CN115087927A

CN115087927A - Photosensitive film and method for producing photosensitive film

Info

Publication number: CN115087927A
Application number: CN202180013363.7A
Authority: CN
Inventors: 海鉾洋行
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-02-13
Filing date: 2021-02-08
Publication date: 2022-09-20
Also published as: JPWO2021161965A1; WO2021161965A1; JP7332780B2

Abstract

The invention provides a photosensitive film and application thereofIn the photosensitive film, when W expressed by mm is taken as the width of the film, x expressed by mm is taken as the distance from one end of the film to the measurement position of the film thickness in the film width direction, Ta expressed by mm is taken as the average value of the film thickness measured in the film width direction, Tg (x) expressed by mm is taken as the target value of the film thickness expressed by the following formula, and T (x) expressed by mm is taken as the thickness of the film measured from one end of the film to the position of the x in the film width direction, the proportion of the relationship of (Tg) x (98.8/100) < T (x) < Tg x) (101.2/100) is 90-100%.

Description

Photosensitive film and method for producing photosensitive film

Technical Field

The present invention relates to a photosensitive film and a method for producing the photosensitive film.

Background

A display device (for example, an organic electroluminescence display device and a liquid crystal display device) provided with a touch panel (for example, an electrostatic capacitance type input device) has a patterned conductive layer inside the touch panel. Examples of the patterned conductive layer include electrode patterns and wirings (e.g., peripheral wirings and lead wirings) corresponding to the sensors of the viewing unit.

In general, in the formation of a patterned layer, since the number of steps for obtaining a desired pattern shape is small, for example, a method of providing a photosensitive resin layer on a substrate using a photosensitive transfer material, and then exposing and developing the photosensitive resin layer through a mask having a desired pattern is widely used (for example, patent document 1).

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2019-128445

Disclosure of Invention

Technical problem to be solved by the invention

Most of film-like photosensitive transfer materials (hereinafter, referred to as "photosensitive films") are wound in a roll shape for easy transportation or transfer to a next step. In use, a so-called roll-to-roll (roll) system is used in which a photosensitive film is drawn from a roll and is bonded to a substrate wound in another roll, for example. However, in a photosensitive film wound in a roll shape, appearance defects may be observed. Examples of the appearance defects include winding displacement and deformation. The "winding displacement" refers to a state in which a part of the photosensitive film is displaced in the photosensitive film wound in a roll. Examples of the deformation include a wrinkle. The occurrence of the appearance defect described above affects the quality of a final product such as a web handling defect and a transfer defect.

The present invention has been made in view of the above circumstances.

An object of one embodiment of the present invention is to provide a photosensitive film in which winding displacement and deformation are suppressed when the photosensitive film is wound.

Another object of the present invention is to provide a method for manufacturing a photosensitive film, which can suppress occurrence of winding displacement and deformation when winding the photosensitive film.

Means for solving the technical problem

The present invention includes the following modes.

[ 1] A photosensitive film satisfying the relationship of Tg (x) x (98.8/100) < T x (x) Tg (x) x (100) x (101.2/100) when W (mm) is the width of the film, x (mm) is the distance from one end of the film in the film width direction to the measurement position of the film thickness, Ta (mm) is the average value of the film thickness measured in the film width direction, Tg (x) is the target value of the film thickness expressed by the following formula, and T (x) is the thickness measured from one end of the film in the film width direction to the x position, wherein the ratio of the film thickness measured from one end of the film in the film width direction to the x position is 90-100%.

[ numerical formula 1]

< 2 > the photosensitive film according to < 1 > having an average thickness of 5 to 55 μm.

< 3 > the photosensitive film according to < 1 > or < 2 > has a length of 500m or more.

< 4 > the photosensitive film according to any one of < 1 > to < 3 > and having a roll-like shape.

< 5 > the photosensitive film according to any one of < 1 > to < 4 > comprising a temporary support and a photosensitive resin layer.

< 6 > the photosensitive film according to any one of < 1 > to < 4 >, which comprises a temporary support, a photosensitive resin layer and a cover film in this order.

< 7 > the photosensitive film according to < 5 > or < 6 >, wherein,

the temporary support has an average thickness of 5 to 20 μm.

< 8 > the photosensitive film according to any one of < 5 > to < 7 >, wherein,

the surface of the temporary support on which the photosensitive resin layer is disposed has an arithmetic average roughness Ra of 0.05 [ mu ] m or less.

< 9 > the photosensitive film according to any one of < 5 > to < 8 >, wherein,

the average thickness of the photosensitive resin layer is 0.1 to 15 μm.

< 10 > the photosensitive film according to < 6 >, wherein,

the average thickness of the coating film is 10 to 20 μm.

< 11 > the photosensitive film according to < 6 > or < 10 > wherein,

The cover film has an arithmetic average roughness Ra of 0.1 [ mu ] m or less on the surface on which the photosensitive resin layer is disposed.

< 12 > a production method which gives a photosensitive film,

in the photosensitive film, when W expressed by millimeter is used as the width of the film, x expressed by millimeter is used as the distance from one end of the film in the film width direction to the measurement position of the film thickness, Ta expressed by millimeter is used as the average value of the film thickness measured in the film width direction, Tg (x) expressed by millimeter is used as the target value of the film thickness expressed by the following formula, and T (x) expressed by millimeter is used as the thickness of the film measured from one end of the film in the film width direction to the position of the x, the proportion of satisfying the relation of (Tg x) x (98.8/100) < T (x) < Tg (x) × (101.2/100) is 90-100%.

[ numerical formula 2]

Effects of the invention

According to one aspect of the present invention, there is provided a photosensitive film in which occurrence of winding displacement and deformation is suppressed when the photosensitive film is wound.

According to another aspect of the present invention, there is provided a method for manufacturing a photosensitive film, in which occurrence of winding displacement and deformation when winding the photosensitive film is suppressed.

Drawings

Fig. 1 is a conceptual diagram illustrating the relationship between tg (x) and t (x).

FIG. 2 is a schematic view showing an example of the structure of a photosensitive film.

Fig. 3 is a schematic diagram showing an example of a pattern of a mask for manufacturing a touch panel.

Fig. 4 is a schematic diagram showing another example of the pattern of the touch panel manufacturing mask.

FIG. 5 is a graph showing the thickness distribution of the leading end portion of the photosensitive film of comparative example 1.

FIG. 6 is a graph showing the thickness distribution at the center of the photosensitive film of comparative example 1.

FIG. 7 is a graph showing the thickness distribution of the rear end portion of the photosensitive film of comparative example 1.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented by making appropriate changes within the scope of the object of the present invention.

In describing the embodiments of the present invention with reference to the drawings, the description of the constituent elements and symbols overlapping in the drawings may be omitted. The components denoted by the same reference numerals in the drawings mean the same components. The size ratio in the drawings does not necessarily indicate the ratio of actual sizes.

In the present invention, the numerical range represented by "to" represents a range in which the numerical values before and after "to" are included as the lower limit value and the upper limit value, respectively. In the numerical ranges recited in the present invention, the upper limit or the lower limit recited in a certain numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In addition, in the numerical ranges of the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.

In the present invention, when a plurality of substances corresponding to each ingredient are present in the composition, the amount of each ingredient in the composition refers to the total amount of the plurality of substances present in the composition, unless otherwise specified.

In the present invention, the term "step" includes not only an independent step, but also a step that can achieve a desired purpose even when it is not clearly distinguished from other steps.

In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, a more preferable mode is a combination of 2 or more preferable modes.

In the present invention, the unsubstituted and unsubstituted groups (atomic groups) include groups having no substituent and groups having a substituent. For example, the expression "alkyl group" includes not only an alkyl group having no substituent (i.e., an unsubstituted alkyl group) but also an alkyl group having a substituent (i.e., a substituted alkyl group).

In the present invention, "(meth) acrylic acid" means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid.

In the present invention, "(meth) acryloyl group" means an acryloyl group, a methacryloyl group, or both an acryloyl group and a methacryloyl group.

In the present invention, "(meth) acrylate" means acrylate, methacrylate, or both acrylate and methacrylate.

In the present invention, "alkali-soluble" refers to a property that the solubility of sodium carbonate in an aqueous solution (100g, concentration of sodium carbonate: 1% by mass) is 0.1g or more at a liquid temperature of 22 ℃.

In the present invention, the chemical structural formula may be described by a structural formula in which a hydrogen atom is omitted.

In the present invention, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams (e.g., electron beams and ion beams). Examples of the light used for exposure include active rays (also referred to as active energy rays). Examples of the active light include a bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, Extreme ultraviolet rays (EUV (Extreme ultraviolet lithography) light), and X-rays.

In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights converted by using a differential refractometer to detect a compound in THF (tetrahydrofuran) by using Gel Permeation Chromatography (GPC) analysis devices using columns of "TSKgel GMHxL", "TSKgel G4000 HxL" and "TSKgel G2000 HxL" (both trade names manufactured by Tosoh Corporation), and using polystyrene as a standard substance.

In the present invention, the "solid component" refers to a component obtained by removing a solvent from all components of an object.

In the present invention, unless otherwise specified, the refractive index is a value measured at a wavelength of 550nm using an ellipsometer.

< photosensitive film >

In the photosensitive film according to the present invention, when W in mm represents the width of the film, x in mm represents the distance from one end of the film in the film width direction to the measurement position of the film thickness, Ta in mm represents the average value of the film thickness measured in the film width direction, tg (x) in mm represents the target value of the film thickness represented by the following formula, and t (x) in mm represents the thickness from one end of the film in the film width direction to the film measured at the x position, the ratio satisfying the relationship of tg (x) x (98.8/100) < t (x) < tg (x) x (101.2/100) is 90% to 100%. According to the photosensitive film of the present invention, the occurrence of winding displacement and deformation when winding the photosensitive film can be suppressed.

[ numerical formula 3]

Hereinafter, the relationship between tg (x) and t (x) represented by the above formula will be described with reference to fig. 1. Fig. 1 is a conceptual diagram illustrating the relationship between tg (x) and t (x). The horizontal axis in fig. 1 represents the distance x from one end of the film in the film width direction to the measurement position of the film thickness. W on the horizontal axis corresponds to the width of the film (i.e., the distance from one end of the film to the other). The vertical axis in fig. 1 represents the thickness t (x) of the film. As shown in fig. 1, the graph of the target value tg (x) of the film thickness represented by the above formula depicts an upwardly convex curve (i.e., a parabola). The intersection of the graph of Tg (x) with the vertical axis is the average Ta of the film thickness measured in the film width direction. Similarly to tg (x), the graph showing "tg (x) × (98.8/100)" and the graph showing "tg (x) × (101.2/100)" each depict upward convex curves. That is, in fig. 1, in the case where t (x) is included in the region between the graph indicating "tg (x) x (98.8/100)" and the graph indicating "tg (x) x (101.2/100)," the relationship of tg (x) x (98.8/100) < t (x) < tg (x) x (101.2/100) can be satisfied. As shown in fig. 1, by satisfying the above relationship, variation in the thickness of the photosensitive film can be reduced. Further, by satisfying the above relationship, that is, by making the sectional shape of the photosensitive film close to the curved shape shown in fig. 1, for example, bubbles are easily removed when laminating the photosensitive film, and therefore the photosensitive film can be uniformly wound. Therefore, according to the photosensitive film of the present invention, it is estimated that the occurrence of winding displacement and deformation when winding the photosensitive film can be suppressed.

In the photosensitive film of the present invention, the ratio satisfying the relationship of tg (x) × (98.8/100) < t (x) < tg (x) × (101.2/100) is calculated by the following procedure.

(1) The thickness (t (x)) of the photosensitive film was measured at 16 points at equal intervals along the width direction of the photosensitive film in each of 3 regions (i.e., the front end portion, the central portion, and the rear end portion) in the longitudinal direction of the photosensitive film. That is, the thickness (T (x)) of the photosensitive film was measured at 48 points in total. The "leading end portion" refers to a region from the leading end of the photosensitive film to 5% of the entire length of the photosensitive film in the longitudinal direction of the photosensitive film. In the photosensitive film wound in a roll (hereinafter, may be simply referred to as a "roll"), the "leading end of the photosensitive film" corresponds to the starting point (the position where the drawing is started) of the photosensitive film in the process of drawing the photosensitive film wound in a roll. The "central portion" refers to a region from the center of the photosensitive film to ± 2.5% of the entire length of the photosensitive film in the longitudinal direction of the photosensitive film. The "rear end portion" refers to a region from the rear end of the photosensitive film to 5% of the entire length of the photosensitive film in the longitudinal direction of the photosensitive film. In the photosensitive film wound in a roll, the "rear end of the photosensitive film" corresponds to the end point of the photosensitive film (the end point of pulling) in the process of pulling out the photosensitive film wound in a roll. Further, since the rear end portion is inside the roll in the rolled state, when the continuous film is formed in the roll shape, the front end of the roll manufactured immediately before substantially contacts the rear end of the roll to be measured, and therefore the front end portion of the roll manufactured immediately before may be substituted for the rear end portion of the roll to be measured. When the longitudinal direction of the photosensitive film cannot be specified, one of 2 directions orthogonal to each other along the surface of the photosensitive film is defined as the longitudinal direction, and the other direction is defined as the width direction.

(2) The width (W) of the photosensitive film was measured in each of the 3 regions.

(3) At each measurement position at 48, the distance (x) from one end of the photosensitive film in the width direction of the photosensitive film to the measurement position of the thickness (T (x)) of the photosensitive film is measured.

(4) The average value (Ta) of the thicknesses of the photosensitive films measured in the width direction of the photosensitive films was obtained by arithmetically averaging the thicknesses (t (x)) of the photosensitive films measured at 48.

(5) At each measurement position at 48, the ratio satisfying the above relationship is calculated by confirming whether or not the relationship of Tg (x) × (98.8/100) < T (x) < Tg (x) × (101.2/100) is satisfied.

In the photosensitive film of the present invention, the proportion satisfying the relationship of Tg (x) x (98.8/100) < T (x) < Tg (x) × (101.2/100) is preferably 92% to 100%, more preferably 95% to 100%, still more preferably 97% to 100%, and particularly preferably 100%. When the ratio satisfying the above relationship is within the above range, the occurrence of appearance defects can be further suppressed.

From the viewpoint of further suppressing the occurrence of appearance defects, the photosensitive film according to the present invention preferably satisfies the relationship of Tg (x) x (99.0/100) < T (x) < Tg (x) × (101.0/100), and more preferably satisfies the relationship of Tg (x) x (99.2/100) < T (x) < Tg (x) × (100.8/100). In the photosensitive film of the present invention, the proportion satisfying the above relationship is the same as the proportion satisfying the above relationship of Tg (x) x (98.8/100) < T (x) tg (x) x (101.2/100).

(elements of composition)

The constituent elements of the photosensitive film according to the present invention are not limited as long as the photosensitive film satisfies the relationship of Tg (x) x (98.8/100) < T (x) < Tg (x) × (101.2/100) at a ratio of 90% to 100%.

In one embodiment, the photosensitive film preferably includes a temporary support and a photosensitive resin layer. In the photosensitive film, the photosensitive resin layer may be laminated directly or via an arbitrary layer on the temporary support. In the photosensitive film, an arbitrary layer may be laminated on the surface of the photosensitive resin layer opposite to the side where the temporary support is disposed. Examples of the optional layer of the photosensitive film include a cover film and other layers described later.

In one embodiment, the photosensitive film preferably includes a temporary support, a photosensitive resin layer, and a cover film in this order. In the photosensitive film, the photosensitive resin layer may be laminated directly or via an arbitrary layer on the temporary support. In the above photosensitive film, the cover film may be laminated on the photosensitive resin layer directly or via an arbitrary layer. Examples of the optional layer of the photosensitive film include other layers described later.

An example of a photosensitive film including a temporary support, a photosensitive resin layer, and a cover film in this order will be described with reference to fig. 2. FIG. 2 is a schematic view showing an example of the structure of a photosensitive film. The photosensitive film 100 shown in fig. 2 includes a temporary support 10, a photosensitive resin layer 12, and a cover film 14. In the photosensitive film 100, a temporary support 10, a photosensitive resin layer 12, and a cover film 14 are sequentially stacked.

Hereinafter, the constituent elements of the photosensitive film according to the present invention will be specifically described. However, the constituent elements of the photosensitive film according to the present invention are not limited to those shown below.

[ temporary support ]

The photosensitive film according to the present invention preferably has a temporary support. The temporary support is a support that can be peeled off from the photosensitive film. For example, in a photosensitive film including a temporary support and a photosensitive resin layer in this order, the temporary support can support the photosensitive resin layer.

The temporary support preferably has a light-transmitting property. Since the temporary support has light transmittance, the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is exposed. In the present invention, "having light transmittance" means that the transmittance of light of a wavelength used in pattern exposure is 50% or more. In the temporary support, the transmittance of light of a wavelength (preferably, a wavelength of 365nm) used for pattern exposure is preferably 60% or more, and more preferably 70% or more, from the viewpoint of improving the exposure sensitivity of the photosensitive resin layer. In the present invention, "transmittance" refers to a ratio of intensity of outgoing light emitted through a layer as a measurement target to intensity of incident light when the light enters in a direction perpendicular to a main surface of the layer as the measurement target (i.e., in a thickness direction). The transmittance was measured using MCPD Series manufactured by Otsuka Electronics co.

From the viewpoint of pattern formability when pattern exposure is performed by the temporary support and transparency of the temporary support, the temporary support preferably has a low haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less.

Examples of the temporary support include a glass substrate, a resin film, and paper. The temporary support is preferably a resin film from the viewpoint of strength, flexibility, and light transmittance.

Examples of the resin film include a polyethylene terephthalate film (i.e., a PET film), a cellulose triacetate film, a polystyrene film, and a polycarbonate film. The resin film is preferably a PET film, and more preferably a biaxially stretched PET film.

The thickness of the temporary support is not limited. The thickness of the temporary support may be determined by, for example, the strength, transparency, and material of the temporary support, and the flexibility required for bonding the photosensitive film to the substrate. The average thickness of the temporary support is preferably 5 μm to 100 μm. From the viewpoint of ease of handling and versatility, the average thickness of the temporary support is preferably 5 μm to 50 μm, more preferably 5 μm to 20 μm, still more preferably 10 μm to 20 μm, and particularly preferably 10 μm to 16 μm.

The average thickness of the components (for example, the temporary support, the photosensitive resin layer, and the cover film) in the photosensitive film is measured by the following method. A cross section in a direction perpendicular to the main surface of the photosensitive film (i.e., in the thickness direction) was observed using a Scanning Electron Microscope (SEM). From the obtained observation image, the thickness of the component to be measured was measured at 10 points. The average thickness of the target component is obtained by arithmetically averaging the measured values.

Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a film thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 μm.

The surface of the temporary support on which the photosensitive resin layer is disposed (i.e., the surface of the temporary support facing the photosensitive resin layer) preferably has an arithmetic average roughness Ra of 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.02 μm or less. The lower limit of the arithmetic average roughness Ra is not limited. The arithmetic average roughness Ra of the surface of the temporary support on which the photosensitive resin layer is disposed may be determined, for example, within a range of 0 μm or more.

The arithmetic average roughness Ra was measured by the following method. The surface profile of the measurement object was obtained under the following conditions using a three-dimensional optical profiler (New View7300, manufactured by Zygo). As the measurement and analysis software, a microprocessing Application (Microcope Application) of MetroPro ver8.3.2 was used. Next, the Surface Map screen is displayed using the software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic average roughness Ra of the surface of the object to be measured is obtained. When the surface of the object to be measured is in contact with the surface of the other layer, the arithmetic average roughness Ra of the surface of the object to be measured exposed by peeling the object to be measured from the other layer may be measured.

The temporary support (particularly, the resin film) is preferably free from, for example, deformation (for example, wrinkles), scratches, and defects. From the viewpoint of pattern formability in pattern exposure by the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, defects, and precipitates contained in the temporary support is preferably small. In the temporary support, the number of particles, foreign matters and defects having a diameter of 1 μm or more is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, more preferably 3/10 mm ² The average particle size is preferably 0/10 mm ² 。

Preferable examples of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of International patent application laid-open No. 2012/081680, paragraphs 0029 to 0040 of International patent application laid-open No. 2018/179370, and paragraphs 0012 to 0032 of Japanese patent application laid-open No. 2019-101405. The contents of these publications are incorporated by reference into this specification.

The temporary support may have a single-layer structure or a multi-layer structure. From the viewpoint of imparting handling properties, a layer containing fine particles (also referred to as a "lubricant layer") may be provided on the surface of the temporary support. The lubricant layer may be provided on one surface of the temporary support or may be provided on both surfaces of the temporary support. The diameter of the particles contained in the lubricant layer is preferably 0.05 μm to 0.8. mu.m. The thickness of the lubricant layer is preferably 0.05 μm to 1.0. mu.m.

[ photosensitive resin layer ]

The photosensitive film according to the present invention preferably has a photosensitive resin layer. The photosensitive resin layer is preferably a negative photosensitive resin layer in which the exposed portion is reduced in solubility in a developer by exposure, and the non-exposed portion is removed by development. However, the photosensitive resin layer is not limited to the negative photosensitive resin layer, and may be a positive photosensitive resin layer in which the exposed portion is exposed to light to improve the solubility in a developer, and the exposed portion is removed by development.

In one embodiment, the photosensitive resin layer preferably contains a polymer a, a polymerizable compound B, and a photopolymerization initiator. In one embodiment, the photosensitive resin layer preferably contains 10 to 90 mass% of the polymer a, 5 to 70 mass% of the polymerizable compound B, and 0.01 to 20 mass% of the photopolymerization initiator, based on the total mass of the photosensitive resin layer. The polymer a, the polymerizable compound B, and the photopolymerization initiator will be described later.

(Polymer A)

The photosensitive resin layer preferably contains a polymer a. The polymer a is preferably an alkali-soluble polymer. The alkali-soluble polymer includes a polymer that is easily soluble in an alkali substance.

The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and particularly preferably less than 190mgKOH/g, from the viewpoint of suppressing swelling of the photosensitive resin layer by the developer to further improve the resolution. The lower limit of the acid value is not limited. From the viewpoint of more excellent developability, the acid value of the polymer A is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, and particularly preferably 170mgKOH/g or more. The acid value of the polymer a can be adjusted by, for example, the type of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.

In the present invention, the acid value is the mass (mg) of potassium hydroxide required to neutralize 1g of the sample. In the present invention, the unit of the acid value is described as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The weight average molecular weight (Mw) of the polymer A is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight of the polymer a is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the characteristics of the developed aggregate, the edge fuse (edge fuse) property and the cut chip (cut chip) property, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight of the polymer a is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property is a degree of easiness of the photosensitive resin layer to be protruded from the end face of the roll when the photosensitive film is wound in a roll shape. The chipping property is the ease of chip scattering when an unexposed film is cut with a cutter. For example, if a chip adheres to the surface of the photosensitive film, the chip is transferred to a mask in the exposure step, which causes a defective product.

The degree of dispersion of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0. In the present invention, the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing the line width thickening and the resolution deterioration at the time of focus position shift at the time of exposure, the polymer a preferably has a structural unit derived from a monomer having an aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.

The content ratio of the structural units derived from the monomer having an aromatic hydrocarbon group in the polymer a is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of the polymer a. The upper limit of the content ratio of the structural units derived from the monomer having an aromatic hydrocarbon group is not limited. The content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer a is preferably 95% by mass or less, more preferably 85% by mass or less, based on the total mass of the polymer a. When the photosensitive resin layer contains a plurality of polymers a, the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). The monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.

Examples of the monomer having a benzyl group include (meth) acrylates having a benzyl group (e.g., benzyl (meth) acrylate and chlorobenzyl (meth) acrylate), and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). The monomer having a benzyl group is preferably benzyl (meth) acrylate.

In one embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer a is a structural unit derived from benzyl (meth) acrylate, the content ratio of the structural unit derived from the benzyl (meth) acrylate monomer in the polymer a is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of the polymer a.

In one embodiment, when the structural unit derived from a monomer having an aromatic hydrocarbon group in the polymer a is a structural unit derived from styrene, the content ratio of the structural unit derived from styrene in the polymer a is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, further preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of the polymer a. When the photosensitive resin layer contains a plurality of polymers a, the content of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.

The polymer a having a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a copolymer obtained by polymerizing a monomer having an aromatic hydrocarbon group and at least one selected from the first monomer described later and the second monomer described later.

The polymer a may be a polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group. The polymer a having no structural unit derived from a monomer having an aromatic hydrocarbon group is preferably a polymer obtained by polymerizing at least one of the first monomers (excluding the monomer having an aromatic hydrocarbon group) described later, and more preferably a copolymer obtained by polymerizing at least one of the first monomers (excluding the monomer having an aromatic hydrocarbon group) described later and at least one of the second monomers (excluding the monomer having an aromatic hydrocarbon group) described later.

In one embodiment, the polymer a is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and more preferably a copolymer obtained by polymerizing at least one of the first monomers described later and at least one of the second monomers described later.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half-ester. The first monomer is preferably (meth) acrylic acid.

The content ratio of the structural unit derived from the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass, based on the total mass of the polymer a.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include a (meth) acrylate compound, an ester compound of vinyl alcohol, and (meth) acrylonitrile. In the present invention, "(meth) acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

As the ester compound of vinyl alcohol, for example, vinyl acetate may be mentioned.

The second monomer is preferably at least one selected from the group consisting of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate, and more preferably methyl (meth) acrylate.

The content ratio of the structural unit derived from the second monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 45% by mass, based on the total mass of the polymer a.

From the viewpoint of suppressing the line width thickening and the resolution deterioration at the time of focus position shift at the time of exposure, the polymer a preferably contains at least one selected from the group consisting of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene. For example, the polymer a is preferably at least one selected from the group consisting of a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene, and a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.

In one embodiment, the polymer a is preferably a polymer containing 25 to 40 mass% of a structural unit derived from a monomer having an aromatic hydrocarbon group, 20 to 35 mass% of a structural unit derived from a first monomer, and 30 to 45 mass% of a structural unit derived from a second monomer.

In one embodiment, the polymer a is preferably a polymer containing 70 to 90 mass% of a structural unit derived from a monomer having an aromatic hydrocarbon group and 10 to 25 mass% of a structural unit derived from the first monomer.

The glass transition temperature (Tg) of the polymer A is preferably from 30 ℃ to 135 ℃. The Tg of the polymer a in the photosensitive resin layer is 135 ℃ or less, whereby thickening of the line width and deterioration of the resolution at the time of focus position shift at the time of exposure can be suppressed. From the above viewpoint, the Tg of the polymer A is more preferably 130 ℃ or lower, still more preferably 120 ℃ or lower, and particularly preferably 110 ℃ or lower. Further, the Tg of the polymer a is preferably 30 ℃ or higher from the viewpoint of improving the edge fuse resistance. From the above viewpoint, the Tg of the polymer a is more preferably 40 ℃ or higher, still more preferably 50 ℃ or higher, particularly preferably 60 ℃ or higher, and most preferably 70 ℃ or higher.

The polymer A may be a commercially available product or a synthetic product. The synthesis of the polymer a is preferably performed, for example, by adding a radical polymerization initiator (e.g., benzoyl peroxide or azoisobutyronitrile) in an appropriate amount to a solution in which at least one of the above-mentioned monomers is diluted with a solvent (e.g., acetone, methyl ethyl ketone, or isopropyl alcohol), followed by stirring with heating. In addition, synthesis may be performed while a part of the mixture is added dropwise to the reaction solution. After the reaction is completed, a solvent may be added to adjust the concentration to a desired level. As the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The photosensitive resin layer may contain 1 kind of the polymer a alone, or may contain 2 or more kinds. When the photosensitive resin layer contains 2 or more kinds of polymers a, the photosensitive resin layer preferably contains 2 or more kinds of polymers a having a structural unit derived from a monomer having an aromatic hydrocarbon group, or contains a polymer a having a structural unit derived from a monomer having an aromatic hydrocarbon group and a polymer a having no structural unit derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content ratio of the polymer a having a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the polymer a.

The content ratio of the polymer a is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive resin layer. From the viewpoint of controlling the development time, the content of the polymer a with respect to the photosensitive resin layer is preferably 90% by mass or less. On the other hand, from the viewpoint of improving the edge fuse resistance, the content ratio of the polymer a to the photosensitive resin layer is preferably 10 mass% or more.

The polymer a may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain. By using a monomer having a group having a branched structure in a side chain or a monomer having a group having an alicyclic structure in a side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer a. The group having an alicyclic structure may be monocyclic or polycyclic.

Specific examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, tert-octyl (meth) acrylate, and the like. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate and tert-butyl methacrylate are more preferable.

Specific examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Also, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned. More specific examples thereof include (meth) acrylic acid (bicyclo [ 2.2.1 ] heptyl-2), (meth) acrylic acid-1-adamantyl ester, (meth) acrylic acid-2-adamantyl ester, (meth) acrylic acid-3-methyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid-3-ethyl adamantyl ester, (meth) acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid-3, 5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-8-ethyl-1-adamantyl ester, and mixtures thereof, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methylinden-5-yl (meth) acrylate, octahydro-4, 7-methylinden-1-ylmethyl (meth) acrylate, 1-methyl (meth) acrylate, tricyclodecane (meth) acrylate, 3-hydroxy-2, 6, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl (meth) acrylate, 3,7, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl (meth) acrylate, (meth) acrylate (norbornyl) acrylate, bornyl (meth) acrylate, and mixtures thereof, Isobornyl (meth) acrylate, phenyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Among these (meth) acrylates, cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate), 1-adamantyl (meth) acrylate, (2-adamantyl (meth) acrylate, (phenyl (meth) acrylate), 1-methyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate is more preferable.

(polymerizable Compound B)

The photosensitive resin layer preferably contains a polymerizable compound B having a polymerizable group. In the present invention, the "polymerizable compound" refers to a compound that is polymerized by the action of a polymerization initiator. The polymerizable compound B is a compound different from the polymer a.

The polymerizable group in the polymerizable compound B is not limited as long as it is a group participating in a polymerization reaction. Examples of the polymerizable group in the polymerizable compound B include a group having an ethylenically unsaturated bond (e.g., a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group), and a group having a cationically polymerizable group (e.g., an epoxy group and an oxetanyl group). The polymerizable group is preferably a group containing an ethylenically unsaturated bond (hereinafter, may be referred to as "ethylenically unsaturated group"), and more preferably an acryloyl group or a methacryloyl group.

From the viewpoint of more excellent photosensitivity of the photosensitive resin layer, the polymerizable compound B is preferably a compound having 1 or more ethylenically unsaturated groups in one molecule (i.e., an ethylenically unsaturated compound), and more preferably a compound having 2 or more ethylenically unsaturated groups in one molecule (i.e., a polyfunctional ethylenically unsaturated compound). From the viewpoint of further improving the resolution and the peelability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and particularly preferably 2 or less.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound having 1 or more (meth) acryloyl groups in one molecule.

From the viewpoint of more excellent balance of photosensitivity, resolution, and peelability in the photosensitive resin layer, the polymerizable compound B is preferably at least one selected from a compound having 2 ethylenically unsaturated groups in one molecule (i.e., a 2-functional ethylenically unsaturated compound) and a compound having 3 ethylenically unsaturated groups in one molecule (i.e., a 3-functional ethylenically unsaturated compound), and more preferably a compound having 2 ethylenically unsaturated groups in one molecule.

From the viewpoint of excellent releasability of the photosensitive resin layer, the ratio of the content of the 2-functional ethylenically unsaturated compound to the content of the polymerizable compound B in the photosensitive resin layer is preferably 60 mass% or more, more preferably more than 70 mass%, and particularly preferably 90 mass% or more. The upper limit of the content of the 2-functional ethylenically unsaturated compound relative to the content of the polymerizable compound B is not limited, and may be 100% by mass. That is, all of the polymerizable compounds B contained in the photosensitive resin layer may be 2-functional ethylenically unsaturated compounds.

Polymerizable compound B1-

The photosensitive resin layer preferably contains a polymerizable compound B1 having 1 or more aromatic rings and 2 ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in one molecule in the polymerizable compound B.

From the viewpoint of further improving the resolution, the content of the polymerizable compound B1 relative to the content of the polymerizable compound B in the photosensitive resin layer is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited. From the viewpoint of peelability, the proportion of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.

Examples of the aromatic ring in the polymerizable compound B1 include aromatic hydrocarbon rings (e.g., benzene ring, naphthalene ring, and anthracene ring), aromatic heterocyclic rings (e.g., thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring), and condensed rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. In addition, the aromatic ring may have a substituent.

From the viewpoint of improving the resolution by suppressing swelling of the photosensitive resin layer by the developer, the polymerizable compound B1 preferably has a bisphenol structure. Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (i.e., 2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (i.e., 2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (i.e., 2, 2-bis (4-hydroxyphenyl) butane). The bisphenol structure is preferably a bisphenol A structure.

Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may be directly bonded to the bisphenol structure. Each polymerizable group may be bonded to the bisphenol structure through 1 or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of addition of the alkyleneoxy group added to the bisphenol structure is not limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.

The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162. The contents of the above publications are incorporated by reference into this specification.

The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloyloxyalkyloxy) phenyl) propane.

Examples of the 2, 2-bis (4- ((meth) acryloyloxyalkyl polyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical CO., Ltd.), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (BPE-500, SHIN-NAKAMURA Chemical CO, Ltd.), 2-bis (4- (methacryloyloxydecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, Hitachi Chemical CO., tdl.), 2-bis (4- (methacryloyloxypentadecyloxy) phenyl) propane (BPE-1300, SHIN-NAKAMURA CHEMICAL CO, LTD.), 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (BPE-200, SHIN-NAKAMURA CHEMICAL CO, LTD.), and ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, SHIN-NAKAMURA CHEMICAL CO, LTD.).

Examples of the polymerizable compound B1 include compounds represented by the following general formula (I).

[ chemical formula 1]

In the general formula (I), R ₁ And R ₂ Each independently represents a hydrogen atom or a methyl group, A represents C ₂ H ₄ B represents C ₃ H ₆ ，n ₁ And n ₃ Each independently is an integer of 1 to 39, n ₁ +n ₃ Is an integer of 2 to 40, n ₂ And n ₄ Each independently is an integer of 0 to 29, n ₂ +n ₄ Is an integer of 0 to 30, and the arrangement of the repeating units of- (A-O) -and- (B-O) -may be random or block. In the case of a block, either of- (A-O) -and- (B-O) -may be a biphenyl side. n is ₂ +n ₄ Preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0. In one embodiment, n ₁ +n ₂ +n ₃ +n ₄ Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.

The photosensitive resin layer may contain 1 polymerizable compound B1 alone, or may contain 2 or more.

From the viewpoint of further excellent resolution, the content ratio of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit of the content ratio of the polymerizable compound B1 is not limited. From the viewpoint of transferability and edge fuse resistance, the content ratio of the polymerizable compound B1 in the photosensitive resin layer is preferably 70 mass% or less, and more preferably 60 mass% or less, with respect to the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include a monofunctional ethylenically unsaturated compound (i.e., a compound having 1 ethylenically unsaturated group in one molecule), a 2-functional ethylenically unsaturated compound having no aromatic ring (i.e., a compound having 2 ethylenically unsaturated groups in one molecule), and an ethylenically unsaturated compound having 3 or more functions (i.e., a compound having 3 or more ethylenically unsaturated groups in one molecule).

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

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate include tricyclodecane dimethanol diacrylate (A-DCP, SHIN-NAKAMURA CHEMICAL CO, LTD. synthesized by Egyptian, Polyporus), tricyclodecane dimethanol dimethacrylate (DCP, SHIN-NAKAMURA CHEMICAL CO, LTD.), 1, 9-nonanediol diacrylate (A-NOD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.), 1, 6-hexanediol diacrylate (A-HD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.), ethylene glycol dimethacrylate, 1, 10-decanediol diacrylate and neopentyl glycol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di (meth) acrylate.

Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (TAISEI FINE CHEMICAL CO. LTD.), UA-32P (SHIN-NAKAMURA CHEMICAL CO., LTD.), and UA-1100H (SHIN-NAKAMURA CHEMICAL CO., LTD.).

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof. In the present invention, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. In the present invention, "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.), alkylene oxide-modified (meth) acrylate compounds (e.g., KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., EBECRYL (registered trademark) 135 manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD., ATM-35E manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD. and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., LTD.), ethoxylated glyceryl triacrylate (e.g., A-GLY-9 AGE manufactured by SHIN-NAMIC CO, GLY-234E), ethoxylated glyceryl triacrylate (e., LTD.), ARONIX M-520(TOAGOSEI CO., LTD.), and ARONIX M-510(TOAGOSEI CO., LTD.).

Examples of the polymerizable compound B other than the polymerizable compound B1 include polymerizable compounds having an acid group as described in paragraphs 0025 to 0030 of Japanese patent application laid-open No. 2004-239942.

In one embodiment, the photosensitive resin layer preferably contains the polymerizable compound B1 and an ethylenically unsaturated compound having 3 or more functional groups, and more preferably contains the polymerizable compound B1 and 2 or more ethylenically unsaturated compounds having 3 or more functional groups. In the above embodiment, the mass ratio of the polymerizable compound B1 to the 3-or more-functional ethylenically unsaturated compound ([ total mass of the polymerizable compound B1 ]: total mass of the 3-or more-functional ethylenically unsaturated compound ]) is preferably 1:1 to 5:1, more preferably 1.2:1 to 4:1, and particularly preferably 1.5:1 to 3: 1. In one embodiment, the photosensitive resin layer preferably contains the polymerizable compound B1 and 2 or more 3-functional ethylenically unsaturated compounds.

The molecular weight of the polymerizable compound B (the weight average molecular weight (Mw) when the polymerizable compound B has a molecular weight distribution) is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The photosensitive resin layer may contain 1 kind of the polymerizable compound B alone, or may contain 2 or more kinds.

The content ratio of the polymerizable compound B in the photosensitive resin layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.

From the viewpoint of resolution and linearity, the value of the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound to the content Mb of the polymer a in the photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. The ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth) acrylic compound, and more preferably contains a (meth) acrylate compound, from the viewpoint of curability and resolution. The ethylenically unsaturated compound in the photosensitive resin layer contains a (meth) acrylic compound, and the content ratio of the acrylic compound to the total mass of the (meth) acrylic compound contained in the photosensitive resin layer is more preferably 60 mass% or less from the viewpoints of curability, resolution, and linearity.

(optional Components)

The photosensitive resin layer may contain a component other than the above-described components (hereinafter, may be referred to as an "optional component"). Examples of the optional component include a photopolymerization initiator, a coloring matter, a surfactant, and an additive other than the above components.

Photopolymerization initiators

The photosensitive resin layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives active light (e.g., ultraviolet light, visible light, and X-ray) to initiate polymerization of a polymerizable compound (e.g., polymerizable compound B).

The photopolymerization initiator is not limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

Examples of the photo radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylphenone structure, a photopolymerization initiator having an α -hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

From the viewpoint of photosensitivity, visibility of exposed portions, visibility of non-exposed portions, and resolution, the photosensitive resin layer preferably contains at least one selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives of 2,4, 5-triarylimidazole dimer as a photo radical polymerization initiator. In addition, 2,4, 5-triarylimidazole dimers and derivatives thereof, in which 2,4, 5-triarylimidazole structures are the same, may be different.

Examples of the derivatives of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

Examples of the photo-radical polymerization initiator include polymerization initiators described in paragraphs 0031 to 0042 of jp 2011-95716 a and polymerization initiators described in paragraphs 0064 to 0081 of jp 2015-14783 a.

Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No.10287-53-3), benzoin methyl ether, anisyl (p, p' -dimethoxybenzyl), and benzophenone.

Examples of commercially available products of the photo radical polymerization initiator include TAZ-110(Midori Kagaku Co., Ltd.), TAZ-111(Midori Kagaku Co., Ltd.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole (Tokyo Chemical Industry Co., Ltd.), Ltd ], 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyl oxime) (trade name: IRGACURE (registered trade name) OXE-01, BASF Co.), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) (trade name: IRGACURE-02, BASF corporation), IRGACURE OXE-03(BASF corporation), IRGACURE OXE-04(BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omnirad 379EG, IGM Resins b.v., inc), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: omnirad 907, IGM Resins b.v., inc), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (trade name: omnirad 127, IGM Resins b.v., inc), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: omnirad 369, IGM Resins b.v., inc), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173, IGM Resins b.v., inc), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184, IGM Resins b.v., inc), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651, IGM Resins b.v., inc), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad TPO H, IGM Resins b.v., inc), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819, IGM Resins b.v., inc), an oxime ester-based photopolymerization initiator (trade name: lunar 6, DKSH Management Ltd.), 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbisimidazol (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, hamford) and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.).

The photo cation polymerization initiator (i.e., photoacid generator) is a compound that receives active light to generate an acid. As the photo cation polymerization initiator, a compound which generates an acid by being sensitive to active rays having a wavelength of 300nm or more, preferably 300 to 450nm, is preferable. Among them, the chemical structure of the photo cation polymerization initiator is not limited. Further, the photo cation polymerization initiator which is not directly sensitive to the active light having a wavelength of 300nm or more may be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by being used in combination with the sensitizer and is sensitive to the active light having a wavelength of 300nm or more.

The photo cation polymerization initiator is preferably a photo cation polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of the pKa is not limited. The pKa of the acid generated by the photo cation polymerization initiator is, for example, preferably-10.0 or more.

Examples of the photo cation polymerization initiator include ionic photo cation polymerization initiators and nonionic photo cation polymerization initiators.

Examples of the ionic photo-cationic polymerization initiator include onium salt compounds (e.g., diaryliodonium salt compounds and triarylsulfonium salt compounds) and quaternary ammonium salt compounds.

The ionic photo-cationic polymerization initiator may be the one described in paragraphs 0114 to 0133 of Japanese patent application laid-open Nos. 2014-85643.

Examples of the nonionic photo cation polymerization initiator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of the trichloromethyl-s-triazine compound, diazomethane compound and imide sulfonate compound include compounds described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494. Examples of the oxime sulfonate compound include compounds described in paragraphs 0084 to 0088 of international publication No. 2018/179640.

The photosensitive resin layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives of 2,4, 5-triarylimidazole dimer.

The photosensitive resin layer may contain 1 kind of photopolymerization initiator alone, or may contain 2 or more kinds.

The content ratio of the photopolymerization initiator in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit of the content ratio of the photopolymerization initiator is not limited. The content ratio of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

Pigments-

From the viewpoint of visibility of an exposed portion, visibility of a non-exposed portion, visibility of a pattern after development, and resolution, the photosensitive resin layer preferably contains a dye (hereinafter, sometimes referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm which is a wavelength range in color development, and a maximum absorption wavelength which changes by an acid, an alkali, or a radical. The detailed mechanism is not clear, but when the photosensitive resin layer contains the pigment N, the adhesion of the layers adjacent to the photosensitive resin layer (for example, the temporary support and the intermediate layer) is improved, and the resolution is further improved.

In the present invention, the term "the maximum absorption wavelength of a dye changes by an acid, an alkali, or a radical" used in reference to a dye means any of a mode in which a dye in a colored state is decolored by an acid, an alkali, or a radical, a mode in which a dye in a decolored state is colored by an acid, an alkali, or a radical, and a mode in which a dye in a colored state changes to a colored state of another color.

Specifically, the dye N may be a compound that develops color by changing from a decolored state upon exposure to light, or may be a compound that develops color by changing from a decolored state upon exposure to light. In the above embodiment, the dye N may be a dye which is generated by exposure and which changes its color development or decoloration state by the action of an acid, an alkali, or a radical. The dye N may be a dye that is generated by exposure and changes its color development or decoloration state by changing the state (for example, pH) in the photosensitive resin layer with an acid, an alkali, or a radical. On the other hand, the dye N may be a dye that changes its color development or decoloration state by being directly stimulated by an acid, an alkali, or a radical without being exposed to light.

The dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, and resolution.

From the viewpoint of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, the photosensitive resin layer preferably contains both a dye whose maximum absorption wavelength changes by a radical and a photo radical polymerization initiator as the dye N.

The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, from the viewpoint of visibility of an exposed portion and visibility of a non-exposed portion.

As an example of the color development mechanism of the pigment N, there is a system in which a photosensitive resin layer containing a photo-radical polymerization initiator, a photo-cationic polymerization initiator (i.e., a photo-acid generator) or a photo-base generator is exposed to light, and a radical-reactive pigment, an acid-reactive pigment or a base-reactive pigment (e.g., a leuco pigment) is developed by the action of a radical, acid or base generated from the photo-radical polymerization initiator, the photo-cationic polymerization initiator or the photo-base generator.

In the dye N, the maximum absorption wavelength in the wavelength range of 400nm to 780nm in color development is preferably 550nm or more, more preferably 550nm to 700nm, and particularly preferably 550 to 650nm, from the viewpoints of visibility of an exposed portion and visibility of a non-exposed portion.

The dye N may have a maximum absorption wavelength in a wavelength range of 400nm to 780nm, which is a wavelength range in which 1 or 2 or more colors are developed. When the dye N has a maximum absorption wavelength in a wavelength range of 400nm to 780nm, which is a wavelength range in which color is developed, of 2 or more, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the dye N is measured by measuring the transmission spectrum of a solution (liquid temperature 25 ℃) containing the dye N in a range of 400nm to 780nm using a spectrophotometer (UV3100, SHIMADZU CORPORATION) under an atmospheric atmosphere, and then detecting a wavelength (maximum absorption wavelength) at which the intensity of the light becomes extremely small.

Examples of the dye that develops color or decolors by exposure include colorless compounds. Examples of the dye decolorized by exposure to light include a leuco compound, a diarylmethane dye, an oxazine dye, a xanthene dye, an iminonaphthoquinone dye, an azomethine dye, and an anthraquinone dye. The dye N is preferably a colorless compound from the viewpoint of visibility of an exposed portion and visibility of a non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), a leuco compound having a fluoran skeleton (fluoran-based dye), a leuco compound having a diarylmethane skeleton (diarylmethane-based dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a leuco compound having an indolphthalein (indolphthalein) -skeleton (indolphthalein-based dye), and a leuco compound having a leucoauramine (Auramine) -skeleton (leuco Auramine-based dye). The leuco compound is preferably a triarylmethane-based dye or a fluorane-based dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane-based dye) or a fluorane-based dye.

From the viewpoint of visibility of exposed portions and visibility of non-exposed portions, the colorless compound preferably has a lactone ring, a rutin ring, or a sultone ring. The lactone ring, rutin ring or sultone ring contained in the colorless compound is reacted with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator, whereby the colorless compound can be changed to a closed ring state to be decolorized or the colorless compound can be changed to an open ring state to be developed. The colorless compound is preferably a compound having a lactone ring, a rutin ring, or a sultone ring, and the lactone ring, the rutin ring, or the sultone ring develops color by radical or acid ring opening, and more preferably a compound having a lactone ring, and the lactone ring develops color by radical or acid ring opening.

Specific examples of the colorless compound include p, p' -hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene Blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluoran, 2-anilino-3-methyl-6- (N-ethyl-p-tolylamino) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-xylylfluoran, 3- (N, N-diethylamino) -6-methyl-7-chlorofluoran, 3- (N, N-diethylamino) -6-methoxy-7-aminofluoran, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluoran, 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, n-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-xylylfluoran, 3-piperidinyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminobenzphthalide, phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide and 3 ', 6 ' -bis (diphenylamino) spiroisobenzofuran-1 (3H),9 ' - [9H ] xanthen-3-one.

Examples of the dye N include dyes. Specific examples of the dye include brilliant green, ethyl violet, methyl green, crystal violet, basic magenta, methyl violet 2B, quinine red, rose bengal, methyl yellow, thymolsulfonephthalein, xylenol blue, methyl orange, p-methyl red, congo red, benzo-erythrosine (BenzoPurpurine)4B, α -naphthyl red, nile blue 2B, nile blue a, methyl violet, malachite green, Parafuchsin (parafuuchsin), victoria pure blue-naphthalenesulfonate, victoria pure blue BOH (Hodogaya Chemical co., Ltd.), oil blue #603 (orn Chemical l, dus co., Ltd.), oil powder red #312 (orn Chemical l industryres co., Ltd.), oil red 5B (orn Chemical co., oil red, red. (orhod.: red., red.: red. (orhod.: red. (orhod., Ltd.), red.: red. (orhod.: dus.: red., Ltd. (orr.: red), red.: red. (orred.: red) Oil green #502(ORIENT CHEMICAL INDUSTRIES CO., LTD.), Spilon Red BEH Special (Hodogaya CHEMICAL Co., Ltd.), m-cresol purple, cresol Red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

The dye N is preferably a dye whose maximum absorption wavelength changes by a radical, and more preferably a dye that develops color by a radical, from the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution.

Pigment N is preferably leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-naphthalene sulfonate.

The photosensitive resin layer may contain 1 kind of pigment N alone, or may contain 2 or more kinds.

From the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, pattern visibility after development, and resolution, the content of the dye N is preferably 0.1% by mass or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass, based on the total mass of the photosensitive resin layer.

The content ratio of the pigment N is a content ratio of the pigment when all the pigment N contained in the photosensitive resin layer is in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by a radical as an example. 2 kinds of solutions were prepared by dissolving a dye (0.001g) and a dye (0.01g) in methyl ethyl ketone (100mL), respectively. To each of the obtained solutions, IRGACURE OXE-01 (BASF) was added as a photo radical polymerization initiator, and then 365nm light was irradiated to generate radicals, thereby bringing all the dyes into a colored state. Next, the absorbance of each solution at a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV3100, SHIMADZU CORPORATION) under an atmospheric atmosphere, and a calibration curve was prepared. Next, the absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that the photosensitive resin layer (3g) was dissolved in methyl ethyl ketone instead of the pigments. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the pigment contained in the photosensitive resin layer was calculated from the calibration curve.

Surfactants-

From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkyl phenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, silicone nonionic surfactants, and fluorine nonionic surfactants.

From the viewpoint of further improving the resolution, the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant. It is considered that the photosensitive resin layer contains a fluorine-based nonionic surfactant, and thereby the penetration of the etching solution into the photosensitive resin layer is suppressed, and the side etching is reduced. Commercially available fluorine-based nonionic surfactants include, for example, Megafac (registered trademark) F-551, F-552(DIC CORPORATION) and Megafac F-554(DIC CORPORATION).

Further, as the surfactant, a nonionic surfactant, a fluorine surfactant, or a silicone surfactant is preferable.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (trade name) produced by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (trade name) produced by BASF), Solsperse (trade name) 20000 (trade name) produced by Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (trade name) and fuw-1002 (trade name) produced by jiwarok Chemical Corporation, PIONIN (trade name) D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT co., ltd., above), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry co., ltd., above), and the like.

Commercially available fluorine-based surfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, F-172, F-482, F-479, F-555, F-482, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (see above, produced by DIC CORPORATION), Fluorad (trade name) FC430, FC431, FC171 (see above, produced by Sumitomo 3M Limited), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (see above, produced by AGC Inc.), PolyFox (trade name) PF636, 656, PF6320, PF6520, PF7002 (see above, produced by OMVA Inc.), Fgene (trade name) 710FL, FM 710, 610FM, FM 601AD, 601, ADH2, 602A, ADH 215M, 245F, 251, 212M, 250, PF 209F, LA, 208, FS 710 LM 710, 650AC, 681, 683 (above, manufactured by NEOS COMPANY LIMITED), and the like.

Further, the fluorine-based surfactant may preferably be an acrylic compound having a molecular structure including a functional group containing a fluorine atom, and in which a portion of the functional group containing a fluorine atom is cleaved upon heating to volatilize the fluorine atom. Examples of such a fluorine-based surfactant include Megafac (trade name) DS series (chemical industry journal (2016, 2, 22 days), and Industrial news (2016, 2, 23 days), manufactured by DIC CORPORATION), such as Megafac (trade name) DS-21.

Further, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is preferably used.

As the fluorine-based surfactant, a block polymer may also be used. The fluorine-containing surfactant may preferably use a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy group (preferably ethyleneoxy group, propyleneoxy group).

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Examples thereof include Megafac (trade name) RS-101, RS-102, and RS-718K, RS-72-K (manufactured by DIC CORPORATION).

As the fluorine-based surfactant, for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms can be used. Among them, from the viewpoint of improving environmental suitability, it is preferable to use a material alternative to perfluorooctanoic acid (PFOA) or perfluorooctane sulfonic acid (PFOS) as the fluorine-based surfactant.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains or the ends thereof.

Specific examples of the Silicone-based surfactant include DOWSIL (trade name) 8032 ADDITIVE, TORAY Silicone DC3PA, TORAY Silicone SH7PA, TORAY Silicone DC11PA, TORAY Silicone SH21PA, TORAY Silicone SH28PA, TORAY Silicone SH29PA, TORAY Silicone SH30PA, TORAY Silicone SH 00 (see above, made by Toray Dow Corning Co., Ltd.), X-22-8452, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-643, X-22-6191, X-22-4515, 642-6004, td-341, KF-6001, KF-6002 (see above, made by TSn-4440, TSF-4452, TSF-4452, TSF 4440, TSF-4452, TSF-4452, manufactured by Momentive performance Materials inc.), BYK307, BYK323, BYK330 (above, manufactured by BYK co., LTD), and the like.

Examples of the surfactant include those described in paragraphs 0120 to 0125 of International publication No. 2018/179640, those described in paragraph 0017 of Japanese patent application laid-open No. 4502784, and those described in paragraphs 0060 to 0071 of Japanese patent application laid-open No. 2009-237362.

The photosensitive resin layer may contain 1 kind of surfactant alone, or may contain 2 or more kinds.

The content ratio of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total mass of the photosensitive resin layer.

Additives-

The photosensitive resin layer may contain known additives, if necessary, in addition to the above components. Examples of the additive include a thermally crosslinkable compound, a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a benzotriazole compound, a carboxybenzotriazole compound, a resin other than the polymer a, and a solvent. The photosensitive resin layer may contain 1 additive alone or 2 or more additives.

The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the cured film obtained and the adhesiveness of the uncured film obtained. In this specification, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound but as a thermally crosslinkable compound.

Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among them, blocked isocyanate compounds are preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when the polymer a and/or the ethylenically unsaturated compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film is lowered, and the function of the film obtained by curing the photosensitive resin layer when used as a protective film tends to be enhanced.

The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected with a blocking agent (so-called mask").

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃, and more preferably 130 to 150 ℃.

The dissociation temperature of the blocked isocyanate means "a temperature of an endothermic peak accompanying deprotection reaction of the blocked isocyanate as measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter".

As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. The differential scanning calorimeter is not limited to this.

Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include active methylene compounds [ malonic diesters (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ]) and oxime compounds (compounds having a structure represented by — C (═ N-OH) -in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).

Among them, the blocking agent having a dissociation temperature of 100 to 160 ℃ preferably contains an oxime compound, for example, from the viewpoint of storage stability.

For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improvement in brittleness of a film, improvement in adhesion to a transfer target, and the like.

The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate to protect it.

Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure, in which an oxime compound is used as a blocking agent, are preferable from the viewpoints that the dissociation temperature is more easily in a preferable range than that of a compound having no oxime structure and the development residue is easily reduced.

The blocked isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and a known polymerizable group, preferably a radical polymerizable group, can be used.

Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, a (meth) acrylamide group, or a styryl group, and a group having an epoxy group such as a glycidyl group.

Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and still more preferably an acryloyloxy group.

As the blocked isocyanate compound, commercially available products can be used.

Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BP, and the like (above, manufactured by SHOWA DENKO K.), and capped Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation).

Further, as the blocked isocyanate compound, a compound having the following structure may be used.

[ chemical formula 2]

The thermally crosslinkable compound may be used alone in 1 kind, or may be used in 2 or more kinds.

When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of japanese patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine or 4-methoxyphenol. Examples of the radical polymerization inhibitor other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin layer, nitrosophenylhydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor.

The photosensitive resin layer may contain a benzotriazole compound. Examples of the benzotriazole compound include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

The photosensitive resin layer may contain a carboxybenzotriazole compound. Examples of the carboxybenzotriazole compound include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. Examples of commercially available products of the carboxybenzotriazole compound include CBT-1(JOHOKU CHEMICAL CO., LTD).

The ratio of the total content of the radical polymerization inhibitor, the benzotriazole compound, and the carboxybenzotriazole compound is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, based on the total mass of the photosensitive resin layer. From the viewpoint of imparting storage stability to the photosensitive resin layer, the ratio of the total content of the above components is preferably 0.01 mass% or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing dye discoloration, the ratio of the total content of the above components is preferably 3% by mass or less.

The photosensitive resin layer may contain a sensitizer. The sensitizer is not limited, and a known sensitizer can be used. Further, as the sensitizer, a dye or a pigment may be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

The photosensitive resin layer may contain 1 sensitizer alone or 2 or more sensitizers.

When the photosensitive resin layer contains a sensitizer, the content of the sensitizer may be appropriately selected according to the purpose, but from the viewpoint of improving sensitivity to a light source and improving curing speed by a balance between polymerization speed and chain transfer, the content is preferably 0.01 to 5% by mass, and more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of international publication No. 2018/179640.

The photosensitive resin layer may contain a resin other than the polymer a. Examples of the resin other than the polymer a include an acrylic resin, a styrene-acrylic copolymer (not limited to a copolymer having a styrene content of 40 mass% or less), a polyurethane resin, a polyvinyl alcohol, a polyvinyl formal, a polyamide resin, a polyester resin, a polyamide resin, an epoxy resin, a polyacetal resin, a polyhydroxystyrene resin, a polyimide resin, a polybenzoxazole resin, a polysiloxane resin, a polyethyleneimine, a polyallylamine, and a polyalkylene glycol.

The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from a solvent-free photosensitive resin composition, the solvent may remain in the photosensitive resin layer. The solvent will be described later.

The photosensitive resin layer may contain, for example, at least one additive selected from the group consisting of metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, organic precipitation inhibitors and inorganic precipitation inhibitors. Additives are described, for example, in paragraphs 0165 to 0184 of Japanese patent laid-open publication No. 2014-85643. The contents of the above publications are incorporated by reference into this specification.

Impurities and the like

The photosensitive resin layer may contain a predetermined amount of impurities. Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, the halide ions, sodium ions and potassium ions are preferably contained in the following amounts because they are easily mixed as impurities.

The content of impurities in the photosensitive resin layer is preferably 80ppm or less, more preferably 10ppm or less, and further preferably 2ppm or less, on a mass basis. The content of the impurities may be 1ppb or more, or 0.1ppm or more on a mass basis.

As a method for making the impurity within the above range, there are a method of selecting a substance having a small impurity content as a raw material of the composition, preventing the impurity from being mixed in when the photosensitive resin layer is produced, and cleaning and removing the impurity. By this method, the amount of impurities can be made within the above range.

The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

The photosensitive resin layer preferably contains a small amount of compounds such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane. The content of these compounds with respect to the total mass of the photosensitive resin layer is preferably 100ppm by mass or less, more preferably 20ppm by mass or less, and still more preferably 4ppm by mass or less. The lower limit may be 10ppb or more, or 100ppb or more, based on the total mass of the photosensitive resin layer. These compounds can be suppressed in the content by the same method as that of the above-mentioned metal impurities. Further, the amount can be determined by a known measurement method.

From the viewpoint of improving reliability and laminatability, the content of water in the photosensitive resin layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%.

(residual monomer)

The photosensitive resin layer may contain a residual monomer corresponding to each structural unit of the polymer a.

From the viewpoint of patterning property and reliability, the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and further preferably 500 mass ppm or less, with respect to the total mass of the polymer a. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 10 mass ppm or more.

From the viewpoint of patterning property and reliability, the residual monomer in each structural unit of the polymer a is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, with respect to the total mass of the photosensitive resin layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

The residual monomer content of the monomers in the synthesis of the polymer A by the polymer reaction is also preferably within the above range. For example, in the case of synthesizing the polymer a by reacting a carboxylic acid side chain with glycidyl acrylate, it is preferable to make the content of glycidyl acrylate within the above range.

The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

(thickness)

The average thickness of the photosensitive resin layer is usually 0.1 to 300. mu.m. The average thickness of the photosensitive resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, further preferably 0.5 μm, and particularly preferably 1 μm or more. The average thickness of the photosensitive resin layer is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 15 μm or less, and particularly preferably 8 μm or less. When the average thickness of the photosensitive resin layer is within the above range, the developability of the photosensitive resin layer can be improved, and the resolution can be improved.

In one embodiment, the average thickness of the photosensitive resin layer is preferably 0.1 to 15 μm, more preferably 0.5 to 5 μm, still more preferably 0.5 to 4 μm, and particularly preferably 0.5 to 3 μm.

(transmittance)

From the viewpoint of more excellent adhesion, the transmittance of light having a wavelength of 365nm in the photosensitive resin layer is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more. The upper limit of the transmittance is not limited. In the photosensitive resin layer, the transmittance of light having a wavelength of 365nm is preferably 99.9% or less.

(method of formation)

The method for forming the photosensitive resin layer is not limited as long as the layer containing the above components can be formed. As a method for forming the photosensitive resin layer, for example, a method in which a photosensitive resin composition is applied to the surface of the temporary support and then a coating film of the photosensitive resin composition is dried can be cited.

Examples of the photosensitive resin composition include a composition containing a polymer a, a polymerizable compound B, an optional component, and a solvent. In order to adjust the viscosity of the photosensitive resin composition and facilitate formation of the photosensitive resin layer, the photosensitive resin composition preferably contains a solvent.

The solvent is not limited as long as it can dissolve or disperse the polymer a, the polymerizable compound B, and any component, and a known solvent can be used. Examples of the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (e.g., methanol and ethanol), a ketone solvent (e.g., acetone and methyl ethyl ketone), an aromatic hydrocarbon solvent (e.g., toluene), an aprotic polar solvent (e.g., N-dimethylformamide), a cyclic ether solvent (e.g., tetrahydrofuran), an ester solvent, an amide solvent, and a lactone solvent.

The photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. The photosensitive resin composition more preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent. The photosensitive resin composition particularly preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

As the solvent, a solvent described in paragraphs 0092 to 0094 of International publication No. 2018/179640 and a solvent described in paragraph 0014 of Japanese patent application laid-open publication No. 2018-177889 can be used. These are incorporated by reference into this specification.

The photosensitive resin composition may contain 1 kind of solvent alone, or may contain 2 or more kinds.

The content ratio of the solvent in the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

The method for preparing the photosensitive resin composition is not limited. As a method for producing a photosensitive resin composition, for example, a method for producing a photosensitive resin composition by preparing solutions in which each component is dissolved in a solvent in advance and mixing the obtained solutions at a predetermined ratio can be cited. The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 to 30 μm before the photosensitive resin layer is formed.

The method of applying the photosensitive resin composition is not limited, and a known method can be used. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

The photosensitive resin layer may be formed by applying a photosensitive resin composition to a coating film described later and drying the coating film.

[ cover film ]

The photosensitive film according to the present invention preferably has a cover film (also referred to as a protective film). According to the cover film, the surface of a layer (e.g., a photosensitive resin layer) in contact with the cover film can be protected. In one embodiment, the photosensitive film more preferably has a cover film in contact with a surface of the photosensitive resin layer opposite to the side on which the temporary support is disposed.

Examples of the cover film include a resin film and paper. From the viewpoint of strength and flexibility, the film-covered resin film is preferable.

Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. The resin film is preferably a polyethylene film, a polypropylene film or a polyethylene terephthalate film.

The thickness of the cover film is not limited. The average thickness of the cover film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 10 μm to 20 μm.

From the viewpoint of further improving the resolution, the arithmetic average roughness Ra of the surface of the cover film on which the photosensitive resin layer is disposed (i.e., the surface of the cover film facing the photosensitive resin layer) is preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. When the arithmetic average roughness of the surface of the cover film on which the photosensitive resin layer is disposed is within the above range, the uniformity of the thickness of the photosensitive resin layer and the resin pattern formed is improved. The lower limit of the arithmetic average roughness Ra is not limited. The arithmetic average roughness Ra of the surface of the cover film on which the photosensitive resin layer is disposed is preferably 0.001 μm or more. The arithmetic average roughness Ra of the surface of the cover film on which the photosensitive resin layer is disposed is measured by the method based on the measurement method of the arithmetic average roughness Ra described in the section of the "temporary support".

[ relationship between temporary support, photosensitive resin layer and protective film ]

In the photosensitive film according to the present invention, it is preferable that the cured film obtained by curing the photosensitive resin layer has an elongation at break of 15% or more at 120 ℃, the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side is 50nm or less, and the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side is 150nm or less.

The photosensitive film according to the present invention preferably satisfies the following formula (R1).

X Y < 1,500: formula (R1)

In the formula (R1), X represents a value (%) of elongation at break at 120 ℃ of a cured film obtained by curing the photosensitive resin layer, and Y represents a value (nm) of arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side.

More preferably, X × Y is 750 or less.

The elongation at break at 120 ℃ is preferably 2 times or more greater than the elongation at break at 23 ℃ of a cured film obtained by curing a photosensitive resin layer.

Elongation at break was measured using a mercury ultra-high pressure lamp at 120mJ/cm ² After exposing and curing the photosensitive resin layer having a thickness of 20 μm, the cured layer was irradiated with light at 400mJ/cm using a high-pressure mercury lamp ² The cured film was further subjected to additional exposure and heated at 145 ℃ for 30 minutes, and then measured by a tensile test.

The photosensitive film according to the present invention preferably satisfies the following formula (R2).

Y is less than or equal to Z: formula (R2)

In the formula (R2), Y represents the value (nm) of the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side, and Z represents the value (nm) of the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side.

[ other layers ]

The photosensitive film according to the present invention may have a layer other than the above-described layer (hereinafter referred to as "other layer"). Examples of the other layer include a thermoplastic resin, an intermediate layer, and a contrast enhancement layer (also referred to as a refractive index adjustment layer).

(thermoplastic resin layer)

The photosensitive film according to the present invention may have a thermoplastic resin layer. In one embodiment, the photosensitive film preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. This is because, since the photosensitive film has the thermoplastic resin layer between the temporary support and the photosensitive resin layer, the following property to the substrate in the step of bonding to the substrate is improved, and the interfusion of air bubbles between the substrate and the photosensitive film is suppressed, resulting in improvement of interlayer adhesiveness.

Alkali soluble resins

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.

The alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion of a layer adjacent to the thermoplastic resin layer. Here, the "acrylic resin" refers to a resin having at least one kind selected from a structural unit derived from (meth) acrylic acid, a structural unit derived from a (meth) acrylate ester, and a structural unit derived from (meth) acrylamide.

In the acrylic resin, the proportion of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylate, and the structural unit derived from (meth) acrylamide is preferably 50% by mass or more with respect to the total mass of the acrylic resin. In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic ester is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

Also, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonic acid group, and a carboxyl group is preferable.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more. The upper limit of the acid value is not limited. The acid value of the alkali-soluble resin is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is not limited, and can be suitably selected from known resins and used. Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of Japanese patent application laid-open No. 2011-95716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of Japanese patent application laid-open No. 2010-237589, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the binder polymer described in paragraphs 0053 to 0068 of Japanese patent laid-open No. 2016-224162.

The content ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass, based on the total mass of the carboxyl group-containing acrylic resin.

The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoint of developability and adhesion of a layer adjacent to the thermoplastic resin layer.

The alkali soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include an ethylenically unsaturated group, a condensation polymerizable group (e.g., a hydroxyl group and a carboxyl group), and an addition polymerization reactive group (e.g., an epoxy group and a (blocked) isocyanate group).

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 1 ten thousand to 10 ten thousand, and particularly preferably 2 ten thousand to 5 ten thousand.

The thermoplastic resin layer may contain 1 alkali-soluble resin alone or 2 or more.

From the viewpoint of developability and adhesion of a layer adjacent to the thermoplastic resin layer, the content ratio of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass, based on the total mass of the thermoplastic resin layer.

-pigments-

The thermoplastic resin layer preferably contains a dye (hereinafter, sometimes referred to as "dye B") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm, which is a wavelength range at the time of color development, and changing the maximum absorption wavelength by an acid, an alkali, or a radical. Preferred embodiments of the dye B are the same as those of the dye N, except for the following points.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, and resolution.

From the viewpoint of visibility of exposed portions, visibility of non-exposed portions, and resolution, the thermoplastic layer preferably contains a dye whose maximum absorption wavelength changes by an acid as the dye B, and a compound that generates an acid by light, which will be described later.

The thermoplastic resin layer may contain 1 type of pigment B alone or 2 or more types.

From the viewpoint of visibility of an exposed portion and visibility of a non-exposed portion, the content ratio of the dye B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, even more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass, based on the total mass of the thermoplastic resin layer.

Here, the content ratio of the dye B refers to the content ratio of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of the dye B will be described by taking a dye that develops color by a radical as an example. 2 kinds of solutions were prepared by dissolving a dye (0.001g) and a dye (0.01g) in methyl ethyl ketone (100mL), respectively. To each of the obtained solutions, IRGACURE OXE-01 (BASF) was added as a photo radical polymerization initiator, and then 365nm light was irradiated to generate radicals, thereby bringing all the dyes into a colored state. Next, the absorbance of each solution at a liquid temperature of 25 ℃ was measured by using a spectrophotometer (UV3100, SHIMADZU CORPORATION) under an atmospheric atmosphere, and a calibration curve was prepared. Next, the absorbance of the solution in which all the coloring matters were developed was measured by the same method as described above except that the thermoplastic resin layer (0.1g) was dissolved in methyl ethyl ketone instead of the coloring matters. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the coloring matter contained in the thermoplastic resin layer was calculated from the calibration curve.

Compounds generating acids, bases or radicals by light-

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, sometimes referred to as "compound C"). The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving active light (e.g., ultraviolet light and visible light). Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

[ photoacid generators ]

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. The photoacid generator may be a photo cation polymerization initiator that may be contained in the photosensitive resin layer, and preferred embodiments are the same except for the aspects described below.

The photoacid generator preferably contains at least one selected from an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.

The photoacid generator is also preferably a photoacid generator having the following structure.

[ chemical formula 3]

[ photobase generators ]

The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, trityl alcohol, O-carbamoylhydroxyamido, O-carbamoyloxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, bis [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane 1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, cobalt hexammine (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, and mixtures thereof, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine and 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine.

[ photo radical polymerization initiator ]

The thermoplastic resin layer may contain a photo radical polymerization initiator. The photo radical polymerization initiator may be a photo radical polymerization initiator that the photosensitive resin layer may contain, for example, and the same is preferred.

The thermoplastic resin layer may contain 1 kind of compound C alone, or may contain 2 or more kinds.

The content ratio of the compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility of exposed portions, visibility of non-exposed portions, and resolution.

Plasticizers-

The thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

The molecular weight of the plasticizer (for the molecular weight of the oligomer or polymer, it means the weight average molecular weight (Mw) or less, the same as in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth) acrylate compound. From the viewpoint of compatibility, resolution, and adhesion of a layer adjacent to the thermoplastic resin layer, the alkali-soluble resin is an acrylic resin, and the plasticizer more preferably contains a (meth) acrylate compound.

Examples of the (meth) acrylate compound used as the plasticizer include the (meth) acrylate compounds described in the above-mentioned "polymerizable compound B". When the thermoplastic resin layer and the photosensitive resin layer are disposed in direct contact in the photosensitive film, the thermoplastic resin layer and the photosensitive resin layer preferably contain the same (meth) acrylate compound. This is because the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound, respectively, and diffusion of components between layers is suppressed, thereby improving storage stability.

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, the (meth) acrylate compound is preferably not polymerized in the exposed portion after exposure, from the viewpoint of adhesion of the layer adjacent to the thermoplastic resin layer.

In one embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule, from the viewpoint of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

In one embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.

The thermoplastic resin layer may contain 1 kind of plasticizer alone, or may contain 2 or more kinds.

From the viewpoint of resolution, adhesion of a layer adjacent to the thermoplastic resin layer, and developability, the content ratio of the plasticizer is preferably 1 to 70 mass%, more preferably 10 to 60 mass%, and particularly preferably 20 to 50 mass%, relative to the total mass of the thermoplastic resin layer.

Surfactants-

The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include surfactants that can be contained in the photosensitive resin layer, and preferred embodiments are the same.

The thermoplastic resin layer may contain 1 kind of surfactant alone or 2 or more kinds thereof.

The content ratio of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, based on the total mass of the thermoplastic resin layer.

Sensitizers

The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include sensitizers that can be contained in the photosensitive resin layer.

The thermoplastic resin layer may contain 1 sensitizer alone or 2 or more sensitizers.

From the viewpoint of improving the sensitivity to a light source, the visibility of exposed portions, and the visibility of non-exposed portions, the content ratio of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the thermoplastic resin layer.

Additives-

The thermoplastic resin layer may contain known additives, if necessary, in addition to the above components.

Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese patent laid-open publication No. 2014-85643. The contents of the above publications are incorporated by reference into this specification.

-thickness-

The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion of the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolution, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

-method of formation-

The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method for forming the thermoplastic resin layer, for example, a method of applying a thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition can be cited.

Examples of the thermoplastic resin composition include compositions containing the above components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. Examples of the solvent include those which can be contained in the photosensitive resin composition, and preferred embodiments are also the same.

The thermoplastic resin composition may contain 1 kind of solvent alone, or may contain 2 or more kinds.

The content ratio of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer. For example, a thermoplastic resin composition may be prepared by preparing solutions in which the components contained in the thermoplastic resin layer are dissolved in a solvent in advance, mixing the obtained solutions at a predetermined ratio, applying the obtained thermoplastic resin composition to the surface of the temporary support, and drying the coating film of the thermoplastic resin composition to form the thermoplastic resin layer. Further, after the photosensitive resin layer is formed on the cover film, a thermoplastic resin layer may be formed on the surface of the photosensitive resin layer.

(intermediate layer)

The photosensitive film according to the present invention preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. The intermediate layer can suppress mixing of components when a plurality of layers are formed and when the intermediate layer is stored.

The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppression of mixing of components at the time of coating a plurality of layers and at the time of storage after coating. In the present invention, "water-soluble" means that the solubility in 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more.

Examples of the intermediate layer include an oxygen blocking layer having an oxygen blocking function, which is described as a "separation layer" in japanese patent laid-open No. 5-72724. By using the oxygen barrier layer as the intermediate layer, the sensitivity at the time of exposure is improved, the time load of the exposure apparatus is reduced, and as a result, the productivity is improved. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers. The oxygen barrier layer used as the intermediate layer is preferably an oxygen barrier layer exhibiting low oxygen permeability, dispersed or dissolved in water or an aqueous alkaline solution (1 mass% aqueous solution of sodium carbonate at 22 ℃).

The intermediate layer preferably contains a resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. The resin contained in the intermediate layer is preferably a water-soluble resin.

From the viewpoint of suppressing mixing of a plurality of interlayer components, the resin contained in the intermediate layer is preferably a resin different from any of the polymer a contained in the photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

The intermediate layer preferably contains polyvinyl alcohol, and more preferably contains polyvinyl alcohol and polyvinyl pyrrolidone, from the viewpoint of oxygen barrier properties and suppression of mixing of components at the time of coating a plurality of layers and at the time of storage after coating.

The intermediate layer may contain 1 kind of resin alone or 2 or more kinds.

From the viewpoint of oxygen barrier properties and suppression of mixing of components at the time of coating a plurality of layers and at the time of storage after coating, the content ratio of the resin in the intermediate layer is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass% with respect to the total mass of the intermediate layer.

The intermediate layer may contain an additive as needed. Examples of the additive include a surfactant.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. By setting the thickness of the intermediate layer within the above range, mixing of components during storage when forming a plurality of layers can be suppressed without reducing the oxygen barrier property, and an increase in the time for removing the intermediate layer during development can be suppressed.

The method for forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method for forming the intermediate layer, for example, a method in which the composition for the intermediate layer is applied to the surface of the thermoplastic resin layer or the photosensitive resin layer, and then the coating film of the composition for the intermediate layer is dried can be cited.

Examples of the composition for the intermediate layer include a composition containing a resin and an optional additive. The composition for an intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for an intermediate layer and facilitate formation of the intermediate layer. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and water-miscible organic solvents.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

(contrast enhancement layer)

The photosensitive film according to the present invention may have a contrast enhancement layer. The contrast enhancement layer is described in, for example, paragraphs 0134 of international publication No. 2018/179640 and paragraphs 0194 to 0196 of japanese patent laid-open publication No. 2014-85643. The contents of these publications are incorporated by reference into this specification.

Average thickness

The average thickness of the photosensitive film is preferably 5 to 55 μm, more preferably 10 to 50 μm, and particularly preferably 20 to 40 μm.

The average thickness of the photosensitive film is determined by the same method as the method for calculating the average value (Ta) of the thickness of the photosensitive film measured in the width direction of the photosensitive film. That is, the average thickness of the photosensitive film is an arithmetic average of the thicknesses (t (x)) of the photosensitive films measured at 48 points in total in the above 3 regions (i.e., the front end portion, the central portion, and the rear end portion).

"size

The length of the photosensitive film according to the present invention is not limited. The length of the photosensitive film according to the present invention is preferably 500m or more. The length of the photosensitive film according to the present invention may be, for example, within a range of 10,000m or less.

"shape

The shape of the photosensitive film according to the present invention is not limited. The photosensitive film according to the present invention is preferably in a roll shape from the viewpoint of versatility and transportability. The photosensitive film can be formed into a roll shape by winding the photosensitive film.

Preparation method

The method for producing a photosensitive film according to the present invention is not limited as long as it can produce a photosensitive film satisfying the relationship of Tg (x) x (98.8/100) < T (x) < Tg (x) × (101.2/100) at a ratio of 90% to 100%. In the method for producing a photosensitive film according to the present invention, for example, the method for forming each layer described in the above "constituent element" can be used. Hereinafter, a preferred example of the method for producing a photosensitive film will be described with reference to fig. 2. The method for producing the photosensitive film is not limited to the method described below.

As a method for producing the photosensitive film 100 shown in fig. 2, for example, there is a method including: a step of forming a photosensitive resin layer 12 by applying a photosensitive resin composition on the temporary support 10; and disposing a cover film 14 on the photosensitive resin layer 12. In the above method, the photosensitive resin composition applied to the temporary support 10 may be dried as necessary. The drying method is not limited, and a known drying method can be used.

From the viewpoint of controlling t (x) relative to tg (x), an extrusion coating apparatus is preferably used for coating the photosensitive resin composition. As a preferable extrusion coating apparatus, for example, an extrusion coating apparatus described in japanese patent application laid-open publication No. 2011-189280 can be cited. From the viewpoint of controlling t (x), it is also preferable to apply the photosensitive resin composition by the extrusion coating method described in japanese patent application laid-open publication No. 2011-189280. According to the extrusion coating apparatus and the extrusion coating method described in Japanese patent application laid-open No. 2011-189280, since variations in the thickness of the photosensitive film can be reduced, T (x) can be controlled so as to satisfy the relationship of Tg (x) x (98.8/100) < T (x) < Tg (x) × (101.2/100).

From the viewpoint of controlling t (x) with respect to tg (x), in the application of the photosensitive resin composition, it is preferable to adjust the height of the height adjustment spacers provided at both ends of the die from which the coating liquid is discharged, for example. In order to apply the photosensitive resin composition thinly and uniformly, it is preferable to adjust the pressure in the decompression chamber which sucks the photosensitive resin composition to the side opposite to the application direction.

In the application of the photosensitive resin composition, the distance between the die and the backup roll is usually set to 30 to 300. mu.m. The distance between the die and the backup roller is set, for example, in accordance with the coating thickness, the coating speed, and the physical properties (e.g., viscosity) of the coating liquid.

As a method of disposing the cover film 14 on the photosensitive resin layer 12, for example, a method of pressure-bonding the cover film 14 on the photosensitive resin layer 12 is exemplified.

Through the above steps, the photosensitive film 100 including the temporary support 10, the photosensitive resin layer 12, and the cover film 14 can be manufactured. The manufactured photosensitive film 100 may be wound in a roll. The roll-shaped photosensitive film 100 can be used in a bonding step with a substrate by a roll-to-roll method, for example.

Application

The photosensitive film according to the present invention can be used for forming a resin pattern and forming a circuit wiring, for example. However, the application of the photosensitive film according to the present invention is not limited to the above application.

The photosensitive film according to the present invention can be used as a photosensitive film for a wiring protective film, for example. The layer structure of the photosensitive film preferably used as the photosensitive film for a wiring protective film includes, for example, the following (1) and (2).

(1) Temporary support/photosensitive resin layer/refractive index adjustment layer/cover film

(2) Temporary support/photosensitive resin layer/cover film

Hereinafter, the constituent elements of the photosensitive film preferably used as the photosensitive film for the wiring protection film will be described. Among these, the components of the photosensitive film preferably used as the photosensitive film for the wiring protection film are not limited to the components shown below.

[ temporary support ]

Examples of the temporary support include the temporary support described in the above "constituent element". The preferable embodiment of the temporary support is the same as that described in the section of the above-mentioned "constituent element".

[ cover film ]

Examples of the temporary support include the cover film described in the above "constituent element". The preferred embodiment of the cover film is the same as that described in the above item of "constituent element".

[ photosensitive resin layer ]

(alkali-soluble resin)

The photosensitive resin layer preferably contains an alkali-soluble resin.

Examples of the alkali-soluble resin include a (meth) acrylic resin, a styrene resin, an epoxy resin, an amide epoxy resin, an alkyd resin, a phenol resin, an ester resin, a urethane resin, an epoxy acrylate resin obtained by reacting an epoxy resin with (meth) acrylic acid, and an acid-modified epoxy acrylate resin obtained by reacting an epoxy acrylate resin with an acid anhydride.

As one preferable embodiment of the alkali-soluble resin, a (meth) acrylic resin is given in view of its excellent alkali developability and thin film formability.

In the present specification, the (meth) acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, relative to the entire structural units of the (meth) acrylic resin.

The (meth) acrylic resin may be composed only of a structural unit derived from a (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than a (meth) acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound with respect to the total structural units of the (meth) acrylic resin is 100 mass% or less.

Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylonitriles.

Examples of the (meth) acrylic acid ester include alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, and 2,2,3, 3-tetrafluoropropyl (meth) acrylate, and alkyl (meth) acrylate is preferable.

Examples of the (meth) acrylamide include acrylamides such as diacetone acrylamide.

Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.

The (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and more preferably methyl (meth) acrylate or ethyl (meth) acrylate.

The (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.

The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic compound copolymerizable with the (meth) acrylic compound, and examples thereof include styrene compounds which may have a substituent at the α -position or aromatic ring, such as styrene, vinyltoluene and α -methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid and crotonic acid.

These polymerizable monomers may be used in a combination of 1 or 2 or more.

In addition, from the viewpoint of improving the alkali developability, the (meth) acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonic acid group.

Among these, (meth) acrylic resins more preferably contain a structural unit having a carboxyl group, and still more preferably have a structural unit derived from the (meth) acrylic acid.

From the viewpoint of excellent developability, the content of the structural unit having an acid group (preferably, the structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is preferably 10% by mass or more with respect to the total mass of the (meth) acrylic resin. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.

The (meth) acrylic resin more preferably has a structural unit derived from the alkyl (meth) acrylate.

The content of the structural unit derived from the alkyl (meth) acrylate in the (meth) acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 90% by mass, based on the total structural units of the (meth) acrylic resin.

The (meth) acrylic resin is preferably a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate, and more preferably a resin composed of only a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate.

Further, as the (meth) acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

From the viewpoint of resolution, the (meth) acrylic resin preferably has at least one member selected from a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate.

From the viewpoint of resolution, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate in the (meth) acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to the total structural units of the (meth) acrylic resin. The upper limit is not particularly limited, and may be 100 mass% or less, preferably 80 mass% or less.

From the viewpoint of resolution, the (meth) acrylic resin preferably further has at least one selected from a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and at least one selected from a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate.

From the viewpoint of resolution, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate is preferably 60/40 to 80/20 in terms of a mass ratio with respect to the total content of the structural unit derived from acrylic acid and the structural unit derived from alkyl acrylate.

The (meth) acrylic resin preferably has an ester group at a terminal thereof, from the viewpoint of excellent developability of the photosensitive resin layer after transfer.

The terminal portion of the (meth) acrylic resin is composed of a site derived from a polymerization initiator used for synthesis. The (meth) acrylic resin having an ester group at the terminal may be synthesized by using a polymerization initiator that generates a radical having an ester group.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, for example.

Further, from the viewpoint of, for example, facilitating the formation of a strong film by thermal crosslinking with the crosslinking component by heating, the alkali-soluble resin is more preferably a resin having a carboxyl group having an acid value of 60mgKOH/g or more (so-called carboxyl group-containing resin), and still more preferably a (meth) acrylic resin having a carboxyl group having an acid value of 60mgKOH/g or more (so-called carboxyl group-containing (meth) acrylic resin).

When the alkali-soluble resin is a resin having a carboxyl group, for example, a thermally crosslinkable compound such as a blocked isocyanate compound is added to thermally crosslink the resin, whereby the three-dimensional crosslinking density can be increased. Further, when the carboxyl group of the resin having a carboxyl group is dehydrated and hydrophobized, the heat and humidity resistance can be improved.

The carboxyl group-containing (meth) acrylic resin having an acid value of 60mgKOH/g or more is not particularly limited as long as the above-mentioned acid value condition is satisfied, and can be appropriately selected from known (meth) acrylic resins.

For example, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of Japanese patent application laid-open No. 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of Japanese patent application laid-open No. 2010-237589, and the like can be preferably used.

Another preferable embodiment of the alkali-soluble resin is a styrene-acrylic acid copolymer. In the present specification, the styrene-acrylic acid copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic acid compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth) acrylic acid compound is preferably 30 mass% or more, and more preferably 50 mass% or more, based on the total structural units of the copolymer.

The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5% by mass to 80% by mass, based on the total structural units of the copolymer.

The content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass to 95% by mass, based on the total structural units of the copolymer.

From the viewpoint of moisture permeability and strength of the cured film obtained, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

Examples of the monomer forming a structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene and α -methylstyrene, and benzyl (meth) acrylate.

Among them, a styrene compound is preferable, and styrene is more preferable.

From the viewpoint of moisture permeability and strength of the cured film obtained, the alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (structural unit derived from styrene).

[ chemical formula 4]

In the case where the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, with respect to the entire structural units of the alkali-soluble resin, from the viewpoint of moisture permeability and strength of the resulting cured film.

From the viewpoint of moisture permeability and strength of the cured film obtained, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 60 mol%, based on the total structural units of the alkali-soluble resin.

From the viewpoint of moisture permeability and strength of the cured film obtained, the content of the structural unit represented by the formula (S) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, even more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%, based on the total structural units of the alkali-soluble resin.

In the present specification, when the content of the "structural unit" is defined in terms of a molar ratio, the "structural unit" is defined to have the same meaning as the "monomer unit". In the present specification, the "monomer unit" may be modified by a polymer reaction or the like after polymerization. The same applies to the following.

The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure from the viewpoints of development residue inhibition, strength of the resulting cured film, and adhesiveness of the resulting uncured film. That is, the alkali-soluble resin preferably contains a structural unit having an aliphatic hydrocarbon ring structure. Among them, the alkali-soluble resin more preferably has a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane ring and isoboronyl ring.

Among them, from the viewpoints of the development residue inhibition property, the strength of the obtained cured film and the adhesion of the obtained uncured film, a ring in which 2 or more aliphatic hydrocarbon rings are condensed is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 ] is more preferable ^2,6 ]A decane ring).

Examples of the monomer forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

From the viewpoints of the residue development inhibition property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the alkali-soluble resin more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[ chemical formula 5]

In the formula (Cy), R ^M Represents a hydrogen atom or a methyl group, R ^Cy Represents a 1-valent group having an aliphatic hydrocarbon ring structure.

R in the formula (Cy) ^M Preferably methyl.

R in the formula (Cy) is R in the formula (Cy) from the viewpoints of the development residue inhibition property, the strength of the obtained cured film and the adhesion of the obtained uncured film ^Cy The aliphatic hydrocarbon compound preferably has a valence of 1 group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably has a valence of 1 group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably has a valence of 1 group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (1) may be a monocyclic structure or a polycyclic structure.

And a cured film obtained from the development residue-inhibiting propertyR of the formula (Cy) from the viewpoints of the strength of (C) and the adhesiveness of the obtained uncured film ^Cy The aliphatic hydrocarbon ring structure in (2) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isoboron ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure.

In addition, from the viewpoint of the development residue inhibitory property, the strength of the obtained cured film and the adhesiveness of the obtained uncured film, R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (1) is preferably a ring structure obtained by fusing 2 or more aliphatic hydrocarbon rings, and more preferably a ring structure obtained by fusing 2 to 4 aliphatic hydrocarbon rings.

In addition, R in the formula (Cy) is R from the viewpoint of the development residue inhibitory property, the strength of the obtained cured film and the adhesiveness of the obtained uncured film ^Cy The aliphatic hydrocarbon ring group, which is a group in which an oxygen atom of — C (═ O) O — in the formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, is preferred, and the cyclohexyl group or the dicyclopentyl group is more preferred, and the dicyclopentyl group is still more preferred.

The alkali-soluble resin may have 1 structural unit having an aliphatic hydrocarbon ring structure alone or 2 or more.

In the case where the alkali-soluble resin contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass, relative to the entire structural unit of the alkali-soluble resin, from the viewpoints of development residue suppression, strength of the resulting cured film, and adhesiveness of the resulting uncured film.

From the viewpoints of the development residue suppression property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol%, based on the entire structural units of the alkali-soluble resin.

From the viewpoints of the development residue suppression property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the content of the structural unit represented by the formula (Cy) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol%, based on the total structural units of the alkali-soluble resin.

In the case where the alkali-soluble resin contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass, based on the total structural units of the alkali-soluble resin, from the viewpoints of the development residue suppression property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film.

From the viewpoints of the development residue suppression property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol%, based on the total structural units of the alkali-soluble resin.

From the viewpoints of the development residue suppression property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the total content of the structural unit represented by the formula (S) and the structural unit represented by the formula (Cy) in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol%, based on the total structural units of the alkali-soluble resin.

From the viewpoints of the development residue suppression property, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, the molar amount nS of the structural unit represented by the formula (S) and the molar amount nCy of the structural unit represented by the formula (Cy) in the alkali-soluble resin preferably satisfy the relationship represented by the following formula (SCy), more preferably satisfy the following formula (SCy-1), and still more preferably satisfy the following formula (SCy-2).

nS/(nS + nCy) is more than or equal to 0.2 and less than or equal to 0.8: formula (SCy)

nS/(nS + nCy) is more than or equal to 0.30 and less than or equal to 0.75: formula (SCy-1)

nS/(nS + nCy) is more than or equal to 0.40 and less than or equal to 0.70: formula (SCy-2)

The alkali-soluble resin preferably contains a structural unit having an acid group from the viewpoint of developability and adhesion to a substrate.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group, and a carboxyl group is preferable.

The structural unit having an acid group is preferably a structural unit derived from (meth) acrylic acid described below, and more preferably a structural unit derived from methacrylic acid.

[ chemical formula 6]

The alkali-soluble resin may have 1 kind of structural unit having an acid group alone, or may have 2 or more kinds.

In the case where the alkali-soluble resin contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass, with respect to the entire structural unit of the alkali-soluble resin, from the viewpoints of developability and adhesion to a substrate.

From the viewpoint of developability and adhesion to a substrate, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on the entire structural unit of the alkali-soluble resin.

From the viewpoint of developability and adhesion to a substrate, the content of the structural unit derived from (meth) acrylic acid in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on the total structural units of the alkali-soluble resin.

The alkali-soluble resin preferably has a reactive group, and more preferably contains a structural unit having a reactive group, from the viewpoint of curability and strength of the resulting cured film.

The reactive group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. Also, in the case where the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

In the present specification, "main chain" represents a relatively longest bond chain in a molecule of a polymer compound constituting a resin, and "side chain" represents a group of atoms branched from the main chain.

As the ethylenically unsaturated group, an allyl group or a (meth) acryloyloxy group is more preferable.

Examples of the structural unit having a reactive group include, but are not limited to, the structural units shown below.

[ chemical formula 7]

The alkali-soluble resin may have 1 kind of structural unit having a reactive group alone, or may have 2 or more kinds.

In the case where the alkali-soluble resin contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass, relative to the entire structural unit of the alkali-soluble resin, from the viewpoints of curability and strength of the resulting cured film.

From the viewpoint of curability and strength of the resulting cured film, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and still more preferably 20 mol% to 50 mol%, based on the total structural units of the alkali-soluble resin.

Examples of a method for introducing a reactive group into the alkali-soluble resin include a method in which a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride is reacted with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group.

A preferable example of the method of introducing a reactive group into the alkali-soluble resin is a method of synthesizing a polymer having a carboxyl group by a polymerization reaction, and then reacting glycidyl (meth) acrylate with a part of the carboxyl group of the obtained resin by a polymer reaction to introduce a (meth) acryloyloxy group into the polymer. By this method, an alkali-soluble resin having a (meth) acryloyloxy group in a side chain can be obtained.

The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃ and more preferably at a temperature of 80 to 90 ℃. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferred. The polymerization reaction is preferably carried out at a temperature of 80 to 110 ℃. In the above-mentioned polymer reaction, a catalyst such as ammonium salt is preferably used.

As the alkali-soluble resin, the following resins are preferred from the viewpoint of further excellent effects in the present invention. The content ratios (a to d) of the respective structural units shown below, the weight average molecular weight Mw, and the like may be appropriately changed according to the purpose.

[ chemical formula 8]

In the resin, a is preferably 20 to 60% by mass, b is preferably 10 to 50% by mass, c is preferably 5.0 to 25% by mass, and d is preferably 10 to 50% by mass.

[ chemical formula 9]

[ chemical formula 10]

In the resin, a is preferably 30 to 65% by mass, b is preferably 1.0 to 20% by mass, c is preferably 5.0 to 25% by mass, and d is preferably 10 to 50% by mass.

[ chemical formula 11]

In the resin, a is preferably 1.0 to 20% by mass, b is preferably 20 to 60% by mass, c is preferably 5.0 to 25% by mass, and d is preferably 10 to 50% by mass.

The alkali-soluble resin may contain a polymer containing a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer X").

The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.

The ring of the cyclic carboxylic acid anhydride structure is preferably a 5-to 7-membered ring, more preferably a 5-or 6-membered ring, and still more preferably a 5-membered ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit having a main chain containing a 2-valent group obtained by removing 2 hydrogen atoms from a compound represented by the following formula P-1, or a structural unit in which a 1-valent group obtained by removing 1 hydrogen atom from a compound represented by the following formula P-1 is bonded to a main chain directly or through a 2-valent linking group.

[ chemical formula 12]

In the formula P-1, R ^A1a Represents a substituent, n ^1a R is ^A1a May be the same or different, Z ^1a Denotes a 2-valent group forming a ring containing-C (═ O) -O-C (═ O) -, n ^1a Represents an integer of 0 or more.

As a group R ^A1a Examples of the substituent include an alkyl group.

As Z ^1a The alkylene group has preferably 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms.

n ^1a Represents an integer of 0 or more. When Z is ^1a When n represents an alkylene group having 2 to 4 carbon atoms ^1a Preferably 0 ~ 4 integer, more preferably 0 ~ 2 integer, more preferably 0.

When n is ^1a When an integer of 2 or more is represented, a plurality of R's are present ^A1a May be the same or different. And, there are a plurality of R ^A1a The ring may be formed by bonding to each other, but preferably the ring is formed without bonding to each other.

The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, still more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, particularly preferably a structural unit derived from anhydrous maleic acid or anhydrous itaconic acid, and most preferably a structural unit derived from anhydrous maleic acid.

The following may be mentioned those having a carboxylic anhydride structureSpecific examples of the structural unit include, but are not limited to, structural units having a carboxylic anhydride structure. In the following structural units, Rx represents a hydrogen atom, a methyl group, or CH ₂ OH radicals or CF ₃ Me represents a methyl group.

[ chemical formula 13]

[ chemical formula 14]

The number of the structural units having a carboxylic anhydride structure in the polymer X may be 1 or 2 or more.

The total content of the structural units having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 35 mol% based on the total structural units of the polymer X.

The photosensitive resin layer may contain only 1 type of polymer X, or may contain 2 or more types.

When the photosensitive resin layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of resolution and developability.

From the viewpoint of improving resolution and developability, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

The acid value of the alkali-soluble resin is preferably from 10mgKOH/g to 200mgKOH/g, more preferably from 60mgKOH/g to 200mgKOH/g, still more preferably from 60mgKOH/g to 150mgKOH/g, and particularly preferably from 60mgKOH/g to 110 mgKOH/g.

In addition, the acid value of the alkali-soluble resin is as follows JIS K0070: 1992.

From the viewpoint of developability, the dispersion degree (weight average molecular weight/number average molecular weight) of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

The photosensitive resin layer may contain only 1 alkali-soluble resin, or may contain 2 or more kinds.

From the viewpoint of photosensitivity, resolution, and developability, the content of the alkali-soluble resin is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and still more preferably 30 to 70 mass% with respect to the total mass of the photosensitive resin layer.

(polymerizable Compound)

The photosensitive resin layer may contain a polymerizable compound.

The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group, and a radical polymerizable group is preferable.

The polymerizable compound preferably contains a polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound").

As the ethylenically unsaturated group, (meth) acryloyloxy group is preferable.

The ethylenically unsaturated compound in the present specification is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.

The preferable embodiment of the ethylenically unsaturated compound is the same as that of the ethylenically unsaturated compound described in the section of the above-mentioned "photosensitive resin layer".

As one of preferable embodiments of the ethylenically unsaturated compound, a compound represented by the following formula (M) (also simply referred to as "compound M") can be mentioned.

Q ² -R ¹ -Q ¹ : formula (M)

In the formula (M), Q ¹ And Q ² Each independently represents (meth) propyleneAcyloxy radical, R ¹ Represents a divalent linking group having a chain structure.

Q in the formula (M) is a group represented by the formula (I) ¹ And Q ² Preferably the same groups.

And, from the viewpoint of reactivity, Q in the formula (M) ¹ And Q ² Preferred is an acryloyloxy group.

As R in formula (M) ¹ From the viewpoints of the development residue inhibition property, rust prevention property, and bending resistance of the resulting cured film, an alkylene group or alkyleneoxyalkylene group (-L) is preferable ¹ -O-L ¹ -) or polyalkyleneoxyalkylene (- (L) ¹ -O) _p -L ¹ -) more preferably a hydrocarbon group or a polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, still more preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

The hydrocarbon group is not particularly limited as long as at least a part thereof has a chain structure, and the part other than the chain structure may be, for example, any of a branched chain, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, and a combination thereof, preferably an alkylene group or a combination of 2 or more alkylene groups and 1 or more arylene groups, more preferably an alkylene group, and further preferably a linear alkylene group.

Further, L is as defined above ¹ Each independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1, 2-propylene group.

p represents an integer of 2 or more, preferably an integer of 2 to 10.

Also, the linkage Q in the compound M is from the viewpoints of the development residue inhibition property, the rust prevention property, and the bending resistance of the obtained cured film ¹ And Q ² The number of atoms of the shortest connecting chain therebetween is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

In this specification, "connection Q ¹ And Q ² The number of atoms of the shortest connecting chain therebetween "means that the group is to be bonded to Q ¹ Attached R ¹ To and Q ² Attached R ¹ The shortest atom number to which the atoms in (b) are linked.

Specific examples of the compound M include 1, 3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 7-heptanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, di (meth) acrylate of hydrogenated bisphenol A, di (meth) acrylate of hydrogenated bisphenol F, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol/propylene glycol) di (meth) acrylate, and polybutylene glycol di (meth) acrylate. The above ester monomers may also be used as mixtures.

Among the above compounds, at least one compound selected from the group consisting of 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate is preferable, at least one compound selected from the group consisting of 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable, and at least one compound selected from the group consisting of 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is even more preferable, from the viewpoint of development residue inhibition, rust prevention and bending resistance of the cured film obtained.

Further, as one of preferable embodiments of the ethylenically unsaturated compound, an ethylenically unsaturated compound having 2 or more functions can be mentioned.

In the present specification, "an ethylenically unsaturated compound having 2 or more functions" means a compound having 2 or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth) acryloyl group is preferable.

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The 2-functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.

Examples of the 2-functional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1, 4-cyclohexanediol di (meth) acrylate.

Commercially available products of 2-functional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK ester A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.), tricyclodecanedimethanol dimethacrylate (trade name: NK ester DCP, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.), 1, 9-nonanediol diacrylate (trade name: NK ester A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD), and 1, 6-hexanediol diacrylate (trade name: NK ester A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.).

The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and may be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compounds having a glycerol tri (meth) acrylate skeleton.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), (alkylene oxide-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) RP-1040 manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., (ATM-35E, A-9300 manufactured by LTD., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., Ltd.), and ethoxylated glycerol triacrylate (NK ester A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)).

The ethylenically unsaturated compound may also be a urethane (meth) acrylate compound.

Examples of the urethane (meth) acrylate include urethane di (meth) acrylates, and examples thereof include propylene oxide-modified urethane di (meth) acrylates, and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylates.

Further, as the urethane (meth) acrylate, there may be mentioned a 3-or more-functional urethane (meth) acrylate. The lower limit of the number of functional groups is preferably 6 or more, more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of the 3-or more-functional urethane (meth) acrylate include 8UX-015A (manufactured by TAISEI FINE CHEMICAL CO. LTD.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), U-15HA (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), AH-600 (trade name.) manufactured by KYOEISHA CHEMICAL Co., LTD., and UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (both manufactured by Nippon Kayaku Co., Ltd.), and the like.

As one of preferable embodiments of the ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group can be mentioned.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

Among them, as the acid group, a carboxyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include 3-to 4-functional ethylenically unsaturated compounds having an acid group [ a substance having a carboxyl group introduced into a pentaerythritol tri-and tetraacrylate (PETA) skeleton (acid value: 80mgKOH/g to 120mgKOH/g) ], 5-to 6-functional ethylenically unsaturated compounds having an acid group [ a substance having a carboxyl group introduced into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton (acid value: 25mgKOH/g to 70mgKOH/g) ], and the like.

These ethylenically unsaturated compounds having 3 or more functions of an acid group may be used in combination with the ethylenically unsaturated compounds having 2 functions of an acid group, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof.

When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic acid anhydrides thereof, the developability and the film strength are further improved.

The ethylenically unsaturated compound having 2 or more functions of a carboxyl group is not particularly limited, and can be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound having a carboxyl group and 2 or more functions include aroneix (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), aroneix (registered trademark) M-520 (manufactured by TOAGOSEI co., ltd.), and aroneix (registered trademark) M-510 (manufactured by TOAGOSEI co., ltd.).

As the ethylenically unsaturated compound having an acid group, a polymerizable compound having an acid group as described in paragraphs 0025 to 0030 of Japanese patent laid-open publication No. 2004-239942, the contents of which are incorporated herein, is preferable.

Examples of the ethylenically unsaturated compound include a compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, a compound obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, a urethane monomer such as a (meth) acrylate compound having a urethane bond, an isophthalic acid compound such as γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate and β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, and an alkyl (meth) acrylate.

These may be used alone or in combination of 2 or more kinds.

Examples of the compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol include bisphenol a-based (meth) acrylate compounds such as 2, 2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypolypropoxy) phenyl) propane, and 2, 2-bis (4- ((meth) acryloyloxypolyoxypolyethoxy) phenyl) propane; polyethylene glycol di (meth) acrylate in which the number of ethylene oxide groups is 2 to 14, polypropylene glycol di (meth) acrylate in which the number of propylene oxide groups is 2 to 14, polyethylene polypropylene glycol di (meth) acrylate in which the number of ethylene oxide groups is 2 to 14 and the number of propylene oxide groups is 2 to 14, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxy tri (meth) acrylate, trimethylolpropane pentaethoxy tri (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane pentaethoxy tri (meth) acrylate, propylene oxide tetraacrylate, propylene oxide tri (meth) acrylate, propylene oxide di (meth) acrylate, propylene oxide (meth) acrylate, and (meth) acrylate, Tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., ATM-35 (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glyceryl triacrylate (for example, SHIN-NAKAMURA CHEMICAL CO., A-GLY-9E manufactured by LTD., etc.).

As the ethylenically unsaturated compound, a compound containing an ester bond is also preferable from the viewpoint of excellent developability.

The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoint of excellent curability and developability, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure.

Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.

As one of preferable embodiments of the ethylenically unsaturated compound, an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably, a 2-functional ethylenically unsaturated compound) can be mentioned.

The ethylenically unsaturated compound is preferably an ethylenically unsaturated compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a 2-functional ethylenically unsaturated compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed, and still more preferably tricyclodecane dimethanol di (meth) acrylate.

The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure or an isoboron structure from the viewpoints of moisture permeability and bending resistance of the obtained cured film and adhesiveness of the obtained uncured film.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

In the ethylenically unsaturated compound contained in the photosensitive resin layer, the proportion of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.

As one of preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains an ethylenically unsaturated compound having 2 or more functions, more preferably contains an ethylenically unsaturated compound having 3 or more functions, and further preferably contains an ethylenically unsaturated compound having 3 or 4 functions.

In addition, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin containing a structural unit having an aliphatic hydrocarbon ring.

Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and further preferably contains a succinic acid-modified product of 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and dipentaerythritol pentaacrylate.

In addition, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

In addition, as one of preferable embodiments of the photosensitive resin layer, from the viewpoint of the development residue suppression property and the rust prevention property, the photosensitive resin layer preferably contains a 2-functional ethylenically unsaturated compound (preferably a 2-functional (meth) acrylate compound) and a 3-functional or higher ethylenically unsaturated compound (preferably a 3-functional or higher (meth) acrylate compound).

The mass ratio of the content of the 2-functional ethylenically unsaturated compound to the content of the 3-or more-functional ethylenically unsaturated compound is preferably 10:90 to 90:10, and more preferably 30:70 to 70: 30.

The content of the 2-functional ethylenically unsaturated compound is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, relative to the total amount of all ethylenically unsaturated compounds.

The content of the 2-functional ethylenically unsaturated compound in the photosensitive resin layer is preferably 10 to 60 mass%, more preferably 15 to 40 mass%, relative to the total mass of the photosensitive resin layer.

In addition, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains the compound M and a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.

Further, as one of preferable embodiments of the photosensitive resin layer, from the viewpoint of substrate adhesion, development residue suppression property, and rust prevention property, the photosensitive resin layer preferably contains the compound M and an ethylenically unsaturated compound having an acid group, more preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, and further preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having 3 or more functions, and an ethylenically unsaturated compound having an acid group, particularly preferred are compounds M, 2-functional ethylenically unsaturated compounds having an aliphatic hydrocarbon ring structure, ethylenically unsaturated compounds having 3 or more functions, ethylenically unsaturated compounds having an acid group, and urethane (meth) acrylate compounds.

Further, as one of preferable embodiments of the photosensitive resin layer, from the viewpoint of substrate adhesion, development residue suppression property and rust prevention property, the photosensitive resin layer preferably contains 1, 9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, preferably contains 1, 9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate and an ethylenically unsaturated compound having a carboxylic acid group, particularly preferred are 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, ethylenically unsaturated compounds having a carboxylic acid group, and urethane acrylate compounds.

The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

The content of the ethylenic unsaturated compound having a 2-or more function in the ethylenic unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, with respect to the total content of all ethylenic unsaturated compounds contained in the photosensitive resin layer.

The ethylenically unsaturated compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, even more preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass, based on the total mass of the photosensitive resin layer.

(polymerization initiator)

The photosensitive resin layer may contain a polymerization initiator.

As the polymerization initiator, a photopolymerization initiator is preferable.

The preferable embodiment of the photopolymerization initiator is the same as that described in the section of the "photosensitive resin layer".

The polymerization initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, relative to the total mass of the photosensitive resin layer. The upper limit is preferably 10 mass% or less, and more preferably 5 mass% or less, based on the total mass of the photosensitive resin layer.

(heterocyclic compound)

The photosensitive resin layer may contain a heterocyclic compound.

The heterocyclic ring of the heterocyclic compound may be any of monocyclic and polycyclic.

Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a nitrogen atom.

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a Rhodanine (Rhodanine) compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound.

Among the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound, and more preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound.

Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[ chemical formula 15]

[ chemical formula 16]

Examples of the tetrazolium compound include the following compounds.

[ chemical formula 17]

[ chemical formula 18]

Examples of the thiadiazole compound include the following compounds.

[ chemical formula 19]

Examples of the triazine compound include the following compounds.

[ chemical formula 20]

Examples of the rhodanine compound include the following compounds.

[ chemical formula 21]

Examples of the thiazole compound include the following compounds.

[ chemical formula 22]

Examples of the benzothiazole compound include the following compounds.

[ chemical formula 23]

Examples of the benzimidazole compound include the following compounds.

[ chemical formula 24]

[ chemical formula 25]

Examples of the benzoxazole compound include the following compounds.

[ chemical formula 26]

The heterocyclic compounds can be used alone in 1 kind, also can be combined with more than 2 kinds.

When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, even more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass, based on the total mass of the photosensitive resin layer.

(aliphatic thiol Compound)

The photosensitive resin layer may contain an aliphatic thiol compound.

By containing the aliphatic thiol compound in the photosensitive resin layer and performing an ene-thiol reaction between the aliphatic thiol compound and the ethylenically unsaturated compound, curing shrinkage of the formed film can be suppressed and stress can be relaxed.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) is preferable.

Among the above, the aliphatic thiol compound is more preferably a polyfunctional aliphatic thiol compound from the viewpoint of adhesiveness of a formed pattern (particularly, adhesiveness after exposure).

In the present specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having 2 or more thiol groups (also referred to as "mercapto groups") in the molecule.

The polyfunctional aliphatic thiol compound is preferably a low-molecular-weight compound having a molecular weight of 100 or more. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.

The number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and still more preferably 2 to 6 functional groups, from the viewpoint of adhesion of a formed pattern.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutoxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, trimethylolethane tris (3-mercaptobutyrate), tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bisthiopropionate, and the like, 1, 4-bis (3-mercaptobutoxy) butane, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexamethylenedithiol, 2' - (ethylenedithiol) diethylthiol, meso-2, 3-dimercaptosuccinic acid, and bis (mercaptoethyl) ether.

Among the above, as the polyfunctional aliphatic thiol compound, at least one compound selected from trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutoxy) butane and 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione is preferable.

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

The photosensitive resin layer may contain 1 kind of aliphatic thiol compound alone, or may contain 2 or more kinds of aliphatic thiol compounds.

When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, still more preferably 5% by mass to 30% by mass, and particularly preferably 8% by mass to 20% by mass, based on the total mass of the photosensitive resin layer.

(thermally crosslinkable Compound)

The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

Examples of the thermally crosslinkable compound include the thermally crosslinkable compounds described in the above item "photosensitive resin layer".

The thermally crosslinkable compound may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(surfactant)

The photosensitive resin layer may contain a surfactant.

Examples of the surfactant include the surfactants described in the above item "photosensitive resin layer".

The surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.80% by mass, based on the total mass of the photosensitive resin layer.

(radical polymerization inhibitor)

The photosensitive resin layer may contain a radical polymerization inhibitor.

Examples of the radical polymerization inhibitor include the radical polymerization inhibitors described in the above item "photosensitive resin layer".

The radical polymerization inhibitor may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive resin layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, relative to the total mass of the photosensitive resin layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin layer is more excellent. On the other hand, when the content is 3% by mass or less, it is more excellent in maintaining sensitivity and suppressing discoloration of the dye.

(Hydrogen-donating compound)

The photosensitive resin layer may contain a hydrogen donating compound.

The hydrogen-donating compound has the effects of further improving the sensitivity of the photopolymerization initiator to active light, suppressing inhibition of polymerization of the polymerizable compound by oxygen, and the like.

Examples of the hydrogen donating compound include amines and amino acid compounds.

Examples of the amines include compounds described in M.R. Sander et al, "Journal of Polymer Society" volume 10, 3173 (1972), Japanese patent publication No. 44-020189, Japanese patent publication No. 51-082102, Japanese patent publication No. 52-134692, Japanese patent publication No. 59-138205, Japanese patent publication No. 60-084305, Japanese patent publication No. 62-018537, Japanese patent publication No. 64-033104, and Research Disclosure No. 33825. More specifically, 4' -bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (also known as leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline and p-methylthiodimethylaniline are mentioned.

Among them, from the viewpoint of sensitivity, curing speed and curability, the amine is preferably at least one selected from the group consisting of 4, 4' -bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

Among these, N-phenylglycine is preferable as the amino acid compound from the viewpoints of sensitivity, curing speed, and curability.

Further, examples of the hydrogen-donating compound include an organometallic compound (tributylstannate, etc.) described in Japanese patent application publication No. 48-042965, a hydrogen donor described in Japanese patent application publication No. 55-034414, and a sulfur compound (trithiane, etc.) described in Japanese patent application publication No. 6-308727.

The hydrogen donating compound may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the photosensitive resin layer contains a hydrogen donating compound, the content of the hydrogen donating compound is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and even more preferably 0.03 to 5.0% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of improvement in curing rate due to a balance between polymerization growth rate and chain transfer.

(impurities)

The photosensitive resin layer may contain a predetermined amount of impurities.

Examples of the impurities include the impurities described in the above "photosensitive resin layer".

(residual monomer)

Examples of the residual monomer corresponding to each structural unit of the polymer a in the photosensitive resin layer include the residual monomers corresponding to each structural unit of the polymer a described in the above item "photosensitive resin layer".

(other Components)

The photosensitive resin layer may contain a component other than the above-described components (hereinafter, also referred to as "other component"). Examples of the other components include a colorant, an antioxidant, and particles (for example, metal oxide particles). Further, other additives described in paragraphs 0058 to 0071 of Japanese patent application laid-open No. 2000-310706 may be mentioned as other components.

Particles-

As the particles, metal oxide particles are preferable.

The metal in the metal oxide particles also includes semimetals such As B, Si, Ge, As, Sb and Te.

For example, the average primary particle diameter of the particles is preferably 1nm to 200nm, more preferably 3nm to 80nm, from the viewpoint of transparency of the cured film.

The average primary particle size of the particles was calculated by measuring the particle sizes of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. In addition, when the shape of the particle is not spherical, the longest side is the particle diameter.

When the photosensitive resin layer contains particles, only 1 kind of metal particles having different types, sizes, etc. may be contained, or 2 or more kinds may be contained.

When the photosensitive resin layer contains no particles or the photosensitive resin layer contains particles, the content of the particles is preferably more than 0% by mass and not more than 35% by mass based on the total mass of the photosensitive resin layer, more preferably the content of the particles is not more than 0% by mass and not more than 10% by mass based on the total mass of the photosensitive resin layer, still more preferably the content of the particles is not more than 0% by mass and not more than 5% by mass based on the total mass of the photosensitive resin layer, still more preferably the content of the particles is not more than 0% by mass and not more than 1% by mass based on the total mass of the photosensitive resin layer, and particularly preferably the particles are not contained.

Colorants-

The photosensitive resin layer may contain a colorant (pigment, dye, or the like), and preferably contains substantially no colorant from the viewpoint of transparency, for example.

When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the photosensitive resin layer.

Antioxidants-

Examples of the antioxidant include 3-pyrazolones such as 1-phenyl-3-pyrazolone (also known as "phenone"), 1-phenyl-4, 4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone and chlorohydroquinone; p-methyl aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

Among them, from the viewpoint of storage stability and curability, 3-pyrazolones are preferable, and 1-phenyl-3-pyrazolones are more preferable as the antioxidant.

When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and further preferably 0.01 mass% or more, with respect to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

(thickness of photosensitive resin layer)

The thickness (layer thickness) of the photosensitive resin layer is not particularly limited, but is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, particularly preferably 10 μm or less, and most preferably 5.0 μm or less, from the viewpoint of developability and resolution. The lower limit is preferably 0.60 μm or more, and more preferably 1.5 μm or more, from the viewpoint of excellent strength of the film obtained by curing the photosensitive resin layer.

(refractive index of photosensitive resin layer)

The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, and more preferably 1.49 to 1.54.

(color of photosensitive resin layer)

The photosensitive resin layer is preferably achromatic. In particular, the total reflection (angle of incidence 8 °, light source: D-65(2 ° field of view)) is in CIE1976 (L) ^* ,a ^* ,b ^* ) In color space, L ^* The value is preferably 10 to 90, a ^* The value is preferably-1.0 to 1.0, b ^* The value is preferably-1.0 to 1.0.

The pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) is preferably achromatic.

In particular, the total reflection (incident angle 8 °, light source: D-65(2 ° field of view)) is in CIE1976 (L) ^* ,a ^* ,b ^* ) L of a pattern in color space ^* The value is preferably 10 to 90, a of the pattern ^* The value is preferably-1.0 to 1.0, b of the pattern ^* The value is preferably-1.0 to 1.0.

(moisture permeability of photosensitive resin layer)

From the viewpoint of rust prevention, the moisture permeability of a pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer is preferably 500 g/(m) at a layer thickness of 40 μm ² 24hr) or less, more preferably 300 g/(m) ² 24hr) or less, more preferably 100 g/(m) ² 24hr) or less.

Further, the moisture permeability was 300mJ/cm at the exposure amount through the i-line ² After exposure of the photosensitive resin layer, post-baking was performed at 145 ℃ for 30 minutes, and measurement was performed using a cured film obtained by curing the photosensitive resin layer.

[ refractive index adjusting layer ]

The photosensitive transfer material preferably has a refractive index adjustment layer.

As the refractive index adjusting layer, a known refractive index adjusting layer can be applied. Examples of the material contained in the refractive index adjustment layer include an alkali-soluble resin, an ethylenically unsaturated compound, a metal salt, and particles.

The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin.

Examples of the alkali-soluble resin and the ethylenically unsaturated compound include the alkali-soluble resin and the ethylenically unsaturated compound described in the above "photosensitive resin layer".

Examples of the particles include metal oxide particles and metal particles.

The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metal in the metal oxide particles also includes semimetals such As B, Si, Ge, As, Sb and Te.

The metal oxide particles are preferably selected from, specifically, zirconium oxide particles (ZrO) ₂ Particles), Nb ₂ O ₅ Particles, titanium oxide particles (TiO) ₂ Particles), silica particles (SiO) ₂ Particles) and composite particles thereof.

Among them, the metal oxide particles are more preferably at least one selected from zirconia particles and titania particles, for example, from the viewpoint of easy adjustment of the refractive index.

Examples of commercially available products of the metal oxide particles include calcined zirconia particles (manufactured by CIK NAOTEK CORPORATION, product name: ZRPGM15 WT% -F04), calcined zirconia particles (manufactured by CIK NAOTEK CORPORATION, product name: ZRPGM15 WT% -F74), calcined zirconia particles (manufactured by CIK NAOTEK CORPORATION, product name: ZRPGM15 WT% -F75), calcined zirconia particles (manufactured by CIK NAOTEK CORPORATION, product name: ZRPGM15 WT% -F76), zirconia particles (NanoUse OZ-S30M, manufactured by Nissan Chemical Industries, Ltd.) and zirconia particles (NanoUse OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

The number of particles may be 1 or more than 2.

The content of the particles in the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 85% by mass, based on the total mass of the refractive index adjustment layer.

When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 85% by mass, based on the total mass of the refractive index adjustment layer.

The refractive index of the refractive index adjustment layer is preferably higher than the refractive index of the photosensitive resin layer.

The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index adjustment layer is preferably 2.10 or less, more preferably 1.85 or less, and particularly preferably 1.78 or less.

The thickness of the refractive index adjustment layer is preferably 50nm to 500nm, more preferably 55nm to 110nm, and still more preferably 60nm to 100 nm.

The refractive index adjustment layer is formed using, for example, a refractive index adjustment layer. The composition for forming the refractive index adjustment layer preferably contains various components and solvents for forming the refractive index adjustment layer. In the composition for forming a refractive index adjusting layer, the preferable ranges of the contents of the respective components with respect to the total solid content of the composition are the same as the preferable ranges of the contents of the respective components with respect to the total mass of the refractive index adjusting layer.

The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjustment layer, and is preferably at least one selected from water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and water-miscible organic solvents.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

The solvent may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.

The method for forming the refractive index adjustment layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, and the like).

[ relationship between temporary support, photosensitive resin layer, and cover film ]

The relationship among the temporary support, the photosensitive resin layer, and the cover film is also preferably satisfied in the photosensitive film preferably used as the photosensitive film for a wiring protection film.

< method for manufacturing resin pattern and method for manufacturing circuit wiring >

The method for producing a resin pattern according to the present invention is not limited as long as the method for producing a resin pattern using the photosensitive film according to the present invention is used. For example, in the case of using a photosensitive film including a temporary support and a photosensitive resin layer, the method for producing a resin pattern according to the present invention preferably includes, in order: a step of bonding the photosensitive film according to the present invention to a substrate (preferably, a substrate having conductivity) by bringing the surface of the photosensitive resin layer opposite to the side on which the temporary support is disposed into contact with the substrate (hereinafter, may be referred to as "bonding step"); a step of performing pattern exposure on the photosensitive resin layer (hereinafter, may be referred to as an "exposure step"); and a step of forming a resin pattern by developing the photosensitive resin layer (hereinafter, sometimes referred to as a "developing step").

The method for producing a circuit wiring according to the present invention is not limited as long as it is a method for producing a circuit wiring using the photosensitive film according to the present invention. The method for manufacturing a circuit wiring according to the present invention preferably includes a step of etching the conductive layer located in a region where the resin pattern is not arranged (hereinafter, may be referred to as an "etching step") in a laminate in which a base material, the conductive layer, and the resin pattern formed using the photosensitive film according to the present invention are sequentially laminated.

Preferably, the method for manufacturing a resin pattern according to the present invention and the method for manufacturing a circuit wiring according to the present invention are each performed by a roll-to-roll method. The roll-to-roll method includes a step of winding out a substrate or a structure including the substrate before any step included in a method for manufacturing a resin pattern or a method for manufacturing a circuit wiring, using the substrate that can be wound up and wound out as the substrate (also referred to as a "winding-out step"); and a step of winding the substrate or the structure including the substrate after any one step (also referred to as a "winding step"), and a mode of performing at least any one step (preferably all steps or all steps except the heating step) while conveying the substrate or the structure including the substrate. The method of unwinding in the unwinding step and the method of winding in the winding step are not limited, and any known method may be used in the manufacturing method to which the roll-to-roll method is applied.

The respective steps included in the method for manufacturing a resin pattern according to the present invention and the method for manufacturing a circuit wiring according to the present invention will be described below. In this connection, unless otherwise specified, the contents described for each step included in the method for manufacturing a resin pattern according to the present invention are also applicable to each step included in the method for manufacturing a circuit wiring according to the present invention.

Bonding Process

The method for producing a resin pattern according to the present invention preferably includes a step of bonding the photosensitive film according to the present invention and a substrate (preferably a substrate having conductivity) by bringing a surface (hereinafter, sometimes referred to as "1 st surface") of the photosensitive film opposite to the side where the temporary support is disposed into contact with the substrate.

In the bonding step, the photosensitive film is preferably brought into pressure contact with the substrate by bringing the 1 st surface of the photosensitive resin layer into contact with the substrate (the conductive layer in the case where the conductive layer is provided on the surface of the substrate). According to the above aspect, since the adhesion between the 1 st surface of the photosensitive resin layer and the substrate is improved, the formed resin pattern can be preferably used as a resist.

When the photosensitive film has a cover film, the cover film is removed from the photosensitive film, and then the photosensitive film is bonded to the substrate.

In the case where a layer other than the cover film (for example, a high refractive index layer and/or a low refractive index layer) is disposed on the 1 st surface of the photosensitive resin layer in the photosensitive film, the 1 st surface of the photosensitive resin layer and the substrate may be bonded to each other through the layer other than the cover film.

The method for pressing the photosensitive film against the substrate is not limited, and a known transfer method and lamination method can be used. The photosensitive film and the substrate are preferably bonded to each other by superposing the 1 st surface of the photosensitive resin layer on the substrate, and applying pressure and heat by using a method such as a roller. In addition, a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving productivity can be used for bonding.

[ base plate ]

The substrate is not limited, and a known substrate can be used. The substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a base and a conductive layer on a part or the entire surface of the base. The substrate may have any layer other than the conductive layer as necessary.

Examples of the substrate include glass, silicon, and a thin film.

The substrate is preferably transparent. In the present invention, "transparent" means that the wavelength is 400 to 700nm and the light transmittance is 80% or more.

The refractive index of the base material is preferably 1.50 to 1.52.

Examples of the transparent Glass substrate include strengthened Glass typified by Gorilla Glass (Gorilla Glass) produced by Corning Incorporated. Further, as the transparent glass substrate, for example, materials used in japanese patent application laid-open nos. 2010-86684, 2010-152809 and 2010-257492 can be used.

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

The substrate constituting the substrate used in the roll-to-roll method is preferably a film substrate. In the case of manufacturing circuit wiring for a touch panel by a roll-to-roll method, the base material is preferably a sheet-like resin composition.

Examples of the conductive layer include conductive layers used for general circuit wiring and touch panel wiring. From the viewpoint of conductivity and fine line formability, the conductive layer is preferably at least one selected from a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and particularly preferably a copper layer or a silver layer.

The substrate may have 1 conductive layer alone or 2 or more conductive layers. The substrate having 2 or more conductive layers preferably has a plurality of conductive layers of different materials.

Examples of the material of the conductive layer include a metal and a conductive metal oxide. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au. Examples of the conductive metal Oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . In the present invention, "conductivity" means that the volume resistivity is less than 1X 10 ⁶ Omega cm. The volume resistivity of the conductive metal oxide is preferably less than 1X 10 ⁴ Ωcm。

In the case of manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

The conductive layer is preferably an electrode pattern corresponding to a sensor of a viewing portion used in the electrostatic capacitance type touch panel or a wiring of a peripheral lead-out portion.

A preferred embodiment of the conductive layer is described, for example, in paragraph 0141 of international publication No. 2018/155193, which is incorporated herein by reference.

The substrate having a conductive layer is preferably a substrate having at least one of a transparent electrode and a wiring. The substrate described above can be preferably used as a substrate for a touch panel. The transparent electrode can suitably function as an electrode for a touch panel. The transparent electrode is preferably formed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), or a thin metal wire such as a metal mesh or a metal nanowire. Examples of the thin metal wires include silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

As a material of the routing wire, a metal is preferable. Examples of the metal as a material of the routing wire include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and an alloy containing 2 or more of these metal elements. The material of the routing wire is preferably copper, molybdenum, aluminum, or titanium, and particularly preferably copper.

Exposure Process

The method for producing a resin pattern according to the present invention preferably includes a step of pattern-exposing the photosensitive resin layer after the bonding step.

The detailed configuration and specific dimensions of the pattern in the pattern exposure are not limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wirings manufactured by a method for manufacturing circuit wirings and to reduce the area occupied by lead-out wirings, at least a part of the pattern (preferably, an electrode pattern of the touch panel and/or a part of the lead-out wirings) preferably includes a thin line having a width of 20 μm or less, and more preferably includes a thin line having a width of 10 μm or less.

The light source used for exposure may be any light source that irradiates light of a wavelength (for example, 365nm or 405nm) capable of exposing the photosensitive resin layer. Specific examples of the Light source include an ultra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

The exposure amount is preferably 5mJ/cm ² ～200mJ/cm ² More preferably 10mJ/cm ² ～100mJ/cm ² 。

In the exposure step, pattern exposure may be performed after the temporary support is peeled from the photosensitive resin layer, or the temporary support may be peeled after pattern exposure is performed through the temporary support. In order to prevent contamination of the photosensitive resin layer due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on exposure, it is preferable to perform pattern exposure through the temporary support. The pattern exposure may be exposure through a mask, or may be direct exposure using an exposure method such as laser light.

(developing Process)

The method for producing a resin pattern according to the present invention preferably includes a step of forming a resin pattern by developing the photosensitive resin layer after the exposure step.

The photosensitive resin layer can be developed using a developer. The type of the developing solution is not limited as long as it can remove an image portion (exposed portion) or a non-image portion (non-exposed portion) of the photosensitive resin layer. As the developer, a known developer (for example, a developer described in japanese patent application laid-open No. 5-72724) can be used.

The developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol/L. The developer may also contain a water-soluble organic solvent and/or a surfactant. As the developer, the developer described in paragraph 0194 of international publication No. 2015/093271 is also preferable.

The developing method is not particularly limited, and may be any of spin-on immersion development, shower and spin development, and immersion development. The shower development is a development treatment of spraying a developing solution onto the exposed photosensitive resin layer to remove an exposed portion or a non-exposed portion.

After the developing step, it is preferable to remove the development residue by spraying a cleaning agent while wiping with a brush.

The liquid temperature of the developing solution is not limited. The liquid temperature of the developing solution is preferably 20 to 40 ℃.

For example, in the case where the photosensitive film contains a thermoplastic resin and an intermediate layer, the thermoplastic resin and the intermediate layer are also removed together with an image portion (exposed portion) or a non-image portion (non-exposed portion) of the photosensitive resin layer in the developing step. In the developing step, the thermoplastic resin layer and the intermediate layer may be removed by dissolving or dispersing in a developer.

Etching Process

The method for manufacturing a circuit wiring according to the present invention preferably includes a step of etching the conductive layer located in a region where the resin pattern is not arranged in a laminate in which a base material, a conductive layer, and a resin pattern formed using the photosensitive film according to the present invention are sequentially laminated. The resin pattern is preferably a resin pattern formed by a method for producing a resin pattern including the bonding step, the exposure step, and the developing step.

In the etching step, the conductive layer is etched by using the resin pattern as a resist. As a method of the etching treatment, a known method can be applied. Examples of the etching treatment include a method described in paragraphs 0209 to 0210 of jp 2017 a-120435, a method described in paragraphs 0048 to 0054 of jp 2010 a-152155, a wet etching method in which the substrate is immersed in an etching solution, and a method based on dry etching (e.g., plasma etching).

The etching solution used in the wet etching method may be an acidic or alkaline etching solution appropriately selected according to the etching target.

Examples of the acidic etching solution include an aqueous solution containing an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components.

Examples of the alkaline etching solution include an aqueous solution containing an alkaline component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and organic amine salts (e.g., tetramethylammonium hydroxide), and a mixed aqueous solution of an alkaline component and a salt (e.g., potassium permanganate). The alkali component may be a combination of a plurality of alkali components.

Removal Process

The method of manufacturing a circuit wiring according to the present invention preferably includes a step of removing the remaining resin pattern (hereinafter, may be referred to as a "removal step"). The removal step is preferably performed after the etching step.

As a method of removing the residual resin pattern, for example, a method of removing the residual resin pattern by a chemical treatment may be mentioned. The method of removing the residual resin pattern is preferably a method of removing the residual resin pattern using a removing liquid. As a method of using the removing liquid, for example, a method of immersing the substrate having the residual resin pattern in the removing liquid while stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes can be mentioned.

Examples of the removing solution include a solution obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.

The method of removing the residual resin pattern using the removing liquid is not limited to the immersion method, and may be a known method other than the immersion method (for example, a spraying method, a shower method, and a spin-coating immersion method).

Other procedures

The method of manufacturing a circuit wiring according to the present invention may include any step other than the above-described step (hereinafter, may be referred to as "another step"). Examples of the exposure step, the development step, and other steps that can be applied to the method for manufacturing circuit wiring according to the present invention include the steps described in paragraphs 0035 to 0051 of japanese unexamined patent application publication No. 2006-23696. Further, as other steps, the following steps may be mentioned. However, the other steps are not limited to the steps described below.

[ Process for peeling off cover film ]

When the photosensitive film according to the present invention has a cover film, the method for producing a resin pattern according to the present invention preferably includes a step of peeling the cover film from the photosensitive film. The method for peeling the cover film is not limited, and a known method can be applied.

[ Process for reducing visible light reflectance ]

The method for manufacturing a circuit wiring according to the present invention may include a step of performing a treatment for reducing visible light reflectance of a part or all of the conductive layer in the substrate.

As a treatment for reducing the visible light reflectance of the conductive layer, for example, oxidation treatment can be given. When the conductive layer contains copper, the visible light reflectance of the conductive layer can be reduced by making copper into copper oxide by oxidation treatment and blackening the conductive layer.

The treatment for reducing the visible light reflectance of the conductive layer is described in paragraphs 0017 to 0025 of jp 2014-150118 a and paragraphs 0041, 0042, 0048 and 0058 of jp 2013-206315 a. The contents of these publications are incorporated by reference into this specification.

[ Process for Forming insulating film and Process for Forming New conductive layer on surface of insulating film ]

The method for manufacturing a circuit wiring according to the present invention preferably further includes a step of forming an insulating film on a surface of the circuit wiring and a step of forming a new conductive layer on a surface of the insulating film. Through the above process, 2 electrode patterns insulated by the insulating film can be formed.

The method of forming the insulating film is not limited. In the step of forming the insulating film, the insulating film may be formed by a method of forming a known permanent film, for example. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.

In the step of forming a new conductive layer on the insulating film, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity, for example.

In the method for manufacturing a circuit wiring according to the present invention, it is also preferable that a substrate having conductive layers on both surfaces of a base material is used, and a circuit is formed for each of the conductive layers sequentially or simultaneously. According to the above method, for example, a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a base material and a second conductive pattern is formed on the other surface of the base material can be formed. Further, according to the method for manufacturing circuit wiring according to the present invention, it is preferable that the circuit wiring for a touch panel is formed on both surfaces of the base material by a roll-to-roll method.

Use of Circuit Wiring

The circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention can be applied to various devices. Examples of the device including the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention include an input device, preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to various display devices (for example, an organic EL display device and a liquid crystal display device).

< method for manufacturing touch Panel >

The method for manufacturing a touch panel according to the present invention is not limited as long as it is a method for manufacturing a touch panel using the photosensitive film according to the present invention.

The method of manufacturing a touch panel according to the present invention preferably includes a step of forming wiring for a touch panel by etching the conductive layer located in a region where the resin pattern is not arranged in a laminate in which a base material, the conductive layer, and the resin pattern formed using the photosensitive film according to the present invention are sequentially laminated. The resin pattern is preferably a resin pattern formed by a method for manufacturing a resin pattern including the bonding step, the exposure step, and the development step.

The embodiments of the respective steps in the method for manufacturing a touch panel according to the present invention are the same as the preferred embodiments described in the above-mentioned section "method for manufacturing a resin pattern and method for manufacturing a circuit wiring". In the method for manufacturing a touch panel according to the present invention, a known method for manufacturing a touch panel can be used in addition to the method for forming the wiring for a touch panel. The method of manufacturing a touch panel according to the present invention may include any process other than the above-described process.

The pattern of the mask used in manufacturing the touch panel is explained with reference to fig. 3 and 4. Fig. 3 is a schematic diagram showing an example of a pattern of a mask for manufacturing a touch panel. Fig. 4 is a schematic diagram showing another example of the pattern of the touch panel manufacturing mask. In fig. 3 and 4, DL virtually represents an alignment frame, and G represents a non-image portion (light-shielding portion). In fig. 3, SL denotes a non-image portion (light-shielding portion). In the method for manufacturing a touch panel according to the present invention, for example, a touch panel in which circuit wirings having patterns corresponding to SL and G are formed can be manufactured by exposing the photosensitive resin layer to light through a mask having the pattern shown in fig. 3. Specifically, the touch panel can be manufactured by the method described in fig. 1 of international publication No. 2016/190405. In an example of the touch panel manufactured, G is a portion where a transparent electrode (i.e., a touch panel electrode) is formed, and SL is a portion where a wiring of the peripheral extraction portion is formed.

According to the method of manufacturing a touch panel of the present invention, a touch panel having at least touch panel wiring is manufactured. The touch panel preferably has a transparent substrate, an electrode, an insulating layer, or a protective layer.

Examples of a detection method in the touch panel include a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. The detection method is preferably an electrostatic capacitance method.

Examples of the Touch panel type include a so-called embedded type (for example, the structures described in fig. 5, 6, 7, and 8 of japanese patent laid-open No. 2012-517051), a so-called external embedded type (for example, the structure described in fig. 19 of japanese patent laid-open No. 2013-168125, and the structures described in fig. 1 and 5 of japanese patent laid-open No. 2012-89102), an OGS (One Glass Solution: single Glass Solution) type, a TOL (Touch-on-Lens: cover Touch) type (for example, the structure described in fig. 2 of japanese patent laid-open No. 2013-54727), various external hung types (for example, GG, G1-G2, GFF, GF2, 1, and G1F), and other structures (for example, the GF structure described in fig. 6 of japanese patent laid-open No. 2013-164871).

Examples

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

< abbreviation >

The abbreviations shown below refer to the following compounds, respectively.

"MAA": methacrylic acid (FUJIFILM Wako Pure Chemical Corporation)

"MMA": methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation)

"PGMEA": propylene glycol monomethyl ether acetate (SHOWA DENKO K.K.)

"St": styrene (FUJIFILM Wako Pure Chemical Corporation)

"V-601": 2, 2' -azobis (isobutyric acid) dimethyl (FUJIFILM Wako Pure Chemical Corporation, polymerization initiator)

< Polymer A-1 >

PGMEA (116.5 parts by mass) was charged into a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. While the liquid temperature in the three-necked flask was maintained at 90 ℃. + -. 2 ℃, a mixed solution containing St (52.0 parts by mass), MMA (19.0 parts by mass), MAA (29.0 parts by mass), V-601(4.0 parts by mass), and PGMEA (116.5 parts by mass) was added dropwise to the three-necked flask over 2 hours. After the completion of the dropwise addition, the mixed solution was stirred for 2 hours while maintaining the liquid temperature at 90 ℃. + -. 2 ℃ to obtain a composition containing 30.0 mass% of the polymer A-1. The acid value of the polymer A-1 was 189 mgKOH/g.

< polymerizable Compound B >

As the polymerizable compound B, the following compounds were prepared.

B-1: NK ester BPE-500(2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane, SHIN-NAKAMURA CHEMICAL CO, LTD.)

B-2: ARONIX M-270 (Polypropylene glycol diacrylate, TOAGOSEI CO., LTD.)

< photopolymerization initiator >

As the photopolymerization initiator, the following compounds were prepared.

C-1: B-CIM (photo radical polymerization initiator, 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, manufactured by Hampford corporation)

C-2: EAB-F (photo radical polymerization initiator (sensitizer), 4' -bis (diethylamino) benzophenone, Tokyo Chemical Industry Co., Ltd.)

< pigment >

As the dye, the following compounds were prepared.

D-1: LCV (leuco crystal violet, YAMADA CHEMICAL CO., LTD., pigment that develops color by free radicals)

< surfactant >

As the surfactant, the following compounds were prepared.

·E-1：Megafac F552(DIC Corporation)

< preparation of thermoplastic resin composition >

A thermoplastic resin composition was prepared by mixing the following ingredients.

Copolymer of benzyl methacrylate, methacrylic acid and acrylic acid (solid content concentration: 30.0% by mass, Mw: 30000, acid value: 153 mgKOH/g): 42.85 parts by mass

NK ester A-DCP (Dicidol diacrylate, SHIN-NAKAMURA CHEMICAL CO, LTD.): 4.63 parts by mass

8UX-015A (multifunctional urethane acrylate compound, TAISEI FINE CHEMICAL CO,. LTD.): 2.31 parts by mass

Aronium TO-2349 (multifunctional acrylate compound having carboxyl group, TOAGOSEI co., LTD.): 0.77 parts by mass

A compound having a structure shown below (photoacid generator, a compound synthesized by the method described in paragraph 0227 of jp 2013-47765 a): 0.32 part by mass

[ chemical formula 27]

A compound having a structure shown below (a dye that develops color by an acid): 0.08 parts by mass

[ chemical formula 28]

E-1: 0.03 parts by mass

Methyl ethyl ketone (SANKYO CHEMICAL co., LTD.): 39.50 parts by mass

PGMEA: 9.51 parts by mass

< preparation of composition for intermediate layer >

The following ingredients were mixed to prepare a composition for an intermediate layer.

Ion-exchanged water: 38.12 parts by mass

Methanol (mitsubashi GAS CHEMICAL COMPANY, INC.): 57.17 parts by mass

Kuraray Poval PVA-205 (polyvinyl alcohol, Kuraray co., LTD.): 3.22 parts by mass

Polyvinylpyrrolidone K-30(NIPPON shokubali co., LTD.): 1.49 parts by mass

Megafac F-444 (fluorine-based nonionic surfactant, DIC CORPORATION): 0.0015 part by mass

< preparation of photosensitive resin composition >

A photosensitive resin composition was prepared by mixing the following components.

Polymer A-1 (30.0% solids): 21.87 parts by mass

B-1: 4.85 parts by mass

B-2: 0.51 part by mass

C-1: 0.89 part by mass

C-2: 0.05 part by mass

D-1: 0.053 part by mass

E-1: 0.02 parts by mass

Phenothiazine (FUJIFILM Wako Pure Chemical Corporation): 0.025 parts by mass

1-phenyl-3-pyrazolone (FUJIFILM Wako Pure Chemical Corporation): 0.001 part by mass

Methyl ethyl ketone (SANKYO CHEMICAL co., LTD.): 30.87 parts by mass

PGMEA: 33.92 parts by mass

Tetrahydrofuran (THF, Mitsubishi Chemical Holdings Corporation): 6.93 parts by mass

< example 1 >

A PET film (Lumiror 16QS62, TORAY INDUSTRIES, INC., arithmetic average roughness (Ra value): 0.02 μm, thickness: 16 μm) was prepared as a temporary support. The width of the PET film was 1.54 m.

The surface of the temporary support was coated with the thermoplastic resin composition using a slit nozzle so that the coating width of the thermoplastic resin composition was 1.53m and the thickness after drying was 2.0 μm. The formed coating film of the thermoplastic resin composition was dried at 80 ℃ for 40 seconds, thereby forming a thermoplastic resin layer. At this time, the pressure in the decompression chamber was set to-200 Pa.

The surface of the formed thermoplastic resin layer was coated with the composition for an intermediate layer using a slit nozzle so that the coating width was 1.53m and the thickness after drying was 1.0 μm. The coating film of the intermediate layer composition was dried at 80 ℃ for 40 seconds to form an intermediate layer. At this time, the pressure of the decompression chamber was set to-1,000 Pa.

The surface of the formed intermediate layer was coated with the photosensitive resin composition using a slit nozzle so that the coating width was 1.53m and the thickness after drying was 2.0 μm. The photosensitive resin layer was formed by drying the coating film of the photosensitive resin composition at 80 ℃ for 40 seconds. At this time, the pressure in the decompression chamber was set to-500 Pa.

A PET film (Lumiror 16QS62, TORAY INDUSTRIES, INC., arithmetic average roughness (Ra value): 0.02 μm, thickness: 16 μm, width: 1.54m) was pressure-bonded as a cover film on the surface of the formed photosensitive resin layer to produce a photosensitive film. The photosensitive film thus produced was wound into a roll of 4,000 m. The average thickness of the photosensitive film measured in the above manner was 35.7. mu.m. The average thickness of each layer of the photosensitive film measured by the above method is shown below.

(average thickness of layers)

Average thickness of temporary support: 15.5 μm

Average thickness of thermoplastic resin layer: 2.1 μm

Average thickness of the intermediate layer: 1.0 μm

Average thickness of photosensitive resin layer: 2.0 μm

Average thickness of cover film: 15.2 μm

< example 2 >

A photosensitive film was produced by following the same procedure as in example 1, except that the pressure in the decompression chamber at the time of forming the photosensitive resin layer was changed to-1,000 Pa. The average thickness of the photosensitive film was 35.9. mu.m. The average thickness of each layer of the photosensitive film measured by the above method is shown below.

(average thickness of layers)

Average thickness of temporary support: 15.5 μm

Average thickness of thermoplastic resin layer: 2.1 μm

Average thickness of the intermediate layer: 1.0 μm

Average thickness of photosensitive resin layer: 2.1 μm

Average thickness of the cover film: 15.2 μm

< example 3 >

Photosensitive films were produced by the same procedure as in example 1 except that the widths of the PET films (Lumirror 16QS62, TORAY INDUSTRIES, inc., arithmetic average roughness (Ra value): 0.02 μm, thickness: 16 μm) used as the temporary support and the coverlay were changed to 0.53m, respectively, and the coating width of the thermoplastic resin composition, the coating width of the composition for the intermediate layer, and the coating width of the photosensitive resin composition were changed to 0.52m, respectively. The average thickness of the photosensitive film was 35.8. mu.m.

< example 4 >

A photosensitive film was produced by following the same procedure as in example 1 except that the width of the PET film (Lumiror 16QS62, TORAY INDUSTRIES, INC., arithmetic average roughness (Ra value): 0.02 μm, thickness: 16 μm) used as the temporary support and the cover film was changed to 0.25m, and the application width of the thermoplastic resin composition, the application width of the composition for an intermediate layer, and the application width of the photosensitive resin composition were changed to 0.24m, respectively. The average thickness of the photosensitive film was 35.8. mu.m.

< example 5 >

A photosensitive film was produced in the same manner as in example 1 except that the PET film (Lumiror 16QS62, TORAY INDUSTRIES, INC., arithmetic average roughness (Ra value): 0.02 μm, thickness: 16 μm) of the temporary support was changed to PET film B (Lumiror 12QS62, TORAY INDUSTRIES, INC., arithmetic average roughness (Ra value): 0.03 μm, thickness: 12 μm). The average thickness of the photosensitive film was 32.5. mu.m. The average thickness of each layer of the photosensitive film measured by the above method is shown below.

(average thickness of layers)

Average thickness of temporary support: 12.0 μm

Average thickness of thermoplastic resin layer: 2.0 μm

Average thickness of the intermediate layer: 1.0 μm

Average thickness of photosensitive resin layer: 2.1 μm

Average thickness of the cover film: 15.5 μm

< example 6 >

A photosensitive film was produced by the same procedure as in example 1, except that the thickness of the photosensitive resin layer was changed to 10.0 μm. The average thickness of the photosensitive film was 44.2. mu.m. The average thickness of each layer of the photosensitive film measured by the above method is shown below.

(average thickness of layers)

Average thickness of temporary support: 15.5 μm

Average thickness of thermoplastic resin layer: 2.0 μm

Average thickness of the intermediate layer: 1.0 μm

Average thickness of photosensitive resin layer: 10.0 μm

Average thickness of the cover film: 15.7 μm

< example 7 >

A photosensitive film was produced by the same procedure as in example 1 except that a photosensitive resin layer was formed by applying a photosensitive resin composition as a temporary support to the surface of a PET film B (Lumiror 12QS62, TORAY INDUSTRIES, INC., arithmetic average roughness (Ra value): 0.03 μm, thickness: 12 μm) without forming a thermoplastic resin layer and an intermediate layer, and the thickness of the photosensitive resin layer was changed to 1.1 μm. The average thickness of the photosensitive film was 28.7. mu.m. The average thickness of each layer of the photosensitive film measured by the above method is shown below.

(average thickness of layers)

Average thickness of temporary support: 12.1 μm

Average thickness of photosensitive resin layer: 1.1 μm

Average thickness of the cover film: 15.5 μm

< comparative example 1 >

A photosensitive film was produced by the same procedure as in example 1, except that the pressure in the decompression chamber at the time of forming the photosensitive resin layer was changed to atmospheric pressure (that is, the photosensitive resin composition was not sucked). The average thickness of the photosensitive film was 35.8. mu.m. The average thickness of each layer of the photosensitive film measured by the above method is shown below.

(average thickness of layers)

Average thickness of temporary support: 15.5 μm

Average thickness of thermoplastic resin layer: 2.0 μm

Average thickness of the intermediate layer: 1.0 μm

Average thickness of photosensitive resin layer: 2.1 μm

Average thickness of the cover film: 15.2 μm

< comparative example 2 >

A photosensitive film was produced by the same procedure as in example 1, except that the pressure in the decompression chamber at the time of forming the photosensitive resin layer, the thermoplastic resin layer, and the intermediate layer was changed to the atmospheric pressure (that is, the photosensitive resin composition and the thermoplastic resin composition were not sucked). The average thickness of the photosensitive film was 35.8. mu.m. The average thickness of each layer of the photosensitive film measured by the above method is shown below.

(average thickness of layers)

Average thickness of temporary support: 15.4 μm

Average thickness of thermoplastic resin layer: 2.0 μm

Average thickness of the intermediate layer: 1.0 μm

Average thickness of photosensitive resin layer: 2.1 μm

Average thickness of cover film: 15.3 μm

< evaluation of thickness distribution >

The thickness of the photosensitive film at 48 points was measured by the above-described method using a contact film thickness meter (TOKYO SEIMITSU CO., LTD., E-ST-100), and it was confirmed whether or not the relationship of Tg (x) x (98.8/100) < T (x) < Tg (x) × (101.2/100) was satisfied at each measurement position. In the photosensitive film, the thickness distribution of the photosensitive film was evaluated by obtaining the ratio of the measurement sites satisfying the above-described relationship. The evaluation results are shown in table 1.

< evaluation of appearance >

The photosensitive film wound in a roll was visually observed to evaluate the presence or absence of appearance defects in the photosensitive film. The specific evaluation items were winding displacement and deformation. The evaluation results are shown in table 1.

[ Table 1]

In Table 1, the numerical values in the column entitled "evaluation of thickness distribution" indicate the proportion of measurement sites satisfying the relationship Tg (x) × (98.8/100) < T (x) < Tg (x) × (101.2/100).

The results shown in table 1 show that the appearance defects in examples 1 to 7 were suppressed as compared with those in comparative examples 1 to 2.

Example 1 and example 2 also satisfy the relationship of Tg (x) x (99.2/100) < T (x) < Tg (x) x (100.8/100). Specifically, in example 1 and example 2, the proportion satisfying the above relationship is 100%.

In the evaluation of the thickness distribution, the thickness (t (x)) of the photosensitive film of comparative example 1 measured at 48 is shown in fig. 5, 6 and 7, respectively. FIG. 5 is a graph showing the thickness distribution at the leading end portion of the photosensitive film of comparative example 1. FIG. 6 is a graph showing the thickness distribution at the center of the photosensitive film of comparative example 1. FIG. 7 is a graph showing the thickness distribution at the rear end portion of the photosensitive film of comparative example 1. In fig. 5, 6, and 7, the horizontal axis represents the distance (x) from one end of the photosensitive film in the width direction of the photosensitive film to the measurement position of the film thickness, and the vertical axis represents the thickness (t (x)) of the photosensitive film. In fig. 5, 6, and 7, the symbols indicated by black triangles represent measured values. In fig. 5, 6, and 7, the 2 curves indicated by the dotted line respectively indicate "tg (x) x (98.8/100)" and "tg (x) x (101.2/100)".

< preparation of photosensitive resin composition >

With reference to example 1, photosensitive resin compositions A-1 to A-10 having the compositions shown in the following tables were prepared, respectively. In addition, the numerical values in the ingredient columns in the following tables represent parts by mass.

[ Table 2]

(Compound B)

The structure of compound B is shown below.

[ chemical formula 29]

(Compound C)

The structure of compound C is shown below.

[ chemical formula 30]

(preparation of P-1 solution)

As the P-1 solution, a 36.3 mass% solution (solvent: propylene glycol monomethyl ether acetate) of a polymer P-1 having the following structure as a solid content was used. The polymer P-1 is an alkali-soluble resin. In the polymer P-1, the numerical values below the right of each structural unit indicate the content ratio (mol%) of each structural unit. A P-1 solution was prepared by the following polymerization step and addition step.

Polymerization procedure

Into a 2000mL flask, propylene glycol monomethyl ether acetate (trade name PGM-Ac manufactured by SANWA KAGAKU SANGYO co., ltd.) (60g) and propylene glycol monomethyl ether (trade name PGM manufactured by SANWA KAGAKU SANGYO co., ltd.) (240g) were introduced. The temperature of the resulting liquid was raised to 90 ℃ while stirring at a stirring speed of 250rpm (revolutions per minute; the same applies hereinafter).

As a preparation of the dropping liquid (1), methacrylic acid (trade name acrylate M, manufactured by MITSUBISHI RAYON co., ltd.) (107.1g), methyl methacrylate (trade name MMA, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, inc.) (5.46g), and cyclohexyl methacrylate (trade name CHMA, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, inc.) (231.42g) were mixed and diluted with PGM-Ac (60g), thereby obtaining the dropping liquid (1).

As the preparation of the dropping liquid (2), dimethyl 2, 2' -azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation, trade name V-601) (9.637g) was dissolved with PGM-Ac (136.56g), to thereby obtain the dropping liquid (2).

The dropping solution (1) and the dropping solution (2) were simultaneously dropped into the above 2000mL flask (specifically, 2000mL flask containing a liquid heated to 90 ℃ C.) over 3 hours.

Next, the vessel of the dropping solution (1) was washed with PGM-Ac (12g), and the washing solution was dropped into the above 2000mL flask. Next, the vessel of the dropping solution (2) was washed with PGM-Ac (6g), and the washing solution was dropped into the above 2000mL flask. In these dropwise addition, the reaction solution in the 2000mL flask was stirred at a stirring speed of 250rpm while maintaining the temperature at 90 ℃. Further, as a post-reaction, stirring was carried out at 90 ℃ for 1 hour.

V-601(2.401g) was added as an initiator to be added to the reaction solution after the subsequent reaction for the first time. The vessel of V-601 was cleaned with PGM-Ac (6g), and a cleaning solution was introduced into the reaction solution. Then, it was stirred at 90 ℃ for 1 hour.

Next, V-601(2.401g) was added to the reaction mixture as a second additional initiator addition. The vessel of V-601 was cleaned with PGM-Ac (6g), and a cleaning solution was introduced into the reaction solution. Then, it was stirred at 90 ℃ for 1 hour.

Next, V-601(2.401g) was added to the reaction mixture as a third additional initiator addition. The vessel of V-601 was cleaned with PGM-Ac (6g), and a cleaning solution was introduced into the reaction solution. Then, it was stirred at 90 ℃ for 3 hours.

-an addition procedure-

After stirring at 90 ℃ for 3 hours, PGM-Ac (178.66g) was introduced into the reaction mixture. Next, tetraethylammonium bromide (manufactured by FUJIFILM Wako Pure Chemical Corporation) (1.8g) and hydroquinone monomethyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation) (0.8g) were added to the reaction solution. Each vessel was washed with PGM-Ac (6g), and a washing solution was introduced into the reaction solution. Then, the temperature of the reaction solution was raised to 100 ℃.

Next, glycidyl methacrylate (manufactured by NOF CORPORATION, trade name BLEMMER G) (76.03G) was added dropwise to the reaction solution over 1 hour. The container of BLEMMERG was washed with PGM-Ac (6G), and a washing solution was introduced into the reaction mixture. Then, the mixture was stirred at 100 ℃ for 6 hours as an addition reaction.

Subsequently, the reaction solution was cooled and filtered through a mesh filter for removing garbage (100 mesh) to obtain a solution of polymer P-1 (1158g) (solid content concentration: 36.3 mass%). The weight-average molecular weight of the resulting polymer P-1 was 27000, the number-average molecular weight was 15000, and the acid value was 95 mgKOH/g. The structure of the polymer P-1 is shown below. Wherein the molar ratio of the repeating units is 51.5:2:26.5:20 in order from the left repeating unit.

[ chemical formula 31]

(preparation of P-2 solution)

A36.5 mass% solution of the solid content of the polymer P-2 was prepared as a P-2 solution in accordance with the following method. The polymer P-2 is an alkali-soluble resin. 82.4g of propylene glycol monomethyl ether was charged into the flask and heated to 90 ℃ under a nitrogen stream. To this liquid, a solution obtained by dissolving 38.4g of styrene, 30.1g of dicyclopentyl methacrylate, and 34.0g of methacrylic acid in 20g of propylene glycol monomethyl ether, and a solution obtained by dissolving 5.4g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 43.6g of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 3 hours. After completion of the dropwise addition, 0.75g of V-601 was added 3 times at intervals of 1 hour. After which the reaction was continued for 3 hours. Then, the mixture was diluted with 58.4g of propylene glycol monomethyl ether acetate and 11.7g of propylene glycol monomethyl ether. The reaction mixture was heated to 100 ℃ under an air stream, and 0.53g of tetraethylammonium bromide and 0.26g of p-methoxyphenol were added. To this, 25.5g of glycidyl methacrylate (manufactured by NOF CORPORATION, BLEMMER GH) was added dropwise over 20 minutes. This was reacted at 100 ℃ for 7 hours to obtain a solution of polymer P-2. The solid content concentration of the obtained solution was 36.5 mass%. With respect to the polymer P-2, the weight average molecular weight in terms of standard polystyrene in GPC was 17000, the dispersity was 2.4, and the acid value was 95 mgKOH/g. The amount of the residual monomer was less than 0.1% by mass as measured by gas chromatography relative to the solid content of the polymer P-2 in any of the monomers. The structure of the polymer P-2 is shown below. Wherein the molar ratio of the repeating units is 41.0:15.2:23.9:19.9 in order from the left repeating unit.

[ chemical formula 32]

(preparation of P-3 solution)

A36.2 mass% solid content solution of the polymer P-3 was prepared as a P-3 solution in accordance with the following method. The polymer P-3 is an alkali-soluble resin. 113.5g of propylene glycol monomethyl ether was charged into a flask, and heated to 90 ℃ under a nitrogen stream. To this liquid, a solution obtained by dissolving 172g of styrene, 4.7g of methyl methacrylate and 112.1g of methacrylic acid in 30g of propylene glycol monomethyl ether and a solution obtained by dissolving 27.6g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 57.7g of propylene glycol monomethyl ether were simultaneously added dropwise over 3 hours. After completion of the dropwise addition, 2.5g of V-601 was added 3 times at intervals of 1 hour. After which the reaction was continued for 3 hours. Then, the mixture was diluted with 160.7g of propylene glycol monomethyl ether acetate and 233.3g of propylene glycol monomethyl ether. The reaction mixture was heated to 100 ℃ under an air stream, and 1.8g of tetraethylammonium bromide and 0.86g of p-methoxyphenol were added. To this was added dropwise 71.9G of glycidyl methacrylate (manufactured by NOF CORPORATION, BLEMMER G) over 20 minutes. This was reacted at 100 ℃ for 7 hours to obtain a solution of polymer P-3. The solid content concentration of the obtained solution was 36.2%. With respect to the polymer P-3, the weight average molecular weight in terms of standard polystyrene in GPC was 18000, the degree of dispersion was 2.3, and the acid value was 124 mgKOH/g. The amount of the residual monomer was less than 0.1% by mass as measured by gas chromatography relative to the solid content of the polymer P-3 in any of the monomers. The structure of the polymer P-3 is shown below. Wherein the molar ratio of the repeating units is 55.1:26.5:1.6:16.8 in order from the left repeating unit.

[ chemical formula 33]

(preparation of P-4 solution)

In the synthesis of the polymer P-3, a 36.2 mass% solution of the solid content of the polymer P-4 (solvent: propylene glycol monomethyl ether acetate) was prepared as a P-4 solution by changing the kind and amount of the monomers. The polymer P-4 is an alkali-soluble resin. The Mw of the resulting polymer P-4 was 18000, dispersity was 2.3, and acid value was 124 mgKOH/g. The structure of the polymer P-4 is shown below. The molar ratio of the repeating units in the formula is 55.1:24.6:1.6:17.0:1.7 in order from the left-hand repeating unit.

[ chemical formula 34]

< preparation of composition for Forming refractive index adjustment layer >

Subsequently, compositions B-1 to B-4 for forming a refractive index adjustment layer, each having a composition described in the following table, were prepared. The numerical values in the following table represent "parts by mass".

[ Table 3]

(Polymer A)

Polymer a in the table above was synthesized as follows.

1-methoxypropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0g) was introduced into a 1L three-necked flask, and the temperature was raised to 70 ℃ under a nitrogen stream with stirring. On the other hand, allyl methacrylate (45.6g) (manufactured by FUJIFILM Wako Pure Chemical Corporation) and methacrylic acid (14.4g) (manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved in 1-methoxypropanol (manufactured by Tokyo Chemical Industry co., ltd.) (270.0g), and V-65 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was further dissolved in 3.94g to prepare a dropping solution, and the dropping solution was dropped into the flask over 2.5 hours. The reaction was maintained under stirring for 2.0 hours as it was.

Then, the temperature was returned to room temperature, and the mixture was added dropwise to stirred ion-exchanged water (2.7L) to carry out reprecipitation to obtain a turbid solution. The turbid solution was filtered by introducing it through a suction filter with filter paper, and the filtrate was washed with ion-exchanged water to obtain a wet powder. After drying at 45 ℃ with air blowing, the amount was confirmed to be constant, and polymer a was obtained as a powder in a yield of 70%.

The ratio of methacrylic acid/allyl methacrylate of the obtained polymer a was 76 mass%/24 mass%. The weight average molecular weight Mw was 38000.

< production of photosensitive films 1 to 16 >

On a temporary support of a polyethylene terephthalate film (lumiror 16KS40, manufactured by TORAY INDUSTRIES, inc.) having a thickness of 16 μm, a photosensitive resin layer was formed by applying any one of the photosensitive resin compositions a-1 to a-10 described in the following table, using a slit nozzle, while adjusting the application amount so that the film thickness after drying becomes the application amount having the thickness described in the following table.

After the solvent was volatilized in a drying zone at 100 ℃, any of the compositions B-1 to B-4 for forming a refractive index adjustment layer was used in combination according to the following table by using a slit nozzle, and the coating amount was adjusted so that the film thickness after drying became the film thickness described in the following table, and the composition was coated on the photosensitive resin layer, and then dried at a drying temperature of 80 ℃ to form a refractive index adjustment layer. A protective film (lumiror 16KS40, manufactured by TORAY INDUSTRIES, inc.) was pressure-bonded to the refractive index adjustment layer, and photosensitive films 1 to 16 were produced.

[ Table 4]

< evaluation of thickness distribution >

The thickness of the photosensitive film at 48 points was measured by the above-described method using a contact film thickness meter (TOKYO SEIMITSU CO., LTD., E-ST-100), and it was confirmed whether or not the relationship of Tg (x) x (98.8/100) < T (x) < Tg (x) × (101.2/100) was satisfied at each measurement position. In the photosensitive film, the thickness distribution of the photosensitive film was evaluated by obtaining the ratio of the measurement sites satisfying the above relationship. The evaluation results are shown in table 5.

< evaluation of appearance >

The photosensitive film wound in a roll was visually observed to evaluate whether or not the photosensitive film had an appearance defect. Specific evaluation items were winding displacement and deformation. The evaluation results are shown in table 5.

[ Table 5]

In Table 5, the numerical values in the column entitled "evaluation of thickness distribution" indicate the proportion of measurement sites satisfying the relationship Tg (x) × (98.8/100) < T (x) < Tg (x) × (101.2/100). The thickness distributions of examples 8 to 23 were all 90% or more, and no winding displacement or deformation was observed.

The inventions of Japanese patent application No. 2020-. All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Description of the symbols

10-temporary support, 12: photosensitive resin layer, 14-cover film, 100-photosensitive film, DL-alignment frame, G-non-image portion (light-shielding portion), SL-non-image portion (light-shielding portion), T (x) -film thickness, Tg (x) -target value of film thickness, Ta-average value of film thickness measured in film width direction, W-film width, x-distance from one end of film in film width direction to film thickness measurement position.

Claims

1. A photosensitive film, in the width of the film is W expressed by millimeter, from the film width direction of the film end to the film thickness measuring position of x expressed by millimeter, in the film width direction of the film thickness measuring average value is represented by millimeter Ta, expressed by the following expression of film thickness target value is expressed by millimeter Tg (x), and in the film width direction of the film end to the x position of T (x), expressed by millimeter T (x), satisfying the relationship of (Tg x) (98.8/100) < T (x) < Tg (x) < X) (101.2/100) ratio of 90% -100%,

2. the photosensitive film according to claim 1, which has an average thickness of 5 to 55 μm.

3. The photosensitive film according to claim 1 or 2, which has a length of 500m or more.

4. The photosensitive film according to any one of claims 1 to 3, which is in the form of a roll.

5. The photosensitive film according to any one of claims 1 to 4, which comprises a temporary support and a photosensitive resin layer.

6. The photosensitive film according to any one of claims 1 to 4, which comprises a temporary support, a photosensitive resin layer and a cover film in this order.

7. The photosensitive film according to claim 5 or 6,

the temporary support has an average thickness of 5 to 20 [ mu ] m.

8. The photosensitive film according to any one of claims 5 to 7, wherein,

the temporary support has an arithmetic average roughness Ra of 0.05 [ mu ] m or less on the surface of the temporary support on which the photosensitive resin layer is disposed.

9. The photosensitive film according to any one of claims 5 to 8, wherein,

the average thickness of the photosensitive resin layer is 0.1-15 μm.

10. The photosensitive film according to claim 6,

the average thickness of the covering film is 10-20 mu m.

11. The photosensitive film according to claim 6 or 10,

the cover film has an arithmetic average roughness Ra of 0.1 [ mu ] m or less on the surface of the cover film on which the photosensitive resin layer is disposed.

12. A method for producing a photosensitive film,

in the photosensitive film, when W expressed by millimeter is used as the width of the film, x expressed by millimeter is used as the distance from one end of the film in the film width direction to the measuring position of the film thickness, Ta expressed by millimeter is used as the average value of the film thickness measured in the film width direction, Tg (x) expressed by millimeter is used as the target value of the film thickness expressed by the following formula, and T (x) expressed by millimeter is used as the thickness of the film measured from one end of the film in the film width direction to the x position, the proportion of the relation of (Tg x) x (98.8/100) < T (x) < Tg (x) × (101.2/100) is 90-100%,