that temperature, and the cross-linking reaction during thermal curing is easy to proceed. It is believed that this can suppress the intrusion of corrosive components such as moisture by increasing the cross-linking density after thermal curing, and the rust resistance is also improved. From the perspective of developability and rust resistance, the minimum value is more preferably 30 Pa or less.

[0137] In the present invention, the storage modulus is measured using a dynamic viscoelasticity measuring device (rheometer, DHR-2) manufactured by TA Instruments. The photosensitive resin composition before curing is measured over a temperature range of 30°C to 200°C. The point where the value changes from decreasing to increasing is read from the resulting storage modulus curve, and this point is taken as the minimum value. This storage modulus curve is believed to be formed because, within the measurement temperature range, the curing reaction of (B) the compound having an ethylenically unsaturated double bond, (D) the thermal crosslinking agent, etc., begins, increasing the crosslinking density and causing the storage modulus value to increase from midway through the measurement temperature range.

[0138] Furthermore, by ensuring that the photosensitive resin composition has two minimum storage moduli before curing, both below 40 Pa, it exhibits excellent developability and superior rust resistance. Having two minimum values ​​indicates that the composition can construct two crosslinked structures with different reaction initiation temperatures. This is presumably due to a further increase in crosslink density after curing, which is believed to result in even better rust resistance.

[0139] In addition, the moisture permeability of the photosensitive resin composition after curing is 300 g / m 2 · 24h or less, it can prevent moisture from penetrating the protective film and reaching the conductor part such as the electrode, and play a good rust prevention role. From the perspective of rust prevention, the moisture permeability is more preferably 250g / m2 Less than 24 hours.

[0140] The moisture permeability value varies depending on the sample thickness, measurement temperature, and humidity conditions. The moisture permeability measurement in the present invention is performed according to the cup method of JIS Z 0208, with a sample thickness of 40 μm and moisture permeability conditions of 65°C and 90%.

[0141] Furthermore, since the alkali-soluble resin (A) has carboxyl groups, during the development process using an aqueous sodium carbonate solution, sodium ions penetrate the surface of the cured protective film and form sodium salts with the carboxylic acid of the alkali-soluble resin. This is believed to facilitate the penetration of moisture, salt, and the like into the protective film, deteriorating its rust resistance. Therefore, by setting the acid equivalent of the alkali-soluble resin (A) to 340 g / mol or greater, the protective film can suppress the uptake of sodium ions during the development process while maintaining good developability. This results in a protective film with even higher rust resistance. From the perspective of rust resistance, a more preferred acid equivalent is 430 g / mol or greater.

[0142] The acid equivalent was measured by potentiometric titration using 0.1 mol / L sodium hydroxide using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. When the composition contains two or more alkali-soluble resins (A), the acid equivalent refers to the acid equivalent of the entire alkali-soluble resin.

[0143] Hereinafter, each component constituting the above-mentioned photosensitive resin composition will be described in detail.

[0144] <(A) Alkali-soluble resin>

[0145] The alkali-soluble resin of the present embodiment is preferably a carboxyl group-containing polymer, and is preferably obtained by copolymerizing at least a monomer having a structure (a1) derived from (meth)acrylic acid and a monomer having a structure (a2) derived from a styrene derivative.

[0146] (a1) The structure derived from (meth) acrylic acid preferably contains 0.1% by mass or more and 25% by mass or less relative to the mass of the alkali-soluble resin. By copolymerizing the structure derived from (meth) acrylic acid containing a carboxyl group, the developability is improved, but at the same time, the hydrophilicity is improved, and the rust resistance for protecting the substrate, electrodes, etc. will deteriorate. Therefore, from the aspects of developability and rust resistance, the content of the structure derived from (meth) acrylic acid is preferably 0.1% by mass or more and 25% by mass or less. From the perspective of preventing discoloration of the surface of the substrate obtained after removing the photosensitive layer of the substrate with a protective film by alkali development, the content is preferably 10% by mass or more, and from the perspective of rust resistance, the content is more preferably 20% by mass or less. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid, including (meth) acrylic acid esters, and the same is true hereinafter.

[0147] (a2) The structure derived from the styrene derivative is preferably 40% by mass or more and 80% by mass or less relative to the mass of the alkali-soluble polymer. By copolymerizing the structure derived from the styrene derivative, the hydrophobicity of the alkali-soluble resin is increased and the rust resistance is improved. It is also believed that by having an aromatic group, the film density of the photosensitive resin laminate after curing is increased and the rust resistance is improved. The film density of the photosensitive resin laminate is closely related to the refractive index. The higher the refractive index, the higher the film density tends to increase. Therefore, the content of the structure derived from the styrene derivative is preferably 40% by mass or more. On the other hand, from the perspective of developability, if the refractive index is too high, the developability deteriorates. Therefore, the content of the structure derived from the styrene derivative is preferably 80% by mass or less, more preferably 50% by mass or more from the perspective of rust resistance, and more preferably 70% by mass or less from the perspective of developability. Here, styrene derivatives can be cited, for example, styrene, α-methylstyrene, p-hydroxystyrene, p-methylstyrene, p-methoxystyrene, and p-chlorostyrene.

[0148] Examples of other copolymers include, in addition to the structural units already described, other monomers copolymerizable with these structural units. Examples of other monomers include fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid esters, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylonitrile, esters of vinyl alcohol such as vinyl acetate; aromatic (meth)acrylates such as benzyl (meth)acrylate; and the like.

[0149] The weight-average molecular weight of the alkali-soluble resin is not particularly limited, but is generally preferably between 5,000 and 100,000 from the perspectives of coatability, film strength, and developability. From the perspectives of the properties of the developed aggregates and the properties of the unexposed film, such as the edge melting and chipping properties of the photosensitive resin laminate, the weight-average molecular weight of the alkali-soluble resin is preferably 5,000 or greater. From the perspective of improving developability, the weight-average molecular weight of the alkali-soluble resin is preferably 100,000 or less. Here, edge melting refers to the phenomenon in which the photosensitive resin composition layer overflows from the end of the roll when the photosensitive resin laminate is wound up. Furthermore, chipping refers to the phenomenon in which chips scatter when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin laminate, they can be transferred to the mask during the subsequent exposure process, resulting in failure.

[0150] The weight average molecular weight of the alkali-soluble resin is more preferably 5,000 to 80,000, and even more preferably 5,000 to 50,000 from the viewpoint of reducing the entanglement density of the molecular chains and lowering the storage modulus of the photosensitive resin composition before curing.

[0151] The weight average molecular weight was measured using a gel permeation chromatograph (GPC) manufactured by JASCO Corporation set under the following conditions. The obtained weight average molecular weight is a polystyrene-equivalent value.

[0152] Pump: Gulliver, PU-1580 model; Column: 4 Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K. connected in series;

[0153] Mobile layer solvent: tetrahydrofuran; Calibration curve: a calibration curve defined using a polystyrene standard sample {a calibration curve based on a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) was used}.

[0154] Furthermore, by setting the glass transition temperature (Tg) of the alkali-soluble resin (A) to 70°C or higher, softening of the protective film in high-temperature environments can be prevented, maintaining a higher film density and exhibiting excellent rust resistance. Since the test temperature for rust resistance testing is 85°C, the glass transition temperature (Tg) is more preferably 100°C or higher, and even more preferably 120°C or higher.

[0155] The glass transition temperature (Tg) of the alkali-soluble resin (A) in the present invention is calculated by the following FOX formula (1):

[0156] [Number 1]

[0157]

[0158] (wherein, Tg represents the Tg of the copolymer. Tg1, Tg2, ..., Tg i ,…,Tg N W1, W2, ..., W represents the Tg (K) of each homopolymer. i ,…,W N represents the mass % of each monomer).

[0159] The content of the alkali-soluble resin (A) in the photosensitive resin composition is 10% to 70% by mass based on the mass of the photosensitive resin composition. From the perspective of rust prevention of the covered portion of the wiring or electrode produced on the substrate, the content is preferably 15% to 65% by mass, and more preferably 20% to 60% by mass.

[0160] In particular, in the present invention, it is more preferred that the (A) alkali-soluble resin contains 0.1% by mass or more and 25% by mass or less of (a1) a structure derived from (meth)acrylic acid and 40% by mass or more and 80% by mass or less of (a2) a structure derived from a styrene derivative, and further, as described below, the (B) compound having an ethylenically unsaturated double bond contains (b1) a compound having three or more polymerizable groups in the molecule and a molecular weight of 430 or less, and (b2) a compound having only one polymerizable group in the molecule and a molecular weight of 350 or less, and consisting solely of atoms selected from the group consisting of C, H, O, N, S, Si, and F. Most preferably, the (b2) compound having only one polymerizable group in the molecule and a molecular weight of 350 or less contains a compound consisting solely of atoms selected from the group consisting of C, H, O, N, and S.

[0161] In addition, it is particularly preferable to use an oxime ester compound as the photopolymerization initiator (C). The photosensitive resin composition of this embodiment can have a storage modulus of 40 Pa or less before curing and a moisture permeability of 300 g / m 2 Photosensitive resin composition with a shelf life of less than 24 hours.

[0162] <(B) Compounds Having Ethylenically Unsaturated Double Bonds>

[0163] The compound having an ethylenically unsaturated double bond of the present embodiment is a compound having polymerizability due to having an ethylenically unsaturated group in its structure. The compound having an ethylenically unsaturated double bond preferably includes (b1) a compound having three or more polymerizable groups in the molecule and a molecular weight of 430 or less, and (b2) a compound having one polymerizable group in the molecule and a molecular weight of 350 or less.

[0164] Furthermore, the compound (b2) having one polymerizable group in the molecule and a molecular weight of 350 or less more preferably includes a compound consisting solely of atoms selected from the group consisting of C, H, O, N, S, Si, and F, and further preferably includes a compound consisting solely of atoms selected from the group consisting of C, H, O, N, and S. Compounds having an ethylenically unsaturated double bond may be used in combination with compounds other than those listed above.

[0165] The lower limit of the molecular weight of the compound (b1) and the compound (b2) is not particularly limited, and the molecular weight may be 50 or more, or 100 or more.

[0166] (b1) Compounds having 3 or more polymerizable groups in the molecule and a molecular weight of 430 or less By containing 3 or more polymerizable groups, the crosslinking density of the protective film is increased, and moisture and the like are not easily permeable. In addition, by increasing the crosslinking density, the glass transition temperature (Tg) of the protective film is increased, and as described above, an improvement in rust resistance can be expected. In addition, by making the molecular weight below 430, the storage modulus of the photosensitive resin composition before curing is reduced, and the developability is good. From the aspect of rust resistance, the polymerizable groups in the molecule are more preferably 4 or more, and from the aspect of developability, the molecular weight is more preferably 360 or less. Regarding (b1) compounds having 3 or more polymerizable groups in the molecule and a molecular weight of 430 or less, as their central skeletons, for example, glycerol, trimethylolpropane, pentaerythritol, etc. are cited. From the aspect of rust resistance and developability, it is more preferable to contain pentaerythritol tetra(meth)acrylate or trimethylolpropane tri(meth)acrylate.

[0167] From the perspective of developability and rust resistance, the content of the compound (b1) having three or more polymerizable groups in the molecule and a molecular weight of 430 or less in the photosensitive resin composition is preferably 10% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the mass of the photosensitive resin composition.

[0168] By including (b2) a compound having one polymerizable group in the molecule, a molecular weight of 350 or less, and composed solely of atoms selected from the group consisting of C, H, O, N, S, Si, and F, the overall reaction rate of the compound having an ethylenically unsaturated double bond can be improved, and the crosslinking density of the protective film can be increased. As described above, improved rust resistance can be expected. From the perspective of developability, a molecular weight of 300 or less is more preferred. From the perspective of rust resistance, it is preferably composed solely of atoms selected from the group consisting of C, H, O, N, and S, and even more preferably composed solely of atoms selected from the group consisting of C, H, and O.

[0169] Examples of (b2) compounds having one polymerizable group in the molecule and a molecular weight of 350 or less, and consisting solely of atoms selected from the group consisting of C, H, O, N, S, Si, and F, include: compounds having (meth)acrylic acid added to one end of a polyalkylene oxide; compounds having (meth)acrylic acid added to one end and the other end alkyl ether, allyl ether, fluoroalkyl, or alkoxysilylated; (meth)acrylamide; and the like. Examples include m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 4-methacryloyloxybenzophenone, EO-modified p-cumylphenol acrylate, nonylphenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,6-hexanediol (meth)acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-(acryloyloxy)propyltrimethoxysilane, 2,2,3,4,4,4-hexafluorobutyl acrylate, pentafluorophenyl acrylate, 6-acrylamidohexanoic acid, and N-phenylacrylamide. From the perspective of rust prevention, m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 4-methacryloyloxybenzophenone, and EO-modified p-cumylphenol acrylate are more preferably included.

[0170] From the perspective of developability and rust resistance, the content of the compound (b2) having one polymerizable group in the molecule and a molecular weight of 350 or less, and consisting solely of atoms selected from the group consisting of C, H, O, N, S, Si, and F, in the photosensitive resin composition is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, based on the mass of the photosensitive resin composition.

[0171] <(C) Photopolymerization Initiator>

[0172] The photopolymerization initiator (C) of this embodiment is a compound that generates free radicals by active light and is capable of polymerizing compounds containing ethylenically unsaturated groups, etc. Among them, from the perspective of rust resistance, oxime ester compounds are preferred, and compounds with a high molar absorption coefficient at 365nm are more preferred. By using an oxime initiator with a high absorption coefficient at a wavelength of 365nm, a highly sensitive protective film can be obtained by i-line exposure. It is speculated that this can obtain high surface curability, which can suppress the intrusion of sodium ions in the above-mentioned development process, and as a result, high rust resistance can be obtained.

[0173] Specific examples of the oxime ester compounds include 1,2-octanedione, 1-[(4-phenylthio)phenyl-, 2-(O-benzoyl oxime)] (manufactured by BASF Japan, Irgacure Oxe01, product name), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF Japan, Japan Co., Ltd., IrgacureOxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (product name TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyl oxime) (product name TR-PBG-326, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)(o-tolyl)methanone O-acetyl oxime (Daito DFI-020 manufactured by Chemix Co., Ltd.), 1,8-octanedione, 1,8-bis[9-(2-ethylhexyl)-6-nitro-9H-carbazol-3-yl]-, 1,8-bis(O-acetyl oxime) (ADEKA Arkls manufactured by ADEKA Corporation) NCI-831, product name), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-371, product name, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-391, product name, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), etc.

[0174] In addition, as an oxime ester compound, the compound represented by the following structural formula (1) has high surface curability and is more excellent in terms of sensitivity and rust prevention:

[0175] [Chemistry 3]

[0176]

[0177] {wherein, X1 represents an H group or a monovalent organic group, and Y1 and Y2 each independently represent a monovalent organic group, and at least one of Y1 and Y2 comprises a structure represented by the following formula (2),

[0178] [Chemistry 4]

[0179]

[0180] (In the formula, R1 represents a monovalent organic group, and R2 represents an alkyl group or an organic group having an aryl group.)

[0181] The monovalent organic group refers to a hydrocarbon group (which may be saturated or unsaturated, linear or branched, and may contain a cyclic structure), and may contain a heteroatom or a halogen atom.

[0182] Examples of the compound represented by formula (1) include 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acetyl oxime) (TR-PBG-326, a product name manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-[6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazole-3-yl]-, 2-(O-acetyl oxime) (product name, TR-PBG-326 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), -yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-371, product name, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-391, product name, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0183] From the viewpoint of rust prevention, it is preferred that Y1 and Y2 each include a structure represented by the above formula (2).

[0184] As oxime ester compounds in which Y1 and Y2 each contain a structure represented by the above formula (2), examples thereof include 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-371 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., product name), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (TR-PBG-391 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., product name).

[0185] The content of the photopolymerization initiator (C) in the photosensitive resin composition is 0.1% to 10% by mass, based on the mass of the photosensitive resin composition, and more preferably 0.3% to 5% by mass from the perspectives of sensitivity and resolution. A content of 0.1% to 10% by mass of the photopolymerization initiator provides sufficient photosensitivity while also preventing problems such as insufficient internal photocuring and reduced visible light transmittance caused by increased surface absorption of active light during irradiation.

[0186] In the photosensitive resin composition of this embodiment,

[0187] The content of the (A) alkali-soluble resin, the (b1) compound, the (b2) compound, and the (C) photopolymerization initiator in the photosensitive resin composition is particularly preferably, based on the total mass of the solid content of the photosensitive resin composition:

[0188] (A) 10% by mass or more and 70% by mass or less of the alkali-soluble resin,

[0189] (b1) the compound is 10% by mass or more and 60% by mass or less,

[0190] (b2) the compound is 1% by mass or more and 30% by mass or less, and

[0191] (C) The photopolymerization initiator is contained in an amount of 0.1% by mass to 10% by mass.

[0192] Thereby, developability, rust prevention, sensitivity, and resolution can be made particularly favorable.

[0193] <(D) Thermal Crosslinking Agent>

[0194] To achieve higher rust prevention performance, it is preferred to further compound (D) a thermal crosslinking agent in the photosensitive resin composition. The thermal crosslinking agent (D) is a compound that, upon heating, undergoes an addition reaction or polycondensation reaction with the (A) alkali-soluble resin or the unreacted (B) compound having an ethylenically unsaturated double bond, as well as the thermal crosslinking agent (D) added simultaneously. The temperature at which the addition reaction or polycondensation reaction occurs is preferably 100°C to 150°C. The addition reaction or polycondensation reaction occurs during the heat treatment after pattern formation by development.

[0195] Specific examples of the thermal crosslinking agent include blocked isocyanate compounds, diol compounds, and the thermal crosslinking agents described in paragraphs

[0054] and thereafter of International Publication No. 2016 / 047691, but the present invention is not limited thereto.

[0196] The blocked isocyanate compound is a compound obtained by reacting a blocking agent with an isocyanate compound having two or more isocyanate groups in the molecule.

[0197] Examples of the isocyanate compound include 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylenediisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 4,4′-dihydroxydiisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenyl diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-phenylene diisocyanate, 2,6-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and hexamethylene diisocyanate.

[0198] Examples of the blocking agent include alcohols, phenols, ε-caprolactam, oximes, active methylene groups, thiols, amines, imides, amides, imidazoles, ureas, carbamates, imides, and sulfites.

[0199] Specific examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., DURANATE SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden Co., Ltd.), toluene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), 4,4′-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Blonate manufactured by Daiei Sangyo Co., Ltd.). PMD-OA01 and PMD-MA01, etc.), 1,3-bis(isocyanatemethyl)cyclohexane-based blocked isocyanates (for example, Takenate B-846N manufactured by Mitsui Chemicals, Inc., CORONET BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (for example, 7950, 7951, and 7990 manufactured by Baxenden). These blocked isocyanate compounds may be used alone or in combination of two or more.

[0200] A diol compound is a compound containing two hydroxyl groups per one molecular chain, and examples thereof include compounds containing hydrocarbon groups such as aliphatic, aromatic, and alicyclic groups in their backbones.

[0201] Specific examples of the diol compound include polytetramethylene glycol (e.g., P4TMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, and PTMG3000 manufactured by Mitsubishi Chemical Corporation), polybutadiene diol (e.g., G-1000, G-2000, and G-3000 manufactured by Nippon Soda Co., Ltd.), hydrogenated polybutadiene diol (e.g., GI-1000, GI-2000, and GO-3000 manufactured by Nippon Soda Co., Ltd.), and polycarbonate diol (e.g., DURANOL T5651, DURANOL T5652, DURANOL T4671, DURANOL G4672, DURANOL G3452, and DURANOL G4673 manufactured by Asahi Kasei Corporation). G3450J, and KURARAY POLYOL C-590, KURARAY POLYOL C-1090, KURARAY POLYOL C-2090, and KURARAY POLYOL C-3090 manufactured by KURARAY Co., Ltd.), polycaprolactone diols (for example, PRAXCELL 205PL, PRAXCELL 210, PRAXCELL 220, and PRAXCELL 220PL manufactured by Daicel Co., Ltd.), polyester diols (for example, KURARAY POLYOL P-530, KURARAY POLYOL P-2030, and KURARAY POLYOL P-2050, and HS2N-220S manufactured by Toyokuni Oil Manufacturing Co., Ltd., etc.), bisphenols (e.g., bisphenol A manufactured by Mitsubishi Chemical Corporation, etc.), and hydrogenated bisphenols (e.g., Rikabinol HB manufactured by Shin Nippon Rika Co., Ltd., etc.). These diol compounds may be used alone or in combination of two or more.

[0202] The (D) thermal crosslinking agent is preferably a blocked isocyanate compound from the viewpoint of rust prevention, and more preferably further contains a diol compound from the viewpoint of developability.

[0203] During the heat treatment after pattern formation by development, the blocked isocyanate compound reacts with the carboxyl groups of the alkali-soluble resin (A), thereby reducing the hydrophilicity of the cured film and improving rust resistance for protecting substrates, electrodes, etc. It is further believed that crosslinking with the alkali-soluble resin (A) increases the crosslink density of the cured film and reduces water diffusivity, thereby improving rust resistance. Furthermore, since the isocyanate groups of the blocked isocyanate are blocked by the blocking agent, reaction with the alkali-soluble resin (A) at room temperature is suppressed, thereby maintaining the stability of the photosensitive resin composition.

[0204] Diol compounds have hydrophilic hydroxyl groups, resulting in excellent developability. Furthermore, during the heat treatment after pattern formation by development, the hydroxyl groups in the diol compound react with the blocked isocyanate compound, maintaining excellent rust resistance. From the perspective of developability, the molecular weight of the diol compound is preferably 300 to 3,000, with a molecular weight of 500 to 2,000 being particularly preferred.

[0205] The content of the (D) thermal crosslinking agent in the photosensitive resin composition is 0.2% by mass to 40% by mass based on the mass of the photosensitive resin composition. From the viewpoint of developability and rust prevention, the content is more preferably 1% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass.

[0206] <(E) Rosin Ester Compound>

[0207] From the perspective of exhibiting higher rust prevention performance, it is preferred to further compound (E) a rosin ester compound in the photosensitive resin composition. The (E) rosin ester compound in this embodiment refers to a compound having an ester bond formed by reacting a compound selected from the group consisting of abietic acid, a dimer of abietic acid, a hydride of abietic acid, and a disproportionate of abietic acid, which is a non-volatile component of rosin and is a tricyclic diterpene having 20 carbon atoms (hereinafter collectively referred to as a "bietic acid derivative") with any one of a hydroxyl compound, a phenolic compound, and a glycidyl compound; or a compound having an ester bond formed by reacting a glycidyl rosin derivative with any one of a carboxyl compound and a phenolic compound.

[0208] Specific examples of the (E) rosin ester compound include Ester Gum series, Pine Crystal series, Super Ester series, Pensel series, and BEAM SET 101, which are products of Arakawa Chemical Co., Ltd.; and Hari Ester series, Neotall series, and Haritack series, which are products of Harima Chemicals Co., Ltd.

[0209] The (E) rosin ester compound is a compound that has an alicyclic structure and an ester structure, which enhances hydrophobicity. Since it has good compatibility with the (A) alkali-soluble resin, the (B) compound having an ethylenically unsaturated double bond, and the (C) photopolymerization initiator in the photosensitive resin composition, it does not hinder the developability of the composition, resulting in an excellent balance of rust prevention, moisture permeability, and developability. When the photosensitive resin composition contains the (E) rosin ester compound, the (A) alkali-soluble resin preferably contains an aromatic structure that may be substituted. This allows the aforementioned properties to be particularly preferred.

[0210] From the viewpoint of rust prevention, the (E) rosin ester compound more preferably has an acid value of 20 mgKOH / g or less. Examples of the products manufactured by Arakawa Chemical Co., Ltd. and Harima Chemicals Co., Ltd. include Pine Crystal KE-100, Ester Gum 105, Super Ester A-115, Super Ester A-125, Pensel A, Pensel C, Pensel D-125, Pensel D-135, Pensel D-160, BEAM SET 101, Hari Ester S, Neotall 125HK, Haritack F105, Haritack FK125, and Haritack PCJ.

[0211] Furthermore, from the perspective of moisture permeability, the (E) rosin ester compound preferably has a softening point of 100°C or higher. Specific examples of compounds meeting these conditions include Ester Gum 105, Super Ester A-115, Super Ester A-125, Pensel A, Pensel C, Pensel D-125, Pensel D-135, Pensel D-160, and Neotall 125HK. A softening point of 110°C or higher is particularly preferred. Specific examples of compounds meeting these conditions include Super Ester A-115, Super Ester A-125, Pensel A, Pensel C, Pensel D-125, Pensel D-135, Pensel D-160, and Neotall 125HK. The (D) rosin ester compound may be used alone or in combination of two or more.

[0212] The content of the (E) rosin ester compound in the photosensitive resin composition is 1% to 20% by mass relative to 100% by mass of the total solids content of the photosensitive resin composition. From the perspectives of moisture permeability and developability, the content is more preferably 5% to 20% by mass. From the perspective of adhesion to the substrate, the content is even more preferably 5% to 15% by mass. When the content of the (E) rosin ester compound is within the range of 1% to 20% by mass, a good balance between moisture permeability and developability is achieved.

[0213] <(F) Compounds Having a Phosphate Structure and an Ethylenically Unsaturated Group and a Molecular Weight Greater than 250>

[0214] The photosensitive resin composition may further contain (F) a compound having a phosphate structure and an ethylenically unsaturated group and having a molecular weight of more than 250 from the viewpoint of rust prevention and adhesion to the substrate.

[0215] The phosphate structure in the compound (F) having a phosphate structure and an ethylenically unsaturated group and a molecular weight greater than 250 can be a phosphate monoester structure, a phosphate diester structure, or a phosphate triester structure, preferably a phosphate monoester structure or a phosphate diester structure. That is, component F preferably includes a compound with a P-OH structure. As ethylenically unsaturated groups, (meth) acryloyl, vinyl, allyl, styryl, vinyl ether, vinyl ester, etc. can be cited, preferably (meth) acryloyl, more preferably (meth) acryloyloxy. From the aspect of rust resistance, the molecular weight of the compound (F) having a phosphate structure and an ethylenically unsaturated group and a molecular weight greater than 250 is preferably 280 or more, more preferably 300 or more, more preferably 320 or more, more preferably 350 or more, more preferably 380 or more, more preferably 400 or more, more preferably 420 or more. The upper limit of the molecular weight of the (F) compound is not particularly limited, and can be 1500 or less, 1000 or less, or 700 or less.

[0216] (F) The compound having a phosphate structure and an ethylenically unsaturated group and having a molecular weight of more than 250 may be used alone or in combination of two or more.

[0217] The content of the compound (F) having a phosphate structure and an ethylenically unsaturated group and having a molecular weight of more than 250 in the photosensitive resin composition is 0.01 to 10% by mass relative to 100% by mass of the total solid content of the photosensitive resin composition. From the perspectives of moisture permeability, developability, and rust resistance, the content is more preferably 0.01 to 5% by mass. From the perspectives of rust resistance and adhesion to the substrate, the content is even more preferably 0.1 to 3% by mass.

[0218] <(G) Rust Inhibitor>

[0219] The rust preventive agent of the present embodiment refers to a compound having an anti-rust effect, and is, for example, a substance that forms a film on a metal surface to prevent corrosion or rusting of the metal.

[0220] As a rust preventive, from the aspects of compatibility and sensitivity with the photosensitive resin composition of this embodiment, heterocyclic compounds containing N, S, O, etc. are preferred, for example, tetrazole and its derivatives, triazole and its derivatives, imidazole and its derivatives, indazole and its derivatives, pyrazole and its derivatives, imidazoline and its derivatives, oxazole and its derivatives, isoxazole and its derivatives, oxadiazole and its derivatives, thiazole and its derivatives, isothiazole and its derivatives, thiadiazole and its derivatives, thiophene and its derivatives, etc. The derivatives described herein include compounds having substituents introduced into the structure of the parent. For example, if it is a tetrazole derivative, it includes compounds having substituents introduced into tetrazole. There is no particular limitation on the substituents, for example, hydrocarbon groups (which may be saturated or unsaturated, linear or branched, and may contain a cyclic structure in the structure), or substituents containing one or more hydroxyl groups, carbonyl groups, carboxyl groups, amino groups, amide groups, nitro groups, cyano groups, mercapto groups, and halogen (fluorine, chlorine, bromine, iodine, etc.) groups having heteroatoms.

[0221] Furthermore, from the perspective of rust prevention, preferred heterocyclic compounds include those having a heterocyclic ring composed of C and N and / or S, wherein the number of N atoms in the heterocyclic ring is 3 or less, the number of S atoms is 3 or less, or the total number of N and S atoms is 3 or less. More preferred heterocyclic compounds include triazole and its derivatives, imidazole and its derivatives, imidazoline and its derivatives, thiazole and its derivatives, isothiazole and its derivatives, thiadiazole and its derivatives, and thiophene and its derivatives. From the perspective of rust prevention and developability, benzotriazole and its derivatives, and imidazole and its derivatives are even more preferred.

[0222] Specific examples of compounds having a heterocyclic ring composed of C and N and / or S, wherein the number of N atoms in the heterocyclic ring is 3 or less, or the number of S atoms is 3 or less, or the total number of N atoms and S atoms is 3 or less are shown below:

[0223] Triazoles, such as 1,2,3-triazole, 1,2,4-triazole, etc.;

[0224] triazole derivatives, such as 3-mercaptotriazole, 3-amino-5-mercaptotriazole, benzotriazole, 1H-benzotriazole-1-acetonitrile, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole, 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole, 1H-benzotriazole-1-methanol, 5-methyl-1H-benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, 5-chlorobenzotriazole, 5-nitrobenzotriazole, and the like;

[0225] Imidazole; imidazole derivatives, such as undecyl imidazole, benzimidazole, 5-carboxybenzimidazole, 6-bromobenzimidazole, 5-chlorobenzimidazole, 2-hydroxybenzimidazole, 2-(1-hydroxymethyl)benzimidazole, 2-methylbenzimidazole, 5-nitrobenzimidazole, 2-phenylbenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, and the like;

[0226] Imidazoline; imidazoline derivatives, such as 2-undecyl imidazoline, 2-propyl-2-imidazoline, 2-phenyl imidazoline, etc.;

[0227] Thiazole; thiazole derivatives, such as 2-amino-4-methylthiazole, 5-(2-hydroxyethyl)-4-methylthiazole, benzothiazole, 2-mercaptobenzothiazole, 2-aminobenzothiazole, 2-amino-6-methylbenzothiazole, (2-benzothiazolylmercapto)acetic acid, 3-(2-benzothiazolylmercapto)propionic acid, etc.;

[0228] Isothiazole; isothiazole derivatives, such as 3-chloro-1,2-benzisothiazole, etc.;

[0229] Thiadiazoles, such as 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, etc.; thiadiazole derivatives, such as 4-amino-2,1,3-benzothiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 2-amino-5-methyl-1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2-mercapto-5-methyl-1,3,4-thiadiazole, etc.;

[0230] Thiophene; thiophene derivatives, such as 2-thiophenecarboxylic acid, 3-amino-2-thiophenecarboxylic acid methyl ester, 3-methylbenzothiophene, etc.

[0231] Among the above-mentioned rust preventive agents, benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, and 5-chlorobenzotriazole are particularly preferred from the viewpoint of rust preventive properties and developability.

[0232] On the other hand, as the component (G), tetrazole and its derivatives, triazole and its derivatives, indazole and its derivatives, and thiadiazole and its derivatives are preferred from the viewpoint of rust prevention and adhesion.

[0233] Specific examples of tetrazoles include 1H-tetrazole. Specific examples of tetrazole derivatives include 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-(dimethylaminoethyl)-5-mercapto-1H-tetrazole, and 5-phenyl-1H-tetrazole.

[0234] Specific examples of indazole include 1H-indazole, and examples of indazole derivatives include 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-bromoindazole, 6-hydroxyindazole, 3-carboxyindazole, and 5-nitroindazole.

[0235] Specific examples of triazole and its derivatives, and thiadiazole and its derivatives include the ones described above.

[0236] Among these, 5-amino-1H-tetrazole, 5-carboxybenzotriazole, 5-aminoindazole, and 5-amino-1,2,3-thiadiazole are particularly preferred from the viewpoint of rust prevention and adhesion.

[0237] In this embodiment, the above-described rust preventive agents may be used alone or in combination of two or more.

[0238] From the viewpoint of rust prevention and developability, the content of the rust inhibitor in the photosensitive resin composition is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.2 to 3% by mass, based on the mass of the photosensitive resin composition.

[0239] <Other ingredients>

[0240] In this embodiment, in addition to components (A) to (G), the photosensitive resin composition may further contain the following components as other components (H): oligomers having a carboxyl group and an ethylenically unsaturated group, polymerization inhibitors such as aluminum salts to which 3 mol of nitrosophenylhydroxylamine have been added, antioxidants, adhesion aids, leveling agents, fillers, defoaming agents, and flame retardants, etc. These components may be used alone or in combination of two or more.

[0241] <Photosensitive Resin Layer>

[0242] The photosensitive resin layer of this embodiment preferably has a thickness of 15 μm or less, and an absorbance of the photosensitive resin layer at a wavelength of 365 nm of 0.01 to 0.05 per μm of the photosensitive resin layer thickness. Excessively thick photosensitive resin layers degrade flexibility, so the thickness of the photosensitive resin layer is preferably 15 μm or less. To ensure conformity to the unevenness of wiring and to ensure rust resistance, the thickness is preferably 3 μm or greater.

[0243] <Details of Photosensitive Resin Laminate>

[0244] The photosensitive resin laminate comprises a photosensitive resin layer containing a photosensitive resin composition and a support film. Specifically, the layer containing the photosensitive resin composition is laminated on the support film. The photosensitive resin laminate may, if desired, have a protective layer on the surface of the photosensitive resin layer opposite to the support film.

[0245] As the support film used in this embodiment, a transparent film that can transmit the light emitted by the exposure light source is preferably used. As such a support film, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, film containing cellulose and its derivatives, etc. can be cited. These films can also use stretched films as needed. The haze of the support film is preferably 5 or less. The smaller the thickness of the support film, the more advantageous it is in terms of resolution and economy, but in order to maintain strength, it is preferably 10 μm to 30 μm.

[0246] An important characteristic of a protective layer used in a photosensitive resin laminate is that the adhesion between the protective layer and the photosensitive resin layer is sufficiently weaker than the adhesion between the support film and the photosensitive resin layer, allowing for easy peeling. Preferred examples of protective layers include polyethylene films and polypropylene films. Furthermore, films with excellent peelability, such as those described in Japanese Patent Application Laid-Open No. 59-202457, can also be used as protective layers. The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.

[0247] The method for producing a photosensitive resin laminate comprises the steps of applying a coating liquid onto a support (e.g., a support film) and drying the coating liquid, and further comprising the step of laminating a protective layer on the photosensitive resin layer as needed. The coating liquid can be obtained by uniformly dissolving the photosensitive resin composition described above in a solvent.

[0248] Examples of the solvent for dissolving the photosensitive resin composition include ketones represented by methyl ethyl ketone (MEK); alcohols represented by methanol, ethanol, or isopropyl alcohol; and the like.

[0249] The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support is 10 mPa·s to 800 mPa·s at 25°C.

[0250] Examples of coating methods include knife coating, Meyer bar coating, roll coating, screen coating, spin coating, inkjet coating, spray coating, dip coating, gravure coating, curtain coating, and die coating. Drying conditions for the coating solution are not particularly limited, but the drying temperature is preferably 50° C. to 130° C., and the drying time is preferably 30 seconds to 30 minutes.

[0251] In this embodiment, the photosensitive resin laminate is preferably used to form a protective film for a conductor portion. In this case, the conductor portion is more preferably a copper electrode, an alloy electrode of nickel, palladium, silver, titanium, molybdenum, or the like with copper, or a transparent electrode. More specifically, the photosensitive resin laminate can be used as a protective film for lead-out wiring in the frame region of a touch panel (touch sensor or force sensor), or as a protective film for the copper electrodes in the sensing region.

[0252] [Resin pattern, cured film pattern, and method for producing the same]

[0253] The formation of a resin pattern using a photosensitive resin laminate can be performed by a method for producing a resin pattern including the following steps:

[0254] a lamination step of laminating the photosensitive resin laminate on a substrate;

[0255] an exposure step of exposing the laminated photosensitive resin laminate to light; and

[0256] A developing step is performed to develop the exposed photosensitive resin laminate.

[0257] Furthermore, in order to use the resin pattern as a protective film for the conductor portion, the method for producing the resin pattern preferably includes a step of subjecting the resin pattern to post-exposure treatment and / or heat treatment after the development step to form a cured film pattern.

[0258] An example of a specific method is shown below. As the substrate, a substrate having copper wiring formed on a flexible copper-clad laminate, a touch panel substrate or a touch sensor substrate (e.g., a force sensor) having a transparent electrode (e.g., ITO, Ag nanowire substrate, etc.) or a metal electrode (e.g., Cu, Al, Ag, Ni, Mo, or alloys of at least two thereof) formed on a glass substrate or a transparent resin substrate can be used. The flexible copper-clad laminate, the substrate for forming touch panel electrodes, or the substrate for forming touch sensor electrodes is a substrate having a copper layer or a transparent electrode, or a metal layer serving as a raw material for a metal electrode, formed on a flexible film.

[0259] Examples of the above-mentioned film include films made of film materials such as polyimide, polyester (PET, PEN), and cycloolefin polymer (COP). The thickness of the above-mentioned film is preferably 10 μm to 100 μm. In addition, as the above-mentioned copper, in addition to pure copper, alloys containing copper as a main component can also be used. The "main component" here means that at least 50% by mass of the alloy is copper. Examples of the alloy metal include alloys of nickel, palladium, silver, titanium, molybdenum, etc. with copper.

[0260] The thickness of the copper layer is preferably 50 nm to 2 μm. From the perspective of uniformity of the copper layer, the thickness of the copper layer is more preferably 100 nm or more.

[0261] A photosensitive resin layer is formed on the copper layer of the substrate by laminating the photosensitive resin laminate onto the substrate. When the photosensitive resin laminate has a protective layer, it is preferred that after peeling off the protective layer, the photosensitive resin laminate is heated and pressed onto the surface of the substrate using a laminator for lamination. In this case, the photosensitive resin laminate can be laminated only on one side of the substrate surface or on both sides. The heating temperature is generally about 40°C to 160°C. The heating and pressing can be performed using a two-stage laminator with twin rollers, or by repeatedly passing the photosensitive resin laminate and the substrate through the rollers. In addition, when a vacuum laminator is used, the protective film has good followability to the unevenness of the substrate based on wiring, etc., which can prevent the disadvantage of air mixing between the photosensitive resin laminate and the substrate.

[0262] Next, an exposure process is performed using an exposure machine. If necessary, the support film is peeled off from the photosensitive resin laminate, and the photosensitive resin layer is exposed to active light through a photomask. The exposure amount is determined by the light source illumination and the exposure time. The exposure amount can be measured using a light meter. As exposure machines, there can be cited scattered light exposure machines using an ultra-high pressure mercury lamp as a light source, parallel light exposure machines with adjusted parallelism, proximity exposure machines with a gap set between the mask and the workpiece, and the like. Furthermore, as exposure machines, there can be cited projection exposure machines with a mask and image size ratio of 1:1, high-intensity reduced projection exposure machines called Stepper (registered trademark), or exposure machines using a concave mirror called Mirror Projection Aligner (registered trademark).

[0263] Alternatively, a direct drawing exposure method can be used during the exposure process. Direct drawing exposure involves drawing directly onto the substrate without using a photomask. Light sources include, for example, solid-state lasers, semiconductor lasers, or ultrahigh-pressure mercury lamps with a wavelength of 350nm to 410nm. The drawing pattern is controlled by a computer. The exposure dose in this case is determined by the light source's illumination and the substrate's travel speed.

[0264] Then, a developing device is used to perform a developing process. After exposure, if there is a support film on the photosensitive resin layer, the support film is removed as needed, and then an alkaline aqueous solution developer is used to develop and remove the unexposed part to obtain a resin pattern. As the alkaline aqueous solution, an aqueous solution of Na2CO3 or K2CO3 (alkaline aqueous solution) is preferably used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, and is generally an aqueous solution of Na2CO3 with a concentration of about 0.2% by mass to 2% by mass and a temperature of about 20°C to 40°C. Surfactants, defoaming agents, and a small amount of organic solvents for promoting development can also be mixed into the alkaline aqueous solution. Considering the effect on the substrate, an amine-based alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution can also be used. The concentration of the alkaline compound in the aqueous solution can be appropriately selected according to the development speed. From the aspects of less odor, excellent handleability, and simple management and post-processing, a 1% by mass, 30°C to 35°C Na2CO3 aqueous solution is particularly preferred. As a developing method, known methods such as alkaline water spraying, showering, shaking immersion, brushing, and scraping can be mentioned.

[0265] After development, the alkali in the alkaline aqueous solution remaining in the resin pattern can be treated with an acid (neutralized) process using an organic acid, an inorganic acid, or an aqueous solution of these acids by known methods such as spraying, shaking, dipping, brushing, or scraping. Furthermore, a water washing process can be performed after the acid treatment (neutralization).

[0266] The resin pattern can be obtained through the above-mentioned steps, and a post-exposure step and / or a heating step can be further performed. By performing the post-exposure step and / or the heating step, the rust resistance is further improved. As the exposure dose in the post-exposure treatment, 200 mJ / cm is preferred. 2 ~1,000mJ / cm 2 In the heating process, the temperature is preferably 40°C to 200°C. From the perspective of the manufacturing process, the heating time is preferably 60 minutes or less. As a heating method, a heating furnace using a suitable method such as hot air, infrared, or far infrared can be used. As an atmosphere for the heating treatment, an N2 atmosphere or an N2 / O2 atmosphere can be mentioned.

[0267] According to this embodiment, a photosensitive resin composition and a photosensitive resin laminate are provided that have excellent rust resistance and developability and are suitable for protecting conductive parts such as wiring and electrodes. Such a photosensitive resin laminate is suitable as a protective film for wiring, electrodes, etc. used in touch panels, touch sensors, or force sensors.

[0268] The touch panel protective film or the touch sensor or force sensor protective film of this embodiment has an infrared absorption spectrum obtained by infrared spectroscopy, and the peak intensity ratio (I / II) of the peak intensity of the spectrum derived from aromatics (I) to the peak intensity of the spectrum derived from aliphatics (II) is 1.5 or more, and the refractive index at a wavelength of 532nm is 1.550 or more. The peak intensity (I) of the spectrum derived from aromatics mentioned here refers to the peak intensity at 700cm in the infrared absorption spectrum measured by the method described in the Examples below. -1 The peak intensity (II) of the spectrum originating from aliphatic groups refers to the peak at 1450 cm -1 The peak intensity ratio mentioned here is expressed by the following formula (2).

[0269] Peak intensity ratio = I / II (2)

[0270] In addition, the refractive index mentioned here means the refractive index measured by the method described in the Examples mentioned later.

[0271] To prevent corrosion of metal wiring, it is necessary to suppress the intrusion of corrosive components such as moisture and salt. Therefore, increasing the hydrophobicity and film density of the protective film is effective. However, when used as a photosensitive material, it is necessary to use an alkaline aqueous solution for development, so a certain degree of hydrophilicity is also required. By including aromatic groups as hydrophobic groups, moderate hydrophobicity can be imparted, forming a protective film with a balance between rust resistance and developability. In addition, film density is closely related to refractive index. The higher the refractive index, the higher the film density tends to be, and the rust resistance and moisture permeability are improved.

[0272] From the perspective of rust prevention and developability, the peak intensity ratio is preferably 1.5 to 4.0, more preferably 2.0 to 3.5. From the perspective of moisture permeability and developability, the refractive index is preferably 1.550 to 1.600, more preferably 1.560 to 1.590. The upper limit of the peak intensity ratio is not particularly limited and may be 6.0 or less, or 5.0 or less. The upper limit of the refractive index is not particularly limited and may be 1.700 or less, or 1.650 or less.

[0273] [Touch panel display device, device having touch sensor or force sensor]

[0274] By forming a cured film of the photosensitive resin laminate of this embodiment on a touch panel substrate, a touch panel display device having a cured film of the photosensitive resin laminate and a device having a cured film of the photosensitive resin laminate and a touch sensor and / or force sensor can be provided.

[0275] Examples of touch panel substrates generally include substrates used for touch panels, touch sensors, or force sensors, such as glass plates, plastic plates, plastic films, and ceramic plates. Touch panel electrodes or metal wiring made of ITO, Cu, Al, Ag, Ni, Mo, or alloys containing at least two of these, which are the target of forming a protective film, may be provided on the substrate, with an insulating layer provided between the substrate and the electrodes.

[0276] A touch panel substrate having touch panel electrodes can be obtained, for example, by the following process: a metal film is formed by sputtering ITO and then Cu on a touch panel substrate such as polyester or COP film, followed by a photosensitive film for etching on the metal film to form a desired resist pattern. Unnecessary Cu is removed using an etching solution such as an aqueous ferric chloride solution, and the resist pattern is then peeled off and removed.

[0277] The method for forming a cured film as a protective film on a touch panel substrate preferably includes the following steps in sequence: a first step of laminating the photosensitive resin laminate of the present embodiment on the touch panel substrate; a second step of curing a specified portion of the protective film by irradiation with active light; a third step of removing portions other than the specified portion of the protective film (portions of the protective film not irradiated with active light) to form a cured product of a patterned protective film; and a fourth step of exposing and / or heat-treating the patterned protective film.

[0278] By preparing a touch panel substrate having a cured film pattern of a photosensitive resin laminate as described above, a touch panel display device having a cured film of a photosensitive resin laminate, or a device having a cured film of a photosensitive resin laminate and a touch sensor and / or force sensor can be preferably provided.

[0279] Example

[0280] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0281] First, the preparation of the binder polymer solution will be described.

[0282] <Preparation of Binder Polymer Solution (A-1)>

[0283] A flask equipped with a stirrer, a reflux cooler, an inert gas inlet, and a thermometer was charged with 100% by mass of methyl ethyl ketone and heated to 75°C under a nitrogen atmosphere. Methacrylic acid (MAA) (20% by mass), methyl methacrylate (MMA) (0.5% by mass), benzyl methacrylate (BzMA) (79.5% by mass), and an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) were uniformly added dropwise over 2 hours. Stirring was continued at 75°C for 10 hours after the addition. After the reaction was complete, the resulting resin solution was diluted with methyl ethyl ketone to obtain a binder polymer solution (solids content: 43% by mass) (A-1) having an acid equivalent of 430 g / mol, a weight-average molecular weight of approximately 20,000, and a glass transition temperature (Tg) of 79°C.

[0284] <Preparation of Binder Polymer Solution (A-2)>

[0285] Using the same method as the above-mentioned binder polymer (A-1), using 21 mass% of methacrylic acid, 40 mass% of styrene (St), and 39 mass% of methyl methacrylate, a binder polymer solution (solid content 41 mass%) (A-2) with an acid equivalent of 410 g / mol, a weight-average molecular weight of approximately 30,000, and a glass transition temperature (Tg) of 123°C was obtained.

[0286] <Preparation of Binder Polymer Solution (A-3)>

[0287] Using the same method as the above-mentioned binder polymer (A-1), using 20% ​​by mass of methacrylic acid, 55% by mass of styrene, and 25% by mass of methyl methacrylate, a binder polymer solution (solid content 50% by mass) (A-3) with an acid equivalent of 430 g / mol, a weight-average molecular weight of approximately 25,000, and a glass transition temperature (Tg) of 121°C was obtained.

[0288] <Preparation of Binder Polymer Solution (A-4)>

[0289] Using the same method as the above-mentioned binder polymer (A-1), 25% by mass of methacrylic acid and 75% by mass of styrene were used to obtain a binder polymer solution (50% by mass) (A-4) having an acid equivalent of 344 g / mol, a weight-average molecular weight of approximately 25,000, and a glass transition temperature (Tg) of 125°C.

[0290] <Preparation of Binder Polymer Solution (A-5)>

[0291] Using the same method as the above-mentioned binder polymer (A-1), using 20 mass% of methacrylic acid, 55 mass% of styrene, 4 mass% of methyl methacrylate, and 21 mass% of n-butyl acrylate (nBA), a binder polymer solution (solid content 49 mass%) (A-5) with an acid equivalent of 430 g / mol, a weight-average molecular weight of approximately 25,000, and a glass transition temperature (Tg) of 67°C was obtained.

[0292] <Preparation of Binder Polymer Solution (A-6)>

[0293] Using the same method as the above-mentioned binder polymer (A-1), using 20 mass% of methacrylic acid, 55 mass% of styrene, 18 mass% of methyl methacrylate, and 7 mass% of n-butyl acrylate, a binder polymer solution (solid content 49 mass%) (A-6) with an acid equivalent of 430 g / mol, a weight-average molecular weight of approximately 30,000, and a glass transition temperature (Tg) of 102°C was obtained.

[0294] <Preparation of Binder Polymer Solution (A-7)>

[0295] In a flask equipped with a stirrer, a reflux cooler, an inert gas inlet, and a thermometer, 62% by mass of propylene glycol monomethyl ether and 62% by mass of toluene were placed. The mixture was heated to 80°C under a nitrogen atmosphere, and 12% by mass of methacrylic acid, 58% by mass of methyl methacrylate, 30% by mass of ethyl acrylate (EA), and an azo polymerization initiator (AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) were uniformly added dropwise over 4 hours. After the addition, stirring was continued at 80°C for 6 hours to obtain a binder polymer solution (solids content 45% by mass) (A-7) having an acid equivalent of 717 g / mol, a weight-average molecular weight of approximately 65,000, and a glass transition temperature (Tg) of 60°C.

[0296] <Preparation of Binder Polymer Solution (A-8)>

[0297] A flask was charged with 1% by mass of 2,2'-azobis(isobutyronitrile) and 200% by mass of PGMEA (propylene glycol methyl ether acetate). Methyl methacrylate (30% by mass), methacrylic acid (20% by mass), glycidyl methacrylate (GMA) (30% by mass), and styrene (20% by mass) were then added and briefly stirred at room temperature. The flask was thoroughly purged with nitrogen by bubbling, and then heated and stirred at 70°C for 5 hours to obtain a binder polymer solution (38% by mass solids) (A-8) with an acid equivalent of 430 g / mol, a weight-average molecular weight of approximately 12,000, and a glass transition temperature (Tg) of 194°C.

[0298] In addition, the measurement of acid equivalent and weight average molecular weight, and the calculation of glass transition temperature (Tg) were performed by the method described in detail in the above <(A) Alkali-soluble resin>.

[0299] <Preparation of Oxime Ester Compound (C-7)>

[0300] [Synthesis of Compound C-7a]

[0301] Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, cooled to 0°C, and aluminum chloride (70.3 g, 0.527 mol) was added. Subsequently, o-toluoyl chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, the temperature was raised to room temperature (25°C, the same below), and stirred for 3 hours. Subsequently, aluminum chloride (75.1 g, 0.563 mol) was added dropwise over 40 minutes, the temperature was raised to room temperature, and stirred for 3 hours. A mixed solution of 156 ml of 35% by mass hydrochloric acid aqueous solution and 392 ml of distilled water was cooled to 0°C, and the reaction solution was added dropwise. The precipitated solid was filtered, washed with distilled water and methanol, and recrystallized from acetonitrile to obtain compound C-7a (yield 164.4 g, yield 77%).

[0302] [Synthesis of Compound C-7b]

[0303] Compound C-7a (20.0 g, 47.9 mmol) obtained above was dissolved in 64 ml of tetrahydrofuran (THF), and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol) were added. Sodium hydroxide (2.0 g, 50.2 mmol) was then added to the reaction mixture, and the mixture was refluxed for 2 hours. After cooling to 0°C, SM-28 (11.1 g, 57.4 mmol, 28% sodium methoxide solution in methanol, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 20 minutes. The mixture was warmed to room temperature and stirred for 2 hours. After cooling to 0°C, isoamyl nitrite (6.73 g, 57.4 mmol) was added dropwise over 20 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction mixture was diluted in 120 ml of acetone and added dropwise to a 0.1N aqueous hydrochloric acid solution cooled to 0°C. The precipitated solid was filtered, washed with distilled water, and then recrystallized from acetonitrile to obtain compound C-7b (amount 17.0 g, yield 64%).

[0304] Compound C-7b (18.0 g, 32.4 mmol) was dissolved in 90 ml of N-methylpyrrolidone (NMP), and triethylamine (Et3N, 3.94 g, 38.9 mmol) was added. Subsequently, after cooling to 0°C, acetyl chloride (AcCl, 3.05 g, 38.9 mmol) was added dropwise over 20 minutes, and then the temperature was raised to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0°C, and the precipitated solid was filtered, washed with 200 ml of isopropanol cooled to 0°C, and dried to obtain the oxime ester compound (C-7) (yield 19.5 g, yield 99%).

[0305] Next, the methods for producing the evaluation films of Examples and Comparative Examples will be described, and further, the evaluation methods and evaluation results of the obtained films will be shown.

[0306] 1. Preparation of evaluation membrane

[0307] The evaluation films in Examples and Comparative Examples were prepared as follows.

[0308] <Production of Photosensitive Resin Laminate>

[0309] According to the composition shown in Table 1 below, various components were weighed into 250 ml plastic bottles. Methyl ethyl ketone was added to a solids concentration of 53% by mass, and the mixture was dissolved and mixed using a stirrer for 5 hours to obtain a photosensitive resin composition. The photosensitive resin composition was then passed through a 3 μm filter to prepare photosensitive resin composition preparations (Examples 1 to 28 and Comparative Examples 1 to 7).

[0310] The photosensitive resin composition preparation liquid was evenly coated on the surface of a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Ltd., FB40) as a support using a doctor blade coater, and dried in a dryer at 95°C for 7 minutes to form a uniform photosensitive resin layer on the support. The thickness of the photosensitive resin layer was 8 μm and 40 μm. Next, a 33 μm thick polyethylene film (manufactured by Tama Poly Co., Ltd., GF-858) was attached to the surface of the photosensitive resin layer as a protective film to obtain a photosensitive resin laminate. In addition, the following evaluation results are shown in Table 1. The names of the material components in the photosensitive resin composition preparation liquid represented by abbreviations in Table 1 are shown in Table 2.

[0311] 2. Dynamic Viscoelasticity Measurement

[0312] <Sample Preparation Method>

[0313] Prepare two photosensitive resin laminates with a thickness of 40 μm, put the surfaces from which the protective films were peeled together, and laminate them using a hot roller laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III). After peeling off the support film of the protective film on one side, further laminate the material obtained by peeling off the protective film of the photosensitive resin laminate with a thickness of 40 μm. Repeat this operation twice to obtain a laminate with a protective film thickness of 160 μm. Set the roller temperature to 100°C, the air pressure to 0.2 MPa, and the lamination speed to 0.5 m / min. Peel off the support films on both sides of the obtained laminate and use it as a sample for dynamic viscoelasticity measurement. After the prepared sample is humidified at 23°C and RH50% for one day, it is tested.

[0314] <Evaluation Method>

[0315] The samples prepared by the above method were subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring apparatus (rheometer) (DHR-2, manufactured by TA Instruments) under the following conditions. The point at which the value changes from decrease to increase was read from the resulting storage modulus curve and was taken as the minimum value. In the case where there were two or more minimum values, each value was read.

[0316] (Measurement conditions)

[0317] Sample size: 2.5cmΦ, thickness 160μm

[0318] Measurement temperature conditions: 30~200℃

[0319] Heating rate: 5℃ / min

[0320] Frequency: 1Hz

[0321] Load: 0.2N

[0322] Strain: 1.0%

[0323] 3. Moisture permeability test

[0324] <Sample Preparation Method>

[0325] The protective film of the photosensitive resin laminate with a thickness of 40 μm was peeled off and laminated on No. 4 filter paper (made by ADVANTEC) using a hot roller laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III). The roller temperature was set to 100°C, the air pressure was set to 0.4 MPa, and the lamination speed was set to 1.0 m / min. After standing for 15 minutes, the entire surface was exposed from the support film side of the protective film using a scattered light exposure machine at the optimal exposure amount of each composition. After standing for 30 minutes, the support film was peeled off and the photosensitive layer was exposed from the photosensitive layer side using a scattered light exposure machine at 350 mJ / cm 2 The sample was exposed to an exposure dose of 100°C and then treated in a hot air circulation oven at 150°C for 30 minutes to prepare the sample. The above-mentioned optimal exposure dose is the same as that defined in the method for preparing samples for developing property evaluation.

[0326] <Evaluation Method>

[0327] The moisture permeability was measured in accordance with the cup method of JIS Z0208 under moisture permeability conditions of a temperature of 65° C. and a humidity of 90%.

[0328] 4. Infrared spectroscopy

[0329] <Sample Preparation Method>

[0330] The photosensitive resin laminate with a thickness of 8 μm was cut into 5 cm × 5 cm pieces and exposed from the support side with the optimal exposure amount of each component. After that, after standing for more than 15 minutes, the protective film was peeled off and a developing device manufactured by Fuji Kiko Co., Ltd. was used to spray a 1% by mass Na2CO3 aqueous solution at 33°C for 45 seconds using a dense cone-shaped nozzle at a developing spray pressure of 0.12 MPa to dissolve and remove the unexposed part of the photosensitive resin layer. At this time, the water washing process was carried out at the same time as the developing process using a flat nozzle at a water washing spray pressure of 0.12 MPa, and the washed sample was dried by blowing air. After development, it was allowed to stand for more than 15 minutes, and then a scattered light exposure machine was used to expose the sample from the photosensitive layer side at a pressure of 350 mJ / cm 2 After allowing to stand for at least 15 minutes, the sample was heated in a hot air circulation oven at 150°C for 30 minutes to produce a 5 cm x 5 cm sample. The optimal exposure is the same as that defined in the method for preparing samples for developing performance evaluation.

[0331] <Evaluation Method>

[0332] The sample prepared by the above method was measured by the ATR method at 400 cm using an infrared spectrophotometer (CONTINU μM FT / IR Microscope manufactured by Thermo Fisher Scientific). -1~4000cm -1 The wavelength region of the aromatic group was determined from the obtained IR spectrum (I) (700 cm -1 near) and the peak derived from aliphatic groups (II) (1450 cm -1 The peak intensity ratio is calculated using the calculation formula shown in the above calculation formula (2).

[0333] 4. Refractive index measurement

[0334] <Sample Preparation Method>

[0335] The photosensitive resin laminate with a thickness of 8 μm was cut into 5 cm × 5 cm pieces and exposed from the support side with the optimal exposure amount of each component. After that, the protective film was peeled off after standing for more than 15 minutes, and a developing device manufactured by Fuji Kiko Co., Ltd. was used to spray a 1% by mass Na2CO3 aqueous solution at 33°C for 45 seconds using a dense cone-shaped nozzle at a developing spray pressure of 0.12 MPa to dissolve and remove the unexposed part of the photosensitive resin layer. At this time, the water washing process was carried out at the same time as the developing process using a flat nozzle at a water washing spray pressure of 0.12 MPa, and the washed sample was dried by blowing air. After development, it was allowed to stand for more than 15 minutes, and then a scattered light exposure machine was used to expose the sample from the photosensitive layer side at a pressure of 350 mJ / cm 2 After allowing to stand for at least 15 minutes, the sample was heated in a hot air circulation oven at 150°C for 30 minutes to produce a 5 cm x 5 cm sample. The optimal exposure is the same as that defined in the method for preparing samples for developing performance evaluation.

[0336] <Evaluation Method>

[0337] The refractive index of the sample prepared by the above method was measured at four arbitrary points in the planar direction and four arbitrary points in the perpendicular direction using a refractometer (Metricon, Prism Coupler Model 2010 / M) with a 532 nm laser source, and the average value was calculated.

[0338] 4. Development evaluation

[0339] <Sample Preparation Method>

[0340] The protective film of the photosensitive resin laminate, with a thickness of 8 μm, was peeled off and simultaneously laminated onto the copper surface of a substrate (size: 5 cm × 10 cm) layered with resin, ITO, and sputtered copper in this order using a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.). The roll temperature was 100°C, the air pressure was 0.4 MPa, and the lamination speed was 1.0 m / min. After standing for 15 minutes, a PET mask and a Stouffer 21-step exposure scale (with an optical density of 0.00 as the first step, and the optical density increasing by 0.15 for each step) were placed side by side on the support film. The optimal exposure for each composition was determined from the PET mask and scale, and exposure was performed using a parallel light exposure machine (HMW-801, manufactured by Orc Manufacturing Co., Ltd.). The PET mask used had a pattern of circular holes with unexposed areas. After standing for at least 15 minutes, the support was peeled off and developed using a Fuji Kiko Co., Ltd. developer using a close-cone nozzle at a development spray pressure of 0.12 MPa for 45 seconds with a 1% by mass Na₂CO₃ aqueous solution at 33°C to dissolve and remove the unexposed portions of the photosensitive resin layer. A water rinse step was performed simultaneously with the development step using a flat nozzle at a water rinse spray pressure of 0.12 MPa. The rinsed sample was then air-dried to prepare a sample for developing evaluation. The optimal exposure is the exposure that results in 8-9 levels of residual film when exposed through a Stouffer 21-level scale.

[0341] <Evaluation Method>

[0342] The surface condition of the portion of the produced protective film-attached substrate from which the photosensitive layer was removed was observed using a microscope and determined as follows.

[0343] A: No change on the substrate surface.

[0344] B: The copper on the substrate surface turns slightly red, but no development residue remains.

[0345] C: The copper on the substrate surface turned red, and development residue occurred.

[0346] In the developability evaluation, a grade of B or higher is considered to be a practically good result in the touch panel manufacturing process.

[0347] 5. Rust resistance of the coating

[0348] <Preparation of Test Base Material>

[0349] A photosensitive resin laminate was prepared as described in Example 2 of Japanese Patent No. 4515123. The protective film of the photosensitive resin laminate was removed and the laminate was laminated onto the copper surface of a flexible substrate measuring 5 cm x 10 cm, which was laminated with resin, ITO, and sputtered copper in this order, using a hot roller laminator. The roller temperature was 100°C, the air pressure was 0.4 MPa, and the lamination speed was 1.5 m / min. After standing for 30 minutes, a PET mask was placed on the support film and a parallel light exposure machine was used from the PET mask side at 120 mJ / cm 2 Exposure is performed. The PET mask uses a mask with a line width / spacing = 80μm / 80μm ​​pattern. After standing for more than 30 minutes, the support film is peeled off, and a developing device manufactured by Fuji Kiko Co., Ltd. is used to spray a 1% by mass Na2CO3 aqueous solution at 30°C using a dense cone nozzle at a developing spray pressure of 0.15MPa. The spraying time is twice the minimum developing time to dissolve and remove the unexposed portion of the photosensitive resin layer. Here, the minimum developing time refers to the minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed. At this time, the water washing process is carried out simultaneously with the developing process using a flat nozzle at a water washing spray pressure of 0.15MPa, and air drying is used to form a resist pattern on the copper.

[0350] Next, the substrate with the resist pattern formed was immersed in an aqueous solution containing 2% by mass hydrochloric acid and 2% by mass iron (III) chloride at a temperature of 30°C for 1.5 times the minimum etching time. The substrate was then rinsed with water and air-dried. The minimum etching time refers to the minimum time required to completely dissolve and remove the copper foil on the substrate under the above conditions.

[0351] After etching, the resist was removed by immersion in a 3 wt% NaOH aqueous solution at 50°C, followed by water rinsing and air drying. This produced a test substrate with ITO laminated on a resin and a copper wiring pattern formed thereon. Describing the copper wiring pattern in more detail, ten copper wires, each 8 cm long and 80 μm wide, were formed with a line width:line spacing ratio of 1:1.

[0352] <Sample Preparation Method>

[0353] The protective film of the photosensitive resin laminate having a thickness of 8 μm of the photosensitive resin layer described in the present invention is peeled off, and at the same time, a hot roller laminator (manufactured by Taisei Laminator Co., Ltd., VA-400III) is used to laminate on the surface of the laminate substrate formed with copper wiring produced by the above method. At this time, the roller temperature is set to 100°C, the air pressure is 0.4 MPa, and the lamination speed is 1.0 m / min. After standing for 30 minutes, the entire surface is exposed from the support film side of the protective film using a scattered light exposure machine with the optimal exposure amount of each composition. After standing for 30 minutes, the support film is peeled off, and a developing device manufactured by Fuji Kiko Co., Ltd. is used to spray a 33°C 1% by mass Na2CO3 aqueous solution for 45 seconds using a tight cone-shaped nozzle at a developing spray pressure of 0.12 MPa for development, and the unexposed portion of the photosensitive resin layer is dissolved and removed. At this time, the water washing process is carried out simultaneously with the developing process using a flat nozzle at a water washing spray pressure of 0.12 MPa, and drying is carried out by blowing air. Then, a scattered light exposure machine was used to expose the photosensitive layer at 350 mJ / cm 2 The sample was exposed to an exposure dose of 100°C and then treated in a hot air circulation oven at 150°C for 30 minutes to prepare the sample. The above-mentioned optimal exposure dose is the same as that defined in the method for preparing samples for developing property evaluation.

[0354] <Evaluation Method>

[0355] Acidic artificial sweat described in JIS L0848 was dripped onto the protective film located directly above the copper wiring of the prepared sample. The sample was then stored in a constant temperature and humidity oven (THN050FA, manufactured by ADVANTEC Toyo Co., Ltd.) at 85°C and 85% RH. After a predetermined period of time, the sample was removed from the oven and microscopically observed from both the protective film side and the side opposite the protective film to confirm discoloration or corrosion of the copper wiring. This was determined as follows.

[0356] A: Discoloration occurred after 500 hours or more in an environment of 85°C and 85% RH.

[0357] B: Discoloration occurred in an environment of 85° C. and 85% RH for 350 hours or more and less than 500 hours.

[0358] C: Discoloration occurred in an environment of 85° C. and 85% RH for 200 hours or more and less than 350 hours.

[0359] D: Discoloration or corrosion occurred in an environment of 85°C and 85% RH within 200 hours.

[0360] Regarding the rust prevention of the coating, a grade of C or higher is practically required in the touch panel manufacturing process, and a grade of B or higher is considered to be a good result.

[0361] Table 1 (Table 1-1 to Table 1-4) shows the compositions of the photosensitive resin compositions used in each example and comparative example, as well as the evaluation results of the photosensitive resin laminates. Table 1-1 shows Examples 1 to 10, Table 1-2 shows Examples 11 to 20, Table 1-3 shows Examples 21 to 28, and Table 1-4 shows Comparative Examples 1 to 7. The compositions of the binder polymers in the photosensitive resin composition preparations, represented by abbreviations in Table 1, are shown in Table 2, and the names of other material components are shown in Table 3.

[0362] [Table 1]

[0363] (Table 1-1)

[0364]

[0365] [Table 2]

[0366] (Table 1-2)

[0367]

[0368] [Table 3]

[0369] (Table 1-3)

[0370]

[0371] [Table 4]

[0372] (Table 1-4)

[0373]

[0374] [Table 5]

[0375] (Table 2)

[0376] Monomer composition (mass %) Acid equivalent Weight average molecular weight Tg(℃) A-1 MAA / MMA / BzMA=20 / 0.5 / 79.5 430 20.000 79 A-2 MAA / MMA / St=21 / 39 / 40 410 30,000 123 A-3 MAA / MMA / St=20 / 25 / 55 430 25,000 121 A-4 MAA / St=25 / 75 344 25,000 125 A-5 MAA / MMA / nBA / St=20 / 4 / 21 / 55 430 25,000 67 A-6 MAA / MMA / nBA / St=20 / 18 / 7 / 55 430 30,000 102 A-7 MAA / MMA / EA=12 / 58 / 30 717 65,000 60 A-8 MAA / MMA / GMA / St=20 / 30 / 30 / 20 430 12,000 194

[0377] [Table 6]

[0378] (Table 3)

[0379]

[0380]

[0381]

[0382] The results shown in Tables 1-1 to 1-3 show that Examples 1 to 28 satisfy the conditions specified in the present invention and thus exhibit excellent developability, rust resistance, and moisture permeability of the films subjected to an alkali development process. On the other hand, the comparative examples (Tables 1-4) do not satisfy any of the conditions specified in the present invention and therefore exhibit poor developability, rust resistance, and moisture permeability of the films subjected to an alkali development process.

[0383] While the embodiments of the present invention have been described above, the present invention is not limited thereto and can be appropriately modified within the scope of the invention.

[0384] Industrial Applicability

[0385] By using the photosensitive resin composition and photosensitive resin laminate of the present invention, the photosensitive resin composition and photosensitive resin laminate have excellent rust resistance and developability, are suitable for protecting conductor parts such as wiring and electrodes, and can be widely used as protective films for wiring, electrodes, etc. for touch panels, touch sensors or force sensors.

Claims

1. A photosensitive resin composition for forming a protective film for a conductor portion, comprising the following components: (A) alkali-soluble resin; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (G) rust inhibitors, The photosensitive resin composition is characterized in that it satisfies the following conditions (1) and (2): (1) The minimum storage modulus of the photosensitive resin composition before curing is 40 Pa or less; (2) The moisture permeability of the photosensitive resin composition after curing is 300 g / m 2 Less than 24 hours, The (A) alkali-soluble resin is a polymer containing a carboxyl group, and includes a structure derived from benzyl methacrylate or a structure derived from styrene. The (B) compound having an ethylenically unsaturated double bond includes: (b1) a compound having three or more polymerizable groups in the molecule and a molecular weight of 430 or less, and (b2) a compound having only one polymerizable group in the molecule and a molecular weight of 350 or less, The (G) rust inhibitor is selected from the group consisting of benzotriazole, 1H-benzotriazole-1-acetonitrile, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole, 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole, 1H-benzotriazole-1-methanol, 5-methyl-1H-benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, 5-chlorobenzotriazole and 5-nitrobenzotriazole.

2. The photosensitive resin composition according to claim 1, wherein The (A) alkali-soluble resin has a glass transition temperature of 70° C. or higher.

3. The photosensitive resin composition according to claim 1 or 2, wherein The (A) alkali-soluble resin includes (a1) a structure derived from (meth)acrylic acid and (a2) a structure derived from styrene.

4. The photosensitive resin composition according to claim 1 or 2, wherein The acid equivalent of the (A) alkali-soluble resin is greater than or equal to 340 g / mol.

5. The photosensitive resin composition according to claim 3, wherein The content of the (a1) structure derived from (meth)acrylic acid is 0.1% by mass or more and 25% by mass or less based on the (A) alkali-soluble resin.

6. The photosensitive resin composition according to claim 3, wherein The content of the styrene-derived structure (a2) is 40% by mass or more and 80% by mass or less based on the alkali-soluble resin (A).

7. The photosensitive resin composition according to claim 1 or 2, wherein The weight average molecular weight of the (A) alkali-soluble resin is 5,000 to 50,000.

8. The photosensitive resin composition according to claim 1 or 2, wherein The content of the (A) alkali-soluble resin is 10% by mass to 70% by mass based on the mass of the photosensitive resin composition.

9. The photosensitive resin composition according to claim 1 or 2, wherein The compound (b2) having only one polymerizable group in the molecule and a molecular weight of 350 or less is a compound composed only of atoms selected from the group consisting of C, H, O, N, S, Si, and F.

10. The photosensitive resin composition according to claim 1 or 2, wherein The compound (b2) having only one polymerizable group in the molecule and having a molecular weight of 350 or less is a compound composed only of atoms selected from the group consisting of C, H, O, N, and S.

11. The photosensitive resin composition according to claim 1 or 2, wherein The molecular weight of the compound (b1) is 360 or less.

12. The photosensitive resin composition according to claim 1 or 2, wherein The content of the compound (b1) is 10% by mass to 60% by mass based on the mass of the photosensitive resin composition.

13. The photosensitive resin composition according to claim 1 or 2, wherein The content of the compound (b2) is 1% by mass to 30% by mass based on the mass of the photosensitive resin composition.

14. The photosensitive resin composition according to claim 1 or 2, wherein The (C) photopolymerization initiator is an oxime ester compound.

15. The photosensitive resin composition according to claim 14, wherein The oxime ester compound is a compound represented by the following structural formula (1): In formula (1), X1 represents an H group or a monovalent organic group, and Y1 and Y2 each independently represent a monovalent organic group, and at least one of Y1 and Y2 includes a structure represented by the following formula (2), In formula (2), R1 represents a monovalent organic group, and R2 represents an alkyl group or an organic group having an aryl group.

16. The photosensitive resin composition according to claim 15, wherein The Y1 and Y2 each include a structure represented by the formula (2).

17. The photosensitive resin composition according to claim 1 or 2, wherein The content of the (C) photopolymerization initiator is 0.1% by mass to 10% by mass based on the mass of the photosensitive resin composition.

18. The photosensitive resin composition according to claim 1 or 2, wherein The composition further comprises (D) a thermal crosslinking agent.

19. The photosensitive resin composition according to claim 18, wherein The (D) thermal crosslinking agent includes a blocked isocyanate compound and / or a diol compound.

20. The photosensitive resin composition according to claim 1 or 2, wherein The combination further comprises (E) a rosin ester compound.

21. The photosensitive resin composition according to claim 20, wherein The (A) alkali-soluble resin includes an aromatic structure which may have a substituent.

22. The photosensitive resin composition according to claim 20, wherein The acid value of the (E) rosin ester compound is 20 mgKOH / g or less.

23. The photosensitive resin composition according to claim 20, wherein The (E) rosin ester compound has a softening point of 100° C. or higher.

24. The photosensitive resin composition according to claim 1 or 2, wherein The composition further comprises (F) a compound having a phosphate structure and an ethylenically unsaturated group and having a molecular weight greater than 250.

25. The photosensitive resin composition according to claim 1 or 2, wherein The storage modulus of the photosensitive resin composition before curing has two minimum values, both of which are below 40 Pa.

26. The photosensitive resin composition according to claim 1 or 2, wherein The content of the (G) rust inhibitor is 0.05% by mass to 10% by mass based on the mass of the photosensitive resin composition. 27 . A photosensitive resin laminate comprising a support film and a photosensitive resin layer provided on the support film, wherein the photosensitive resin layer is formed from the photosensitive resin composition for forming a protective film for a conductor portion according to claim 1 .

28. A method for producing a pattern, comprising the steps of laminating the photosensitive resin laminate according to claim 27 on a substrate, exposing the laminate to light, and then developing the laminate to produce a pattern.

29. A method for manufacturing a cured film pattern, comprising the following steps: a step of laminating the photosensitive resin laminate according to claim 27 on a substrate, exposing it to light, and then developing it to form a pattern; and This pattern is subjected to a post-exposure treatment and / or a heat treatment step for curing. 30 . A method for manufacturing a touch panel display device, a device having a touch sensor, or a device having a force sensor, comprising the method for manufacturing a cured film pattern according to claim 29 .

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