JP7490040B2 - Photosensitive resin laminate, and method and device for manufacturing a pattern using the photosensitive resin laminate - Google Patents

Description

The present invention relates to a photosensitive resin laminate, and a pattern manufacturing method and device using the photosensitive resin laminate. More specifically, the present invention relates to a photosensitive resin laminate suitable for forming planarizing films, protective films, and interlayer insulating films for electronic components such as liquid crystal display devices, organic EL display devices, touch panel display devices, integrated circuit elements, solid-state imaging elements, and semiconductor elements, or for solder resists or interlayer insulating films for rigid printed wiring boards and flexible printed wiring boards, and a pattern manufacturing method using the same.

In recent years, as electronic devices have become more sophisticated, diverse, and smaller and lighter, more and more devices are equipped with transparent touch panels (touch sensors) on the entire surface of display elements such as liquid crystal displays. Characters, symbols, pictures, etc. displayed on display elements are viewed and selected through the transparent touch panel, and functions of the device are increasingly being switched by operating the transparent touch panel. Touch panels are used not only in large electronic devices such as personal computers and televisions, but also in small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, as well as in display devices for office automation and factory automation equipment, and electrodes made of transparent conductive electrode materials are provided on the touch panel. ITO (Indium-Tin-Oxide), indium oxide, and tin oxide are known as transparent conductive electrode materials, and these materials are mainly used as electrode materials for substrates for liquid crystal display elements, etc., because they have high visible light transmittance.

Existing touch panel types include resistive film type, optical type, pressure type, capacitance type, electromagnetic wave induction type, image recognition type, vibration detection type, ultrasonic type, etc., and various types have been put to practical use. In recent years, the use of capacitance type touch panels has progressed the most. In a capacitance type touch panel, when a conductive fingertip touches a touch input surface, a capacitance coupling occurs between the fingertip and a conductive film to form a capacitor. For this reason, a capacitance type touch panel detects the coordinates of the touch position by capturing the change in charge at the touch position of the fingertip. In particular, a projected capacitance type touch panel is capable of detecting multiple points of a fingertip, and therefore has good operability in that complex instructions can be given, and is therefore increasingly being used as an input device on the display surface of devices with small display devices such as mobile phones and portable music players. In general, in a projected capacitance type touch panel, in order to express two-dimensional coordinates by the X axis and the Y axis, multiple X electrodes and multiple Y electrodes perpendicular to the multiple X electrodes form a two-layer structure, and ITO is used as the electrode material.

The frame area of a touch panel is an area where the touch position cannot be detected, so narrowing the area of this frame area is an important factor in improving the product value. Metal wiring is required in the frame area to transmit the detection signal of the touch position, but in order to narrow the frame area, the width of the metal wiring must be narrowed. Since the conductivity of ITO is not high enough, copper is generally used for the metal wiring.

However, when a touch panel such as the one described above is touched by a fingertip, corrosive components such as moisture and salt may penetrate into the interior through the sensing area. If corrosive components penetrate into the interior of the touch panel, the metal wiring will corrode, increasing the electrical resistance between the electrodes and the driving circuitry, or there is a risk of disconnection. To prevent this, a protective film with anti-corrosion properties is required on the metal wiring. In general, the lower the moisture permeability of the protective film, the greater the anti-corrosion properties of the metal wiring tends to be.

In addition, since the metal wiring for transmitting the detection signal is connected to other components at the terminal portion, it is necessary to ensure conductivity, and the protective film must be removed from the terminal portion. As a method for providing a protective film in a required portion, a method of providing a photosensitive layer made of a photosensitive resin composition and exposing and developing this photosensitive layer has been disclosed (for example, Patent Documents 1 and 2). Usually, when applying the photosensitive resin composition to a substrate, either a method of applying a solution of the photosensitive resin composition to the substrate and drying it, or a method of laminating a photosensitive resin laminate, in which a support, a photosensitive layer, and a protective film are laminated in this order, on the substrate is used. In the manufacture of touch panels, the latter photosensitive resin laminate is often used.

An example of a method for manufacturing a touch panel substrate using the above-mentioned photosensitive resin laminate is described below. First, the protective film of the photosensitive resin laminate is peeled off from the photosensitive layer. Next, using a vacuum laminator, the photosensitive layer and the support are laminated on the touch panel substrate in the order of the substrate, photosensitive layer, and support. Next, the photosensitive layer is exposed to ultraviolet light such as i-line (365 nm) emitted by an ultra-high pressure mercury lamp through a photomask having a pattern, thereby polymerizing and curing the exposed portion. Next, the support is peeled off. Next, the unexposed portion of the photosensitive layer is dissolved or dispersed and removed with a developer such as an aqueous solution having a weak alkalinity, thereby obtaining a protective film pattern on the substrate. Furthermore, the protective film pattern can be further improved in protective film durability by a post-exposure process and/or a heating process.

Polyolefin films are generally used as protective films for photosensitive resin laminates, but polyolefin films have protruding defect structures called fisheyes. As a result, the areas of the photosensitive layer in contact with the fisheyes in the protective film are pressed and made thinner, and when the film is developed after exposure, pattern defects can occur in those areas. To solve this problem, pattern-forming materials have been proposed that are used as protective films with reduced fisheyes (Patent Documents 3 and 4).

For example, Patent Document 3 describes that the number of air voids generated between the substrate surface and the photosensitive layer can be reduced by using a protective film containing ⁵ or less fisheyes with a diameter of 80 μm or more per square meter. However, a protective film with extremely few fisheyes and excellent smoothness has a problem that a part of the photosensitive layer is transferred to the protective film side when the film is placed in a vacuum environment for a long period of time in vacuum lamination.

To address these problems, Patent Document 4 describes the use of a protective film in which the area present in the protective film is ^2,000 μm2 or more and the number of fisheyes with a maximum height from the film surface of 1 to 7 μm is 50 to 1,000 per ^m2 . However, when a protective film is used, the photosensitive layer is crushed due to the protruding shape of the fisheyes and/or the contact area with the photosensitive layer increases, causing the photopolymerizable compound in the photosensitive layer to pass through the protective film (hereinafter referred to as bleed-out) at localized locations, preventing sufficient curing in the exposure step and reducing rust prevention properties.

On the other hand, in Patent Document 5, a protective film is
It is described that the use of a protective film that satisfies at least one of the following conditions: (i) it is a polypropylene film; and (ii) it has a free volume of less than 0.2 ^nm3 has the effect of suppressing the phenomenon in which the photopolymerizable compound in the photosensitive resin bleeds out. However, there is no disclosure about the size or number of fisheyes in the protective film.

International Publication No. 2013/084872 JP 2013-76821 A Japanese Patent Application Laid-Open No. 11-153861 JP 2006-72259 A JP 2011-215366 A

In recent years, protective films formed on metal wiring of touch panels are required to have both better rust resistance and developability. In order to provide both, low molecular weight photopolymerizable compounds are often used, which causes a problem that the photopolymerizable compounds in the photosensitive layer tend to bleed out. None of the above patent documents has been able to sufficiently suppress the bleed-out problem.
Furthermore, a protective film having excellent smoothness and very few fisheyes has a problem that a part of the photosensitive layer adheres to the protective film side when placed in a vacuum environment for a long time in vacuum lamination, and a part of the photosensitive layer is transferred to the protective film side when the protective film is peeled off. None of the above-mentioned patent documents have been able to sufficiently suppress the transfer problem.

The problem that the present invention aims to solve is to provide a photosensitive resin laminate that, when placed in the vacuum environment of vacuum lamination for a long period of time, is unlikely to cause a portion of the photosensitive layer to abnormally adhere to the protective film side and to be transferred to the protective film side when the protective film is peeled off, and that can suppress bleeding out of the photopolymerizable compound in the photosensitive layer from the protective film that occurs over time.

As a result of intensive research into solving the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by having a protective film including, on the surface in contact with the photosensitive layer, a region measuring 10 m in length and 0.1 m in width, having an area of 2,000 μm2 or ^more and having more than 5 but less than 20 fisheyes with a maximum height of 1 μm or more from the protective film surface.
That is, the present invention is as follows.
[1]
A photosensitive resin laminate comprising a support, a photosensitive layer, and a protective film laminated in this order, the protective film including, on a surface in contact with the photosensitive layer, a region measuring 10 m in length x ^0.1 m in width, in which the number of fisheyes having an area of 2,000 μm2 or more and a maximum height of 1 μm or more from the surface of the protective film is more than 5 and less than 20.
[2]
2. The photosensitive resin laminate according to item 1, wherein the protective film comprises polypropylene.
[3]
3. The photosensitive resin laminate according to item 2, wherein the protective film is a polypropylene film.
[4]
4. The photosensitive resin laminate according to any one of items 1 to 3, wherein the photosensitive layer has a thickness of less than 15 μm.
[5]
5. The photosensitive resin laminate according to any one of items 1 to 4, wherein the photosensitive layer has a minimum viscosity of 1,000 Pa·s or less before curing.
[6]
The photosensitive layer comprises the following components:
6. The photosensitive resin laminate according to any one of items 1 to 5, comprising: (A) an alkali-soluble resin; (B) a photopolymerizable compound; and (C) a photopolymerization initiator.
[7]
7. The photosensitive resin laminate according to any one of items 1 to 6, wherein the photopolymerizable compound (B) includes at least a compound having a molecular weight of 430 or less.
[8]
8. The photosensitive resin laminate according to any one of items 1 to 7, which is used to protect either a metal film or a metal oxide film.
[9]
9. The photosensitive resin laminate according to any one of items 1 to 8, which is used as either a protective film for a touch panel or a protective film for a force sensor.
[10]
10. The photosensitive resin laminate according to any one of items ¹ to ⁹ , wherein the protective film has an average number of fisheyes having an area of 2,000 μm2 or more and a maximum height of 1 μm or more from the surface of the protective film of more than 5 and less than 20 per m2 of a surface of the protective film in contact with the photosensitive layer.
[11]
A pattern producing method comprising peeling off the protective film of the photosensitive resin laminate according to any one of items 1 to 10, laminating the photosensitive layer on a substrate in a vacuum atmosphere, exposing the substrate to light, and developing the substrate to produce a pattern.
[12]
Item 12. A device having a touch panel display device or a touch sensor having a pattern manufactured by the pattern manufacturing method according to item 11.

According to the present invention, even if the laminate is left in a vacuum environment for a long period of time, the photosensitive layer is less likely to be transferred to the protective film when the protective film is peeled off, and bleeding out of the photopolymerizable compound in the photosensitive layer from the protective film, which occurs over time, can be suppressed. The present invention also provides a method for producing a resin pattern and a method for producing a cured film pattern using the photosensitive resin laminate.

Fig. 1 is a schematic diagram for explaining the problem of transfer, which is one of the issues to be addressed by the present invention, in which Fig. 1(a) is a schematic diagram of a step of peeling off a protective film from a photosensitive resin laminate, and Figs. 1(b) and 1(c) are enlarged schematic diagrams of the area enclosed by a dotted line shown for convenience in Fig. 1(a). FIG. 2 is a schematic diagram for explaining the problem of bleed-out, which is one of the problems to be solved by the present invention.

The following provides a detailed explanation of the embodiment of the present invention (hereinafter, also referred to as the "present embodiment"). Note that the present invention is not limited to the present embodiment, and can be modified in various ways within the scope of the gist of the present invention.

<Photosensitive resin laminate>
The photosensitive resin laminate of the present embodiment is a photosensitive resin laminate formed by laminating a support, a photosensitive layer, and a protective film in this order.

<Protective film>
The protective film preferably includes, on the surface in contact with the photosensitive layer, a region of 10 m length ^{x 0.1} m width in which the area of the film is 2,000 μm2 or more and the number of fisheyes with a maximum height of 1 μm or more from the film surface is more than 5 and less than 20. Here, "length" means the machine direction (MD) of the photosensitive resin laminate, and "width" means the transverse direction (TD) perpendicular to the MD.
In addition, the protective film preferably has an average number of fisheyes having an area of 2,000 ^μm2 or more and a maximum height of 1 μm or more from the film surface of more than 5 and less than 20 per ^m2 of the surface of the protective film in contact with the photosensitive layer.

If the area of 10 m long x 0.1 m wide where there are more than five fish eyes is included, the problem of a part of the photosensitive layer being transferred to the protective film side is suppressed when it is placed in the vacuum environment of the vacuum lamination for a long time. Although not limited to theory, the reason will be explained below with reference to FIG. 1. The photosensitive resin laminate (10) is typically a wound body in which a support (1), a photosensitive layer (2), and a protective film (3) are laminated in this order and wound around a core material (4). As shown in FIG. 1(a) and its enlarged schematic diagram (b) within the dotted line frame, the photosensitive resin laminate (10) is used in the manufacture of various devices by peeling off the protective film from the photosensitive layer and bonding the photosensitive layer to a conductor-attached substrate or the like in the vacuum environment of the vacuum laminator chamber (20). The vacuum environment is typically about 50 to 1,000 Pa. However, when the photosensitive resin laminate is placed in a vacuum environment for a long time, minute air particles between the protective film (1) and the photosensitive layer (2) escape, improving the tackiness with the protective film, and if the smoothness between the protective film and the photosensitive layer is too high, the adhesion may become abnormally high. Then, as shown in FIG. 1(a) and the enlarged schematic diagram (c) of the dotted line frame, the photosensitive layer may be transferred (5) to the protective film. In particular, the photosensitive resin laminate near the core material is exposed to a vacuum environment for a longer period of time during the manufacturing process, so the transfer problem is more prominent inside than outside the wound body. On the other hand, by including an area of 10 m long x 0.1 m wide with more than five fisheyes, it is difficult for air to escape near the fisheyes, which promotes peeling between the protective film and the photosensitive layer, and it is thought that the transfer of the photosensitive layer to the protective film can be reduced.

In addition, if the area includes a 10m x 0.1m region with less than 20 fisheyes, the above-mentioned transfer problem can be suppressed while also effectively suppressing bleed-out. Without being limited to theory, the reason for this will be explained below with reference to FIG. 2. In localized areas where fisheyes (6) exist, the photosensitive layer (2) is crushed and/or the contact area between the protective film (3) and the photosensitive layer (2) increases due to the fisheye protrusions. Then, as shown diagrammatically by the dotted arrow (7) in FIG. 2, it is considered that the photopolymerizable compound in the photosensitive layer passes through the protective film (bleeds out), and sufficient curing does not proceed in the exposure process, resulting in a problem of reduced developability and rust prevention. On the other hand, by including a 10m x 0.1m region with less than 20 fisheyes, it is possible to suppress such localized crushing of the photosensitive layer and an increase in the contact area, and it is considered that both the above-mentioned transfer and bleed-out problems can be effectively suppressed.

The protective film may include, on the surface in contact with the photosensitive layer, an area of 10 m length x 0.1 m width in which the number of fisheyes is, for example, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 14 or more, or 16 or more.
The protective film may include an area of 10 m length x 0.1 m width on the surface in contact with the photosensitive layer, in which the number of fisheyes is, for example, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, or 9 or less.

It is preferable that the number (average number) of fisheyes having an area of 2,000 μm2 or more and a maximum height of 1 ^μm or more from the surface of the protective film, averaged over the entire area of the protective film in contact with the photosensitive layer, is more than 5 fisheyes/ ^m2 and less than 20 fisheyes/ ^m2 .
The average number of fisheyes when averaged over the entire area of the protective film in contact with the photosensitive layer may be, for example, 6/ ^m2 or more, 7/ ^m2 or more, 8/ ^m2 or more, 9/ ^m2 or more, 10/ ^m2 or more, 12/ ^m2 or more, 14/ ^m2 or more, or ¹⁶ /m2 or more.
The average number of fisheyes may be, for example, 19/ ^m2 or less, 18/ ^m2 or less, 17/ ^m2 or less, 16/ ^m2 or less, 15/ ^m2 or less, 14/ ^m2 or less, 13/ ^m2 or less, 12/ ^m2 or less, 11/ ^m2 or less, 10/ ^m2 or less, or 9/ ^m2 or less.
In particular, fish eyes with an area exceeding ^2,000 μm2, a maximum length exceeding 80 μm, or a maximum height exceeding 1 μm cause serious bleed-out, so it is preferable that the average number of fish eyes is less than 20 per square ^meter .

In the present invention, a fisheye refers to an optically non-uniform region in which interference fringes (Newton rings) are observed when a film is irradiated with reflected light. A fisheye typically has a core of foreign matter within the region, but it does not have to have one. The area and length of the fisheye refer to the area and length of the region surrounded by the outermost periphery of the interference fringes (Newton rings). The maximum length refers to the length of the longest line segment that passes through the center of gravity of the area of the region and has intersections with the outermost periphery at both ends.

Examples of foreign matter include components with different viscosities or molecular weights from the raw resin of the film, gel-like matter, unmelted resin, oxidized and deteriorated resin, pieces of the raw packaging material, dust, etc. If these are mixed in during the film molding process, the foreign matter acts as a nucleus to form a fisheye, which is a defective structure, in the film.
The number and size of fisheyes formed in the film can be controlled by adjusting the raw material composition, kneading conditions, melting conditions, etc., or by filtering after melting. For example, a protective film with fisheyes within the range of this embodiment can be produced by removing all foreign matter that would become fisheyes by filtration and then adding particles that will become foreign matter.

The presence or absence of fisheyes is measured for the protective film to be measured using an optical microscope. The presence or absence of a region of 10 m length x 0.1 m width where there are more than 5 but less than 20 fisheyes on the entire surface of the protective film to be measured that contacts the photosensitive layer is judged. The area and maximum length of the fisheyes are measured from an image taken at a magnification of 200 times or more.
The maximum height of the fisheyes is measured using a laser microscope with an objective lens of 50x magnification. If the interference fringes of the fisheyes are strong and measurement is difficult, the sample containing the fisheyes may be previously vapor-deposited with gold and then measured. In a similar manner, the average number of fisheyes can be measured by averaging the number of fisheyes over the entire area of the protective film to be measured.

The materials contained in the protective film are not particularly limited and can be appropriately selected depending on the purpose, but examples include polypropylene resin, polyethylene resin, ethylene-propylene copolymer resin, polyethylene terephthalate resin, etc. These may be used alone or in combination of two or more types. The protective film may also be a laminate film consisting of two or more layers laminated together, and an example of such a laminate film is a laminate film consisting of a polypropylene resin film and an ethylene-propylene copolymer resin film laminated together.

From the viewpoints of suppressing the movement of the photopolymerizable compound and air in the resin, appropriate adhesion to the photosensitive layer, and smoothness of the film surface, it is preferable that the protective film contains polypropylene, and it is more preferable that the protective film is a polypropylene film.
Here, "the protective film contains polypropylene" means that the protective film is a single layer or laminate film that contains at least one polypropylene resin (homopolymer) composed of propylene as a monomer and/or a propylene copolymer resin containing propylene as one of the comonomers. "The protective film is a polypropylene film" means that the protective film is a single layer or laminate film that is made of a polypropylene resin (homopolymer) composed of propylene as a monomer and/or a propylene copolymer resin containing propylene as one of the comonomers.

The thickness of the protective film is not particularly limited and can be selected appropriately depending on the purpose, but for example, 5 to 100 μm is preferable, 8 to 50 μm is more preferable, and 10 to 30 μm is particularly preferable.

The adhesive strength between the protective film and the photosensitive layer is preferably smaller than the adhesive strength between the photosensitive layer and a layer (e.g., the support) other than the protective film adjacent to the photosensitive layer. The protective film may be surface-treated to adjust the adhesive strength with the photosensitive layer. For example, the surface treatment may be performed by forming a primer layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol on the surface of the protective film. The primer layer may be formed by applying a polymer coating solution to the surface of the protective film and then drying at 30 to 150°C, preferably 50 to 120°C, for 1 to 30 minutes. In addition, the support may be surface-treated to increase the adhesive strength between the support and the photosensitive layer, and examples of such methods include coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

<Support>
The support is not particularly limited and can be appropriately selected according to the purpose, but it is preferable that the support is peelable from the photosensitive layer and has good light transmittance, and more preferably has good surface smoothness. Examples of such supports include 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, and cellulose derivative film. As these films, those that have been stretched as necessary can also be used. The haze of the support is preferably 5 or less. The thinner the film thickness of the support, the more advantageous it is in terms of image forming properties and economic efficiency, but from the viewpoint of maintaining strength, a support having a thickness of 10 to 30 μm is preferably used.

<Photosensitive layer>
The photosensitive layer contains (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, and may contain an appropriately selected polymerization inhibitor and other components as necessary.

The photosensitive layer preferably has a thickness of 15 μm or less. The thickness of the photosensitive resin layer is preferably 15 μm or less from the viewpoints of flexibility and reducing bleed-out, and is preferably 3 μm or more from the viewpoints of conforming to the unevenness of the wiring and ensuring rust resistance. The photosensitive layer may also have two or more layers.

The photosensitive layer preferably has a minimum viscosity of 1,000 Pa·s or less before curing. A minimum viscosity of 1,000 Pa·s or less provides good developability. The minimum viscosity is preferably 500 Pa·s or less, more preferably 300 Pa·s or less, and even more preferably 200 Pa·s or less. There is no particular lower limit, but it may be 10 Pa·s or more, 30 Pa·s or more, or 50 Pa·s or more.

((A) Alkali-soluble resin)
The alkali-soluble resin (A) used in the present invention is not limited as long as it is a polymer containing a carboxyl group, and examples thereof include acrylic copolymers such as (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylonitrile and (meth)acrylamide, polyimide precursors, carboxyl group-containing polyimides, carboxyl group-containing urethane resins, and acid-modified epoxy (meth)acrylate compounds.

The acid value (mgKOH/g) of (A) the alkali-soluble resin is 60 or more, and preferably 60 to 200. From the viewpoints of reducing moisture permeability and improving the rust resistance of the conductor, the acid value is preferably 200 or less, and from the viewpoint of improving developability, the acid value is 60 or more, and from the viewpoint of the balance between the rust resistance of the conductor and low-temperature developability, the acid value is more preferably 80 to 180, and even more preferably 90 to 160.

The acid value is measured by potentiometric titration using 0.1 mol/L potassium hydroxide using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. (A) The alkali-soluble resin may have an ethylenically unsaturated group at the end of the main chain and/or in the side chain.

The weight average molecular weight of the alkali-soluble resin (A) is 4,000 to 500,000 from the viewpoints of coatability, coating film strength, tackiness of the transfer film, and developability. The weight average molecular weight of the alkali-soluble resin is preferably 4,000 or more from the viewpoints of the properties of the development aggregate, tackiness when used as a transfer film, edge fuse property, cut chip property, and other properties of the unexposed film, and from the viewpoints of adhesion to the substrate after the transfer film is formed on the underlying substrate with a conductor and cured, and is preferably 500,000 or less from the viewpoint of maintaining developability. Here, edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end surface of the roll when wound into a roll as a transfer film. Cut chip property is a phenomenon in which chips fly off when the unexposed film is cut with a cutter. If the scattered chips adhere to the upper surface of the transfer film, they are transferred to a mask in a subsequent exposure process, etc., causing defects. The weight average molecular weight of the alkali-soluble resin (A) is more preferably 5,000 to 30,000. The weight average molecular weight according to this embodiment is measured using a gel permeation chromatography (GPC) manufactured by JASCO Corporation under the following conditions. The weight average molecular weight thus obtained is a polystyrene-equivalent value.
Pump: Gulliver, PU-1580 type Column: Showa Denko K.K.'s Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 columns in series
Mobile phase solvent: tetrahydrofuran Calibration curve: calibration curve determined using a polystyrene standard sample {calibration curve using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.)}

The hydroxyl value (mgKOH/g) of the (A) alkali-soluble resin is preferably 40 or less, more preferably 30 or less. By having a hydroxyl value of 40 or less, the moisture permeability of the cured product after the photosensitive resin composition is exposed to light and thermally cured can be reduced, improving the rust resistance of the conductor.

The hydroxyl value of the alkali-soluble resin (A) can be measured as follows. First, the solution of the alkali-soluble resin (A) to be measured for the hydroxyl value is placed on an aluminum plate and heated for 4 hours at a temperature 10°C higher than the boiling point of the solvent in the solution to completely remove the solvent. 1 g of the solid content of the alkali-soluble resin (A) thus obtained is precisely weighed, and 10 mL of a 10% by mass pyridine acetic anhydride solution is added thereto to dissolve uniformly, and the mixture is heated at 100°C for 1 hour. After heating, 10 mL of water and 10 mL of pyridine are added and heated at 100°C for 10 minutes. Then, the hydroxyl value is measured by neutralization titration with a 0.1 mol/L ethanol solution of potassium hydroxide using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.).
The hydroxyl value can be calculated by the following formula.
Hydroxyl value = (A - B) x f x 28.05 / sample (g) + acid value In the formula, A represents the amount (mL) of 0.1 mol/L potassium hydroxide ethanol solution used in the blank test, B represents the amount (mL) of 0.1 mol/L potassium hydroxide ethanol solution used in titration, and f represents a factor.

((B) Photopolymerizable Compound)
The photopolymerizable compound according to the present embodiment is a compound having an ethylenically unsaturated double bond, for example, 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 its molecule, and more preferably includes (b2) a compound having one polymerizable group in its molecule.In addition, the compound having an ethylenically unsaturated double bond can be used in combination with other compounds than those mentioned above.

By including a compound having three or more polymerizable groups in the molecule (b1) of the (B) component, the crosslink density of the protective film increases, moisture and the like become less likely to penetrate, and the rust prevention of the conductor can be reduced. (b1) A compound having three or more polymerizable groups in the molecule has three or more moles of a group to which an alkylene oxide group can be added as a central skeleton in the molecule, and is obtained by adding an alkylene oxide group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group to this group and converting the obtained alcohol into a (meth)acrylate. In addition, the central skeleton may not be modified with an alkylene oxide group, and (meth)acrylic acid may be reacted directly with the central skeleton. Examples of compounds that can become the central skeleton include glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, isocyanurate rings, and the like. From the viewpoint of improving the rust resistance of the conductor, it is more preferable that the photosensitive resin composition contains dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or ditrimethylolpropane tri(meth)acrylate. In addition, it is more preferable that the photosensitive resin composition contains at least a compound having a molecular weight of 430 or less as a compound having three or more polymerizable groups in the molecule (b1). When the molecular weight of the component (b1) is 430 or less, the developability of the photosensitive resin composition layer is improved. Examples of compounds having a molecular weight of 430 or less include compounds having glycerin, trimethylolpropane, pentaerythritol, or the like as a central skeleton. From the viewpoint of achieving both the developability of the photosensitive resin composition layer and the improvement of the rust resistance of the conductor, it is preferable that the component (B) contains pentaerythritol tetra(meth)acrylate, or trimethylolpropane tri(meth)acrylate. There is no particular lower limit for the molecular weight, but the molecular weight may be 100 or more, or 150 or more.

By further including a compound having one polymerizable group in the molecule (b2) without the compound (b1) or in addition to the compound (b1), the reaction rate of the entire compound having an ethylenically unsaturated double bond (B) is improved, and the rust prevention of the conductor can be expected to be improved. In addition, the developability of the photosensitive resin composition layer may also be improved. Examples of compounds having one polymerizable group in the molecule (b2) include a compound in which (meth)acrylic acid is added to one end of a polyalkylene oxide, a compound in which (meth)acrylic acid is added to one end and the other end is alkyl ether or allyl etherified, and the like. Examples include m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 4-methacryloyloxybenzophenone, EO-modified paracumylphenol acrylate, nonylphenoxyethyl acrylate, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, 4-normal octylphenoxypentapropylene glycol acrylate, and 1,6-hexanediol (meth)acrylate. From the viewpoint of improving the rust prevention properties of the conductor, it is more preferable to include m-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate, 4-methacryloyloxybenzophenone, EO-modified paracumylphenol acrylate, and nonylphenoxyethyl acrylate.

Other examples of (B) compounds (b3) having an ethylenically unsaturated double bond include compounds having (meth)acryloyl groups at both ends of a polyalkylene oxide chain, compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain in which a polyethylene oxide chain and a polypropylene oxide chain are bonded randomly or in blocks, and compounds in which bisphenol A is modified with an alkylene oxide and has (meth)acryloyl groups at both ends.

Other examples of (B) compounds (b3) having an ethylenically unsaturated double bond include urethane compounds which are reaction products of diisocyanate compounds and compounds having a hydroxyl group and a (meth)acrylic group in one molecule.

The content of the compound having an ethylenically unsaturated double bond (B) in the photosensitive resin composition is preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass, based on the mass of the photosensitive resin composition, from the viewpoints of resolution, adhesion of the cured film to the conductor, and rust prevention of the conductor.

((C) Photopolymerization initiator)
The photopolymerization initiator (C) according to this embodiment is a compound that generates radicals by actinic rays and can polymerize an ethylenically unsaturated group-containing compound, etc. The photopolymerization initiator (C) according to this embodiment is a compound that generates radicals by actinic rays and can polymerize an ethylenically unsaturated group-containing compound, etc. Examples of the photopolymerization initiator (C) include aromatic ketones such as benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylated benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxy)- ... oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime); benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; and phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The photopolymerization initiators may be used alone or in combination of two or more.

Among these, from the viewpoint of improving the rust prevention of the conductor, reducing the moisture permeability of the cured film, and improving the chemical resistance, oxime ester compounds are preferred, and among these, compounds with a high molar absorption coefficient at 365 nm are more preferred. By using an oxime initiator with a high absorption coefficient at a wavelength of 365 nm, a highly sensitive protective film can be obtained by i-line exposure. Among these, from the viewpoint of rust prevention, oxime ester compounds are preferred, and among these, compounds with a high molar absorption coefficient at 365 nm are more preferred. By using an oxime initiator with a high absorption coefficient at a wavelength of 365 nm, a highly sensitive protective film can be obtained by i-line exposure. It is presumed that this provides high surface curability, suppresses the intrusion of sodium ions during the development process as described above, and as a result, provides high rust prevention of the conductor.

Specific examples of oxime ester compounds include 1,2-octanedione, 1-[(4-phenylthio)phenyl-, 2-(O-benzoyloxime)] (manufactured by BASF Japan Ltd., product name: Irgacure Oxe01), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF Japan Ltd., product name: Irgacure Oxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, product name, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (TR-PBG-326, product name, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)(orthotolyl)methanone O-acetyloxime (Daito Chemistry Co., Ltd. DFI-020), 1,8-octanedione, 1,8-bis[9-(2-ethylhexyl)-6-nitro-9H-carbazol-3-yl]-, 1,8-bis(O-acetyloxime), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)octanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2 -dione-2-(O-benzoyloxime) (product name TR-PBG-371, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (product name TR-PBG-391, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), etc.

The content of the (C) photopolymerization initiator in the photosensitive resin composition is 0.1% by mass to 10% by mass based on the mass of the photosensitive resin composition, and from the viewpoint of sensitivity and resolution, it is more preferably 0.3% by mass to 5% by mass. If the content of the photopolymerization initiator is within the range of 0.1% by mass to 10% by mass, the photosensitivity is sufficient, and problems such as insufficient internal photocuring due to increased absorption at the surface of the composition when irradiated with active light and reduced visible light transmittance can be suppressed.

((D) Thermal Crosslinking Agent)
From the viewpoint of achieving higher rust-preventive performance, it is preferable to further compound (D) a thermal crosslinking agent in the photosensitive resin composition. (D) Thermal crosslinking agent means a compound that undergoes an addition reaction or a condensation polymerization reaction with (A) an alkali-soluble resin and (D) a thermal crosslinking agent added at the same time by heat. The temperature at which the addition reaction or the condensation polymerization reaction occurs is preferably 100°C to 150°C. The addition reaction or the condensation reaction occurs during a heat treatment after a pattern is formed by development.

Specific examples of thermal crosslinking agents include, but are not limited to, blocked isocyanate compounds, diol compounds, epoxy compounds, and the thermal crosslinking agents described in paragraphs [0054] and after of WO 2016/047691.

A blocked isocyanate compound is a compound obtained by reacting an isocyanate compound that has two or more isocyanate groups in the molecule with a blocking agent.

Examples of isocyanate compounds include 1,6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-hydroxydiisocyanate, 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.

Examples of blocking agents include alcohols, phenols, ε-caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, carbamates, imines, and sulfites.

Specific examples of blocked isocyanate compounds 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, etc.), and tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc., etc.). , 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Bronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanate methyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Inc., and Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951, and 7990 manufactured by Baxenden). These blocked isocyanate compounds may be used alone or in combination of two or more types.

The diol compound refers to a compound containing two hydroxyl groups per molecular chain, and examples of the compound include a compound containing a hydrocarbon group, such as an aliphatic, aromatic, or alicyclic group, in the skeleton.
Specific examples of the diol compound include polytetramethylene diols (e.g., P4TMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, and PTMG3000, manufactured by Mitsubishi Chemical Corporation), polybutadiene diols (e.g., G-1000, G-2000, and G-3000, manufactured by Nippon Soda Co., Ltd.), hydrogenated polybutadiene diols (e.g., GI-1000, GI-2000, and GO-3000, manufactured by Nippon Soda Co., Ltd.), polycarbonate diols (e.g., Duranol T5651, Duranol T5652, Duranol T4671, Duranol G4672, Duranol G3452, and Duranol G34, manufactured by Asahi Kasei Corporation), 50J, 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 (e.g., Plaxel 205PL, Plaxel 210, Plaxel 220, and Plaxel 220PL manufactured by Daicel Co., Ltd.), polyester diols (e.g., Kuraray Polyol P-530, Kuraray Polyol P-2030, and Kuraray Polyol P-2050 manufactured by Kuraray Co., Ltd., and HS2N-220S manufactured by Toyokuni Oil Mills Co., Ltd.), bisphenols (e.g., Bisphenol A manufactured by Mitsubishi Chemical Co., Ltd.), and hydrogenated bisphenols (e.g., Rikabinol HB manufactured by New Japan Chemical Co., Ltd.). These diol compounds may be used alone or in combination of two or more types.

The (D) thermal crosslinking agent is preferably a blocked isocyanate compound from the viewpoints of storage stability of the transfer film and reducing moisture permeability of the cured film, and more preferably used in combination with a diol compound from the viewpoint of improving the developability of the photosensitive resin composition layer.

The content of the thermal crosslinking agent (D) in the photosensitive resin composition is 0.2% by mass to 40% by mass based on the mass of the photosensitive resin composition, and from the viewpoints of developability and low water permeability, it is more preferably 1% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass.

The blocked isocyanate compound reacts with the hydroxyl group of the alkali-soluble resin (A) or the diol compound used in combination during heat treatment after pattern formation by development, so that the moisture permeability of the cured film is reduced and the rust prevention properties for protecting the substrate, electrodes, etc. are improved. Furthermore, the blocked isocyanate compound crosslinks with the alkali-soluble resin (A) to increase the crosslink density of the cured film and reduce the diffusibility of water, which is thought to reduce the moisture permeability of the cured film and improve the rust prevention properties of the conductor. In addition, since the isocyanate group of the blocked isocyanate is blocked with a blocking agent, the reaction with the alkali-soluble resin (A) or the diol compound at room temperature is suppressed, and the stability of the photosensitive resin composition and the transfer film is maintained.

The diol compound has a hydrophilic hydroxyl group, so that the developability is good. In addition, in the heat treatment after the pattern formation by development, the hydroxyl group of the diol compound reacts with the blocked isocyanate compound, so that the excellent rust prevention of the conductor is maintained. From the viewpoint of developability, the molecular weight of the diol compound is preferably 300 to 3,000, and more preferably 500 to 2,000. On the other hand, if unreacted hydroxyl groups remain after thermal curing, the moisture permeability of the cured film may deteriorate, which may cause the rust prevention performance of the conductor to be impaired. Therefore, the diol compound is preferably added so that the hydroxyl value of the photosensitive resin composition is 20 mgKOH/g or less, and more preferably 15 mgKOH/g or less. By having a hydroxyl value of 20 or less of the photosensitive resin composition, the moisture permeability of the cured product of the photosensitive resin composition can be reduced, and the rust prevention of the conductor is improved.

((E) Rosin ester compound)
From the viewpoint of achieving a lower water permeability, it is preferable to further blend (E) a rosin ester compound in the photosensitive resin composition. The (E) rosin ester compound according to the present embodiment is a compound having an ester bond obtained by reacting a compound selected from the group consisting of rosin acid, a dimer of rosin acid, a hydrogenated product of rosin acid, and a disproportionated product of rosin acid, which is a non-volatile component of pine resin, with any one of a hydroxyl compound, a phenol compound, and a glycidyl compound, or a compound having an ester bond obtained by glycidylating a rosin acid derivative and reacting it with any one of a carboxyl compound and a phenol compound.

(E) Specific examples of rosin ester compounds include products from Arakawa Chemical Industries, Ltd. such as the Ester Gum series, Pine Crystal series, Super Ester series, Pencel series, and Beamset 101, and products from Harima Chemical Industries, Ltd. such as the Harie Star series, Neotol series, and Haritac series.

(E) Rosin ester compound is a compound that has high hydrophobicity due to having an alicyclic structure and an ester structure, but has good compatibility with (A) alkali-soluble resin, (B) photopolymerizable compound, and (C) photopolymerization initiator in the photosensitive resin composition, so it does not inhibit the developability of the composition, and therefore has an excellent balance of performance such as low-temperature developability of the transfer film, moisture permeability of the cured film, and rust prevention of the conductor.

From the viewpoint of the rust prevention of the conductor, it is more preferable that the rosin ester compound (E) has an acid value of 20 mgKOH/g or less. Examples of the above-mentioned products of Arakawa Chemical Co., Ltd. and Harima Chemical Co., Ltd. include Pine Crystal KE-100, Ester Gum 105, Super Ester A-115, Super Ester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, Beamset 101, Harie Star S, Neotoll 125HK, Haritac F105, Haritac FK125, and Haritac PCJ.

Furthermore, from the viewpoint of reducing the moisture permeability of the cured film, it is more preferable that the (E) rosin ester compound has a softening point of 100°C or higher. Specific compounds that meet these conditions include, for example, Ester Gum 105, Super Ester A-115, Super Ester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, and Neotol 125HK. It is particularly preferable that the compound has a softening point of 110°C or higher. Specific compounds that meet these conditions include, for example, Super Ester A-115, Super Ester A-125, Pencel A, Pencel C, Pencel D-125, Pencel D-135, Pencel D-160, and Neotol 125HK. (F) The rosin ester compound may be used alone or in a mixture of two or more kinds.

The content of the (E) rosin ester compound in the photosensitive resin composition is 1% by mass to 20% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. From the viewpoints of moisture permeability and developability, it is more preferably 5% by mass to 20% by mass, and from the viewpoint of adhesion to the substrate, it is even more preferably 5% by mass to 15% by mass. If the content of the (E) rosin ester compound is within the range of 1% by mass to 20% by mass, a good balance of performance between the low-temperature developability of the transfer film and the moisture permeability of the cured film is achieved.

(F) Rust Inhibitors
The rust inhibitor according to the present embodiment refers to a compound having a rust-preventing effect, and is, for example, a substance that forms a coating on a metal surface to prevent corrosion or rust of the metal.

From the viewpoint of compatibility and sensitivity with the photosensitive resin composition according to this embodiment, the rust inhibitor is preferably a heterocyclic compound containing N, S, O, etc., such as 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, and thiophene and its derivatives. The derivatives described here include compounds in which a substituent has been introduced into the parent structure. For example, in the case of a tetrazole derivative, a compound in which a substituent has been introduced into tetrazole is included. The substituent is not particularly limited, but examples include a hydrocarbon group (which may be saturated or unsaturated, straight-chain or branched, and may contain a cyclic structure in its structure), or a substituent containing one or more functional groups having a heteroatom, such as a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an amide group, a nitro group, a cyano group, a thiol group, and a halogen group (fluorine, chlorine, bromine, iodine, etc.).

Furthermore, from the viewpoint of rust prevention, the heterocyclic compound is preferably a compound having a heterocyclic ring composed of C and N and/or S, and in the same heterocyclic ring, the number of N atoms is 3 or less, the number of S atoms is 3 or less, or the total number of N atoms and S atoms is 3 or less. More preferred heterocyclic compounds are 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 viewpoint of rust prevention and developability, the compound is more preferably benzotriazole and its derivatives, and imidazole and its derivatives.

Specific examples of compounds having a heterocycle composed of C and N and/or S, in which the number of N atoms in the same heterocycle is 3 or less, 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:
Triazoles, for example, 1,2,3-triazole, 1,2,4-triazole, etc.;
Triazole derivatives, for example, 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, etc.;

Imidazole; imidazole derivatives, for example, undecylimidazole, 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, etc.;
Imidazoline; imidazoline derivatives, for example, 2-undecylimidazoline, 2-propyl-2-imidazoline, 2-phenylimidazoline, etc.;
Thiazole; thiazole derivatives, for example, 2-amino-4-methylthiazole, 5-(2-hydroxyethyl)-4-methylthiazole, benzothiazole, 2-mercaptobenzothiazole, 2-aminobenzothiazole, 2-amino-6-methylbenzothiazole, (2-benzothiazolylthio)acetic acid, 3-(2-benzothiazolylthio)propionic acid, and the like;

Isothiazole; isothiazole derivatives such as 3-chloro-1,2-benzisothiazole;
Thiadiazole, for example, 1,2,3-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, etc.; thiadiazole derivatives, for example, 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.;
Thiophene; thiophene derivatives such as 2-thiophenecarboxylic acid, methyl 3-amino-2-thiophenecarboxylate, and 3-methylbenzothiophene.

Among the above-mentioned rust inhibitors, benzotriazole, 5-carboxybenzotriazole, 1-hydroxybenzotriazole, and 5-chlorobenzotriazole are particularly preferred from the viewpoints of rust prevention for the conductor and low-temperature developability of the transfer film.
On the other hand, from the viewpoints of the rust prevention properties of the conductor and the adhesion of the cured film to the substrate, tetrazole and derivatives thereof, triazole and derivatives thereof, indazole and derivatives thereof, and thiadiazole and derivatives thereof are preferred as the component (F).

Specific examples of tetrazole 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.

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

Specific examples of triazole and its derivatives, and thiadiazole and its derivatives have already been described above. Among them, 5-amino-1H-tetrazole, 5-carboxybenzotriazole, 5-aminoindazole, and 5-amino-1,2,3-thiadiazole are particularly preferred from the viewpoint of the rust prevention properties of the conductor and the adhesion of the cured film to the substrate. In this embodiment, one of the rust inhibitors described above may be used alone, or two or more of them may be used in combination.

From the viewpoint of the rust prevention of the conductor or the low-temperature developability of the transfer film, the content of the rust inhibitor in the photosensitive resin composition is preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and even more preferably 0.2% by mass to 3% by mass, based on the mass of the photosensitive resin composition.

(Other ingredients)
In the present embodiment, in addition to the components (A) to (F), other components (G) such as an oligomer having a carboxyl group and an ethylenically unsaturated group, a polymerization inhibitor such as an aluminum salt to which 3 moles of nitrosophenylhydroxylamine have been added, an antioxidant, an adhesion aid, a leveling agent, a filler, an antifoaming agent, and a flame retardant can also be contained in the photosensitive resin composition, and these can be used alone or in combination of two or more kinds.

In this embodiment, the hydroxyl value (mgKOH/g) of the photosensitive resin composition is preferably 20 or less, and more preferably 15 or less. By making the hydroxyl value of the photosensitive resin composition 20 or less, the moisture permeability of the cured product of the photosensitive resin composition can be reduced, thereby improving the rust resistance of the conductor.

Examples of the solvent that dissolves the photosensitive resin composition include ketones such as methyl ethyl ketone (MEK); and alcohols such as methanol, ethanol, or isopropanol.
The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition to be applied onto a support is 3 mPa·s to 3,000 mPa·s at 25°C.

Examples of coating methods include doctor blade coating, Mayer bar coating, roll coating, screen coating, spinner coating, inkjet coating, spray coating, dip coating, gravure coating, curtain coating, and die coating. There are no particular restrictions on the drying conditions of the coating liquid, but the drying temperature is preferably 50°C to 130°C, and the drying time is preferably 30 seconds to 30 minutes.

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

<Pattern Manufacturing Method>
The formation of a pattern using the photosensitive resin laminate of the present embodiment includes the following steps:
The method includes a step of laminating a photosensitive layer on a substrate under a vacuum atmosphere by peeling off the protective film of the photosensitive resin laminate of this embodiment; a step of exposing; and a step of developing. More specifically, a resin pattern can be produced by a method including a vacuum lamination step of laminating the photosensitive resin laminate described above on a substrate; an exposure step of exposing the laminated photosensitive layer; and a development step of developing the exposed photosensitive layer. Furthermore, in order to use the resin pattern as a protective film for the conductor portion, it is preferable to form a cured film pattern by subjecting the resin pattern to a post-exposure treatment and/or a heat treatment after the development step.

An example of a specific method is shown below. As the substrate, a substrate in which copper wiring is formed on a copper-clad laminate, a glass substrate, a transparent resin substrate on which a transparent electrode (e.g., ITO, Ag nanowire substrate, etc.) or a metal electrode (e.g., Cu, Al, Ag, Ni, Mo, and alloys of at least two of these, etc.) is formed, a touch panel substrate or a touch sensor substrate (e.g., a force sensor, etc.) can be used. A flexible copper-clad laminate, a substrate for forming a touch panel electrode, or a substrate for forming a touch sensor electrode is a substrate formed by forming a copper layer or a transparent electrode, or a metal layer that is the raw material for the metal electrode, on a flexible film.

Examples of the film include films made of film materials such as polyimide, polyester (PET, PEN), and cycloolefin polymer (COP). The thickness of the film is preferably 10 μm to 100 μm. In addition to pure copper, the copper may be an alloy containing copper as a main component. Here, "main component" means that at least 50 mass % of the alloy is copper. Examples of alloy metals include alloys of copper with nickel, palladium, silver, titanium, molybdenum, etc.
The thickness of the copper layer is preferably 50 nm to 2 μm, and from the viewpoint of uniformity of the copper layer, the thickness of the copper layer is more preferably 100 nm or more.

By carrying out a process of vacuum laminating a photosensitive resin laminate on the substrate as described above, a photosensitive layer is formed on the copper layer of the substrate. The transfer film is laminated by heat pressing onto the substrate surface using a laminator. In this case, the transfer film may be laminated on only one side of the substrate surface or on both sides. The heating temperature is generally about 40°C to 160°C. Heat pressing may be performed using a two-stage laminator equipped with two rolls, or may be performed by repeatedly passing the transfer film and substrate through the rolls multiple times. In addition, when a vacuum roll laminator is used, the protective film has good conformability to unevenness caused by wiring on the substrate, and the defect of air being mixed between the transfer film and substrate can be prevented. On the other hand, when a vacuum roll laminator is used, the oxygen concentration that suppresses radical polymerization is significantly low, so the photopolymerization initiator is cleaved and the dark reaction is easily promoted. Therefore, the roll temperature is preferably 40°C to 100°C, and even more preferably 40°C to 80°C.

Next, an exposure step is performed using an exposure machine. If necessary, the support is peeled off, and the photosensitive layer is exposed to active light through a photomask. The exposure amount is determined by the light source illuminance and exposure time. The exposure amount may be measured using an actinometer. Examples of exposure machines include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine with adjusted parallelism, and a proximity exposure machine with a gap between the mask and the workpiece. Further examples of exposure machines include a projection type exposure machine with a mask to image size ratio of 1:1, a high-illuminance reduction projection exposure machine called a stepper (registered trademark), or an exposure machine using a concave mirror called a mirror projection aligner (registered trademark).

In addition, a direct imaging exposure method may be used in the exposure process. Direct imaging exposure is a method of directly imaging and exposing the substrate without using a photomask. As a light source, for example, a solid-state laser with a wavelength of 350 nm to 410 nm, a semiconductor laser, or an ultra-high pressure mercury lamp is used. The imaging pattern is controlled by a computer. In this case, the exposure dose is determined by the light source illuminance and the substrate movement speed.

Next, a development step is performed using a developing device. After exposure, if there is a support film on the photosensitive resin layer, the support film is removed as necessary, and then the unexposed portion is developed and removed using an alkaline aqueous developer to obtain a resin pattern. As the alkaline aqueous solution, it is preferable to use an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ (alkaline aqueous solution). The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution with a concentration of about 0.2% by mass to 2% by mass and at about 20°C to 40°C is generally used. When the temperature of the developer is high, moisture tends to evaporate easily under a negative pressure environment due to exhaust gas or the like as a countermeasure against odor, and the developer tends to become concentrated over time, resulting in a loss of stable productivity. Therefore, the developer temperature is preferably less than 30°C. In addition, a surfactant, an antifoaming agent, a small amount of an organic solvent to promote development, etc. may be mixed into the alkaline aqueous solution. In consideration of the influence on the substrate, an amine-based alkaline aqueous solution such as an aqueous tetramethylammonium hydroxide (TMAH) solution can also be used. The concentration of the alkaline compound in the aqueous solution can be appropriately selected depending on the development speed. From the viewpoints that the developer has little odor, is easy to handle, and is easy to manage and after-treatment, a 1% by mass Na ₂ CO ₃ aqueous solution at 25°C to 30°C is particularly preferred. Development methods include known methods such as alkaline water spray, shower, rocking immersion, brushing, and scraping.

After development, the base of the alkaline aqueous solution remaining in the resin pattern can be acid-treated (neutralized) using an organic acid, an inorganic acid, or an aqueous solution of these acids by known methods such as spraying, rocking immersion, brushing, scraping, etc. Furthermore, after the acid treatment (neutralization), a step of washing with water can also be carried out.

Although a resin pattern can be obtained through each of the above steps, a post-exposure step and/or a heating step may be further performed. By performing a post-exposure step and/or a heating step, the rust prevention property is further improved. The exposure dose in the post-exposure treatment is preferably 200 mJ/cm ² to 1,000 mJ/cm ² , and the heating step is preferably performed at 40°C to 200°C, and from the viewpoint of the manufacturing process, the heating treatment time is preferably 60 minutes or less. As the method of the heating treatment, a suitable heating furnace such as hot air, infrared, or far infrared can be used, and the atmosphere of the heating treatment can be an N ₂ atmosphere or an N ₂ /O ₂ atmosphere.

According to this embodiment, the photosensitive layer has good tackiness, low-temperature lamination properties, and low-temperature developability, and the cured film has good moisture permeability and adhesion to a conductive substrate, and a photosensitive resin composition and photosensitive resin laminate suitable for protecting conductor parts such as wiring and electrodes can be provided. Such a photosensitive resin laminate is suitable, for example, as a protective film for wiring and electrodes for touch panels, touch sensors, or force sensors, or as a solder resist for printed wiring boards.

<<Touch panel display device, device having touch sensor or force sensor>>
By forming a cured film of the photosensitive resin laminate according to this embodiment on a touch panel substrate, it is possible to provide a touch panel display device having a cured film of a photosensitive layer, and a device having a cured film of a transfer film and a touch sensor and/or a force sensor.
Examples of the substrate for a touch panel include substrates generally used for touch panels, touch sensors, or force sensors, such as glass plates, plastic plates, plastic films, ceramic plates, etc. On this substrate, electrodes or metal wiring for a touch panel made of ITO, Cu, Al, Ag, Ni, Mo, or alloys containing at least two of these materials, on which a protective film is to be formed, are provided, and an insulating layer may be provided between the substrate and the electrodes.

A touch panel substrate having a touch panel electrode can be obtained, for example, by the following procedure. A metal film or metal oxide film is formed on a touch panel substrate such as polyester or COP film by sputtering ITO and Cu in that order, and then a photosensitive film for etching is attached to the metal film or metal oxide film to form a desired resist pattern. Unnecessary Cu is removed with an etching solution such as an aqueous iron chloride solution, and the resist pattern is then peeled off and removed.

The method for forming a cured film as a protective film on a substrate for a touch panel preferably includes, in this order, a first step of laminating the transfer film according to this embodiment onto the substrate for a touch panel, a second step of curing a predetermined portion of the protective film by irradiation with active light, a third step of removing the portion of the protective film other than the predetermined portion (the portion of the protective film not irradiated with active light) to form a cured product of the patterned protective film, and a fourth step of exposing and/or heat-treating the patterned protective film.

By producing a touch panel substrate having a cured film pattern of a photosensitive resin laminate as described above, it is possible to provide a touch panel display device having a cured film of a transfer film, or a device having a cured film of a transfer film and a touch sensor and/or a force sensor.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

1. Preparation of Evaluation Samples The photosensitive resin laminates in Examples 1 to 4 and Comparative Examples 1 to 4 were prepared as follows.

<Preparation of photosensitive resin roll>
The compounds shown in Table 1 below were prepared, and the photosensitive resin composition having the composition ratio (values in the table are parts by mass) shown in Table 2 below was mixed with methyl ethyl ketone (MEK) as a solvent for dissolving them, and the mixture was stirred well to obtain a photosensitive resin composition preparation liquid in the form of a homogeneous solution. The photosensitive resin composition preparation liquid was uniformly applied to the surface of a polyethylene terephthalate film with a thickness of 16 μm as a support using a bar coater, and then dried to form a photosensitive layer. The thickness of the photosensitive layer was 8 μm.

Next, a protective layer film shown in Table 2 below was laminated onto the surface of the photosensitive layer on the side not laminated with the support to obtain a photosensitive resin laminate.

Then, the obtained photosensitive resin laminate was wound up to 200 m on a 3-inch ABS core to obtain a photosensitive resin roll.

2. Evaluation of Transferability The transferability of the photosensitive resin laminate was evaluated as follows.
First, the prepared photosensitive resin roll was set on the unwinding shaft in the chamber of a vacuum laminator (manufactured by MCK Co., Ltd.). Next, the degree of vacuum in the chamber was reduced to 50 Pa using a vacuum pump and maintained for 1 hour. Next, the pressure in the chamber was returned to atmospheric pressure, and then a photosensitive resin laminate having an area of 10 m x 0.1 m was cut out from the photosensitive resin roll. Next, the protective film was peeled off at a speed of 100 mm/sec, and it was visually confirmed whether or not the photosensitive layer was attached to the surface of the protective film. If the photosensitive layer was attached, the area of the photosensitive layer was measured.
<Evaluation method>
◯: No adhesion of the photosensitive layer to the surface of the peeled protective film was observed.
×: A photosensitive layer was found to adhere to the surface of the peeled protective film, and the area of the adhered photosensitive layer was less than 100 ^mm2 .
XX: A photosensitive layer was found to adhere to the surface of the peeled protective film, and the area of the adhered photosensitive layer was 100 ^mm2 or more.

3. Evaluation of Rust Prevention of Coated Parts <Preparation of Test Substrate>
A photosensitive resin laminate was prepared as described in Example 2 of Japanese Patent No. 4515123, and the photosensitive resin laminate was laminated on the copper surface of a flexible substrate having a size of 10 cm x 10 cm, in which resin, ITO, and sputtered copper were laminated in this order, using a hot roll laminator while peeling off the protective film. At that time, the roll temperature was 100°C, the air pressure was 0.4 MPa, and the lamination speed was 1.5 m/min. After leaving it for 30 minutes, a PET mask was placed on the support film and exposed from the PET mask side at 120 mJ/ ^cm2 using a parallel light exposure machine. A PET mask with a line/space = 80 μm/80 μm pattern was used. After that, after leaving it for 30 minutes or more, the support film was peeled off, and a 1% by mass Na ₂ CO ₃ aqueous solution at 30° C. was sprayed with a full cone type nozzle at a development spray pressure of 0.15 MPa for twice the minimum development time using a developing device manufactured by Fuji Kiko Co., Ltd., to dissolve and remove the unexposed part of the photosensitive resin layer. Here, the minimum development time refers to the minimum time required for the unexposed part of the photosensitive resin composition layer to be completely dissolved and removed. At that time, the water washing process was performed with a flat type nozzle at a water washing spray pressure of 0.15 MPa for the same time as the development process, and the resist pattern was formed on the copper by drying with an air blow.

Next, the substrate on which the resist pattern was formed was etched by dipping in an aqueous solution of 2% by mass hydrochloric acid and 2% by mass ferric chloride at a liquid temperature of 30° C. for 1.5 times the minimum etching time. Then, the substrate was washed with water and air-dried. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions.
After the etching, the substrate was immersed in a 3 wt% NaOH aqueous solution at a liquid temperature of 50°C, the resist was removed by a dip method, and then washed with water and air-dried. This resulted in a test substrate in which ITO was laminated on the resin and a copper wiring pattern was formed on top of the ITO. More specifically, the copper wiring pattern was formed with 10 copper lines, each 8 cm long and 80 μm wide, with a line:space ratio of 1:1.

<Sample preparation method>
The photosensitive resin laminate according to the present invention was laminated on the copper wiring-containing surface of the substrate formed by the above-mentioned method, while peeling off the protective film of the photosensitive resin laminate according to the present invention, using a hot roll laminator (TAISEI LAMINATOR CO., LTD., VA-400III). At that time, 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 30 minutes, the optimal exposure amount for each composition was exposed from the support film side of the protective film by a scattered light exposure machine. After standing for 30 minutes, the support film was peeled off, and a 1% by mass Na ₂ CO ₃ aqueous solution at 35°C was sprayed for a predetermined time of 60 seconds using a developing device manufactured by Fuji Kiko Co., Ltd. at a development spray pressure of 0.12 MPa with a full cone type nozzle to perform development, and the unexposed portion of the photosensitive resin layer was dissolved and removed. At that time, the water washing process was performed with a flat type nozzle at a water washing spray pressure of 0.12 MPa for the same time as the development process, and the film was dried by air blowing. Thereafter, the sample was exposed from the photosensitive layer side with a scattered light exposure machine at an exposure dose of 350 mJ/ ^cm2 , and then treated in a hot air circulation oven at 150°C for 30 minutes to prepare a sample. The above optimal exposure dose and the specified time are defined in the same manner as in the method for preparing a sample for evaluating developability.

<Evaluation method>
An acidic artificial sweat solution as described in JIS L0848 was dropped onto the protective film located directly above the copper wiring of the prepared sample, and then the sample was stored in a thermo-hygroscopic oven (THN050FA, manufactured by Advantec Toyo Co., Ltd.) at 85°C and 85% RH. After a predetermined time had passed, the sample was removed from the oven and observed under a microscope from the protective film side and the side opposite the protective film to check for discoloration or corrosion of the copper wiring, and judged as follows.
A: Discoloration occurs after 500 hours or more in an environment of 85°C and 85% RH B: Discoloration occurs from 350 hours to less than 500 hours in an environment of 85°C and 85% RH C: Discoloration occurs from 200 hours to less than 350 hours in an environment of 85°C and 85% RH D: Discoloration or corrosion occurs in less than 200 hours in an environment of 85°C and 85% RH In terms of rust resistance of the coating, a rank of C or higher is practically necessary in the touch panel manufacturing process, and a rank of B or higher is considered to be a good result.

4. Measurement of viscosity of photosensitive layer before curing <Sample preparation method>
Two photosensitive resin laminates with a photosensitive layer thickness of 40 μm were prepared, and the surfaces from which the protective film had been peeled off were laminated together using a hot roll laminator (TAISEI LAMINATOR CO., LTD., VA-400III). After peeling off the support on one side, the protective film of the photosensitive layer with a thickness of 40 μm was peeled off and the laminate was further laminated twice to obtain a photosensitive resin laminate with a photosensitive layer thickness of 160 μm. The roll temperature was 100° C., the air pressure was 0.2 MPa, and the lamination speed was 0.5 m/min. The supports on both sides of the obtained laminate were peeled off to obtain a sample for viscosity measurement. The prepared sample was conditioned at 23° C. and RH 50% for one day, and then tested.

<Evaluation method>
The viscosity of the sample prepared by the above method was measured under the following conditions using a dynamic viscoelasticity measuring device (rheometer) (DHR-2, manufactured by TA Instruments), and the point at which the value changed from decreasing to increasing was read as the minimum value from the obtained viscosity curve. When there were two or more minimum values, each value was read.
(Measurement condition)
Sample size: 2.5 cm diameter, thickness 160 μm
Measurement temperature conditions: 30 to 200°C
Heating rate: 5°C/min Frequency: 1Hz
Load: 0.2N
Strain: 1.0%

The materials and compositions (parts by weight) of the photosensitive resin laminates used in each Example and Comparative Example, and the evaluation results of the protective films are shown in Tables 1 and 2.

The results shown in Table 2 indicate that Examples 1 to 4 satisfy the requirements set forth in the present invention, and thus have excellent transferability in a vacuum environment and rust prevention properties for the metal wiring coating.

On the other hand, Comparative Examples 1 to 4 do not satisfy any of the requirements stipulated in the present invention, and therefore show poor transferability in a vacuum environment or poor rust resistance of the metal wiring coating.

Although the present embodiment has been described above, the present invention is not limited to this embodiment, and can be modified as appropriate without departing from the spirit of the invention.

The photosensitive resin laminate of the present invention has good rust resistance and yield and is suitable for protecting conductors such as wiring and electrodes, and can be widely used as a protective film for wiring, electrodes, etc., in touch panels, touch sensors, force sensors, and solder resist applications for printed wiring boards.

REFERENCE SIGNS LIST 1 Support 2 Photosensitive layer 3 Protective film 4 Core material 5 Transfer 6 Fish eye 7 Bleed out 10 Photosensitive resin laminate 20 Vacuum laminator chamber

Claims (12)

A photosensitive resin laminate having a support, a photosensitive layer, and a protective film laminated in this order, the protective film including, on a surface in contact with the photosensitive layer, a region of 10 m length x ^{0.1 m} width, in which the number of fisheyes having an area of 2,000 μm2 or more and a maximum height of 1 μm or more from the surface of the protective film is more than 5 and less than 20,
The photosensitive layer comprises the following components:
(A) an alkali-soluble resin,
(B) a photopolymerizable compound; and (C) a photopolymerization initiator,
The photosensitive resin laminate includes a compound having three or more polymerizable groups in the molecule, and the photopolymerizable compound (B) includes a compound having three or more polymerizable groups in the molecule.
However, this does not include a photosensitive resin laminate in which the protective film is made of a polyethylene film and the photosensitive layer contains a photopolymerization initiator containing a 2,4,5-triarylimidazole dimer and N-phenylglycine and/or a coumarin derivative. A photosensitive resin laminate having a support, a photosensitive layer, and a protective film laminated in this order, the protective film including, on a surface in contact with the photosensitive layer, a region of 10 m length x ^{0.1 m} width, in which the number of fisheyes having an area of 2,000 μm2 or more and a maximum height of 1 μm or more from the surface of the protective film is more than 5 and less than 20,
The photosensitive layer comprises the following components:
(A) an alkali-soluble resin,
(B) a photopolymerizable compound,
(C) A photosensitive resin laminate containing a photopolymerization initiator and a polymerization inhibitor.
However, this does not include a photosensitive resin laminate in which the protective film is made of a polyethylene film and the photosensitive layer contains a photopolymerization initiator containing a 2,4,5-triarylimidazole dimer and N-phenylglycine and/or a coumarin derivative. The photosensitive resin laminate according to claim 1 or 2, wherein the protective film comprises polypropylene. The photosensitive resin laminate according to claim 3, wherein the protective film is a polypropylene film. The photosensitive resin laminate according to any one of claims 1 to 4, wherein the thickness of the photosensitive layer is less than 15 μm. The photosensitive resin laminate according to any one of claims 1 to 5, wherein the minimum viscosity of the photosensitive layer before curing is 1,000 Pa·s or less. The photosensitive resin laminate according to any one of claims 1 to 6, wherein the (B) photopolymerizable compound contains at least a compound having a molecular weight of 430 or less. The photosensitive resin laminate according to any one of claims 1 to 7, which is used to protect either a metal film or a metal oxide film. The photosensitive resin laminate according to any one of claims 1 to 8, which is used as either a protective film for a touch panel or a protective film for a force sensor. The photosensitive resin laminate according to any one of claims ¹ to ⁹ , wherein the protective film has an average number of fisheyes having an area of 2,000 µm2 or more and a maximum height of 1 µm or more from the surface of the protective film, the average number of fisheyes being more than 5 and less than 20 per m2 of a surface of the protective film in contact with the photosensitive layer. A pattern manufacturing method comprising peeling off the protective film of the photosensitive resin laminate according to any one of claims 1 to 10, laminating the photosensitive layer on a substrate in a vacuum atmosphere, exposing the substrate to light, and developing the substrate to produce a pattern. A device having a touch panel display device or a touch sensor having a pattern manufactured by the pattern manufacturing method according to claim 11.

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