WO2021161965A1 - Film photosensible et procédé de fabrication associé - Google Patents

Film photosensible et procédé de fabrication associé Download PDF

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Publication number
WO2021161965A1
WO2021161965A1 PCT/JP2021/004621 JP2021004621W WO2021161965A1 WO 2021161965 A1 WO2021161965 A1 WO 2021161965A1 JP 2021004621 W JP2021004621 W JP 2021004621W WO 2021161965 A1 WO2021161965 A1 WO 2021161965A1
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WIPO (PCT)
Prior art keywords
mass
film
compound
meth
resin layer
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PCT/JP2021/004621
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English (en)
Japanese (ja)
Inventor
洋行 海鉾
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN202180013363.7A priority Critical patent/CN115087927A/zh
Priority to JP2022500405A priority patent/JP7332780B2/ja
Publication of WO2021161965A1 publication Critical patent/WO2021161965A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present disclosure relates to a photosensitive film and a method for producing a photosensitive film.
  • a display device for example, an organic electroluminescence display device and a liquid crystal display device
  • a touch panel for example, a capacitance type input device
  • the patterned conductive layer include an electrode pattern corresponding to a sensor in the visual recognition portion and wiring (for example, peripheral wiring and take-out wiring).
  • a photosensitive resin layer is provided on a substrate using a photosensitive transfer material, and then a photosensitive resin layer is provided.
  • a method of exposing the photosensitive resin layer through a mask having a desired pattern and then developing the photosensitive resin layer is widely adopted (for example, Patent Document 1).
  • photosensitive films Most of the film-shaped photosensitive transfer materials (hereinafter referred to as "photosensitive films”) are wound into rolls in order to facilitate transportation or transfer to the next process.
  • a so-called roll-to-roll method is used in which the photosensitive film is pulled out from the roll and bonded to, for example, another roll-shaped substrate.
  • poor appearance may be observed in the photosensitive film wound in a roll shape. Examples of the poor appearance include winding misalignment and deformation.
  • the “winding deviation” means a state in which a part of the photosensitive film is displaced in the photosensitive film wound in a roll shape. Examples of the deformation include wrinkles.
  • the occurrence of the above-mentioned poor appearance affects the quality of the final product such as poor web handling and transfer defects.
  • One aspect of the present disclosure is to provide a photosensitive film that suppresses winding deviation and deformation when winding a photosensitive film.
  • Another aspect of the present disclosure is an object of the present invention to provide a method for producing a photosensitive film that suppresses winding deviation and deformation when winding a photosensitive film.
  • the present disclosure includes the following aspects. ⁇ 1> W in millimeters for the width of the film, x in millimeters for the distance from one end of the film in the width direction of the film to the measurement position of the thickness of the film, and the thickness of the film measured in the width direction of the film. Measured at Ta in millimeters, Tg (x) in millimeters for the target value of film thickness represented by the following formula, and x at one end of the film in the width direction of the film.
  • T (x) expressed in millimeters
  • ⁇ 2> The photosensitive film according to ⁇ 1>, which has an average thickness of 5 ⁇ m to 55 ⁇ m.
  • ⁇ 3> The photosensitive film according to ⁇ 1> or ⁇ 2>, which has a length of 500 m or more.
  • ⁇ 4> The photosensitive film according to any one of ⁇ 1> to ⁇ 3>, which has a roll-like shape.
  • ⁇ 5> The photosensitive film according to any one of ⁇ 1> to ⁇ 4>, which comprises 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 ⁇ m to 20 ⁇ m.
  • ⁇ 8> The photosensitive according to any one of ⁇ 5> to ⁇ 7>, wherein the arithmetic average roughness Ra of the surface of the temporary support on the side on which the photosensitive resin layer is arranged is 0.05 ⁇ 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 ⁇ m to 15 ⁇ m.
  • ⁇ 10> The photosensitive film according to ⁇ 6>, wherein the average thickness of the cover film is 10 ⁇ m to 20 ⁇ m.
  • T (x) expressed in millimeters
  • a photosensitive film that suppresses winding deviation and deformation when winding the photosensitive film.
  • a method for producing a photosensitive film that suppresses winding deviation and deformation when winding the photosensitive film.
  • FIG. 1 is a conceptual diagram for explaining the relationship between Tg (x) and T (x).
  • FIG. 2 is a schematic view showing an example of the configuration of the photosensitive film.
  • FIG. 3 is a schematic view showing an example of a pattern of a mask for manufacturing a touch panel.
  • FIG. 4 is a schematic view showing another example of the pattern of the touch panel manufacturing mask.
  • FIG. 5 is a graph showing the thickness distribution of the tip portion of the photosensitive film of Comparative Example 1.
  • FIG. 6 is a graph showing the thickness distribution of the central portion 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.
  • the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. ..
  • process is included in the term “process” as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes. ..
  • the groups (atomic groups) not described as substituted and unsubstituted include a group having no substituent and a group having a substituent.
  • the notation "alkyl group” includes not only an alkyl group having no substituent (ie, an unsubstituted alkyl group) but also an alkyl group having a substituent (ie, a substituted alkyl group).
  • (meth) acrylic acid means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid.
  • the "(meth) acryloyl group” means both an acryloyl group, a methacryloyl group, or an acryloyl group, and a methacryloyl group.
  • (meth) acrylate means acrylate, methacrylate, or both acrylate and methacrylate.
  • alkali-soluble means the property that the solubility of sodium carbonate in an aqueous solution (100 g, sodium carbonate concentration: 1% by mass) is 0.1 g or more at a liquid temperature of 22 ° C.
  • the chemical structural formula may be described by a structural formula in which a hydrogen atom is omitted.
  • exposure includes not only exposure using light but also drawing using particle beams (for example, electron beam and ion beam) unless otherwise specified.
  • the light used for exposure include active rays (also referred to as active energy rays).
  • active light beam include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV (Extreme ultraviolet lithium) light), and X-rays.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are "TSKgel GMHxL”, “TSKgel G4000HxL”, and “TSKgel G2000HxL” (all products manufactured by Toso Co., Ltd.) unless otherwise specified. It is a molecular weight converted by detecting a compound in THF (tetrahexyl) with a differential refractometer by a gel permeation chromatography (GPC) analyzer using a column of (name) and using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • solid content means a component obtained by removing a solvent from all the components of an object.
  • the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.
  • the photosensitive film according to the present disclosure has W in millimeters for the width of the film, x in millimeters for the distance from one end of the film in the width direction of the film to the measurement position of the thickness of the film, in the width direction of the film. From Ta, which is the average value of the measured film thickness in millimeters, Tg (x), which is the target value of the film thickness expressed by the following formula in millimeters, and one end of the film in the width direction of the film.
  • T (x) When the thickness of the film measured at the position of x is T (x) expressed in millimeters, Tg (x) ⁇ (98.8/100) ⁇ T (x) ⁇ Tg (x) ⁇ ( The ratio satisfying the relationship of 101.2 / 100) is 90% to 100%. According to the above-mentioned photosensitive film according to the present disclosure, the occurrence of winding deviation and deformation when winding the photosensitive film is suppressed.
  • FIG. 1 is a conceptual diagram for explaining 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 width direction of the film to the measurement position of the film thickness. W on the horizontal axis corresponds to the width of the film (ie, the distance from one end of the film to the other).
  • the vertical axis in FIG. 1 represents the film thickness T (x).
  • the graph of the target value Tg (x) of the film thickness represented by the above formula draws an upwardly convex curve (that is, a parabola).
  • Tg (x) The intersection of the graph of Tg (x) and the vertical axis is the average value Ta of the film thickness measured in the width direction of the film. Similar to Tg (x), the graph representing "Tg (x) x (98.8 / 100)" and the graph representing "Tg (x) x (101.2 / 100)" are on the top, respectively. Draw a convex curve. That is, in FIG. 1, T (x) is between the graph representing "Tg (x) x (98.8 / 100)” and the graph representing "Tg (x) x (101.2 / 100)".
  • the ratio of satisfying the relationship of Tg (x) ⁇ (98.8/100) ⁇ T (x) ⁇ Tg (x) ⁇ (101.2 / 100) is determined by the following procedure. calculate. (1) In each of the three longitudinal regions of the photosensitive film (that is, the front end portion, the center portion, and the rear end portion), the thickness of the photosensitive film (T (T)) is along the width direction of the photosensitive film. x)) is measured at 16 equally spaced locations. That is, the thickness (T (x)) of the photosensitive film is measured at a total of 48 locations.
  • the "tip portion” is a region from the tip of the photosensitive film in the longitudinal direction of the photosensitive film to 5% of the total length of the photosensitive film.
  • the "tip of the photosensitive film” is photosensitive in the process of pulling out the photosensitive film wound into a roll.
  • the "central portion” is a region from the center of the photosensitive film in the longitudinal direction of the photosensitive film to ⁇ 2.5% of the total length of the photosensitive film.
  • the “rear end portion” is a region from the rear end of the photosensitive film in the longitudinal direction of the photosensitive film to 5% of the total length of the photosensitive film.
  • the "rear end of the photosensitive film” corresponds to the end point (the end point of the drawing) of the photosensitive film in the process of pulling out the photosensitive film wound in a roll shape. ..
  • the tip of the roll manufactured immediately before is substantially the rear end of the roll to be measured when the film is continuously formed into a roll shape, so that the measurement target is to be measured. As the rear end portion of the roll, the tip portion of the previously manufactured roll may be substituted.
  • the longitudinal direction of the photosensitive film cannot be specified, one of the two directions along the surface of the photosensitive film and orthogonal to each other is set to the longitudinal direction and the other is set to the width direction.
  • the width (W) of the photosensitive film is measured in each of the above three regions.
  • 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.
  • the ratio of satisfying the relationship of Tg (x) ⁇ (98.8/100) ⁇ T (x) ⁇ Tg (x) ⁇ (101.2 / 100) is 92% to 100. %, More preferably 95% or more to 100%, further preferably 97% to 100%, and particularly preferably 100%.
  • the ratio satisfying the above relationship is within the above range, the occurrence of poor appearance can be further suppressed.
  • the photosensitive film according to the present disclosure has Tg (x) ⁇ (99.0/100) ⁇ T (x) ⁇ Tg (x) ⁇ (101.0 / 100) from the viewpoint of further suppressing the occurrence of appearance defects. It is preferable to satisfy the relationship of Tg (x) ⁇ (99.2 / 100) ⁇ T (x) ⁇ Tg (x) ⁇ (100.8 / 100).
  • the ratio satisfying the above relationship is the relationship of Tg (x) ⁇ (98.8 / 100) ⁇ T (x) ⁇ Tg (x) ⁇ (101.2 / 100) described above. It is the same as the ratio that satisfies.
  • the components of the photosensitive film according to the present disclosure satisfy the relationship of Tg (x) ⁇ (98.8/100) ⁇ T (x) ⁇ Tg (x) ⁇ (101.2 / 100) in the photosensitive film. As long as the proportion is 90% to 100%, there is no limitation.
  • the photosensitive film preferably includes a temporary support and a photosensitive resin layer.
  • the photosensitive resin layer may be laminated on the temporary support directly or via an arbitrary layer.
  • an arbitrary layer may be laminated on the surface of the photosensitive resin layer opposite to the side on which the temporary support is arranged. Examples of the optional layer in the photosensitive film include a cover film and other layers described later.
  • the photosensitive film preferably includes a temporary support, a photosensitive resin layer, and a cover film in this order.
  • the photosensitive resin layer may be laminated on the temporary support directly or via an arbitrary layer.
  • the cover film may be laminated on the photosensitive resin layer directly or via an arbitrary layer. Examples of the arbitrary layer in the photosensitive film include other layers described later.
  • FIG. 2 is a schematic view showing an example of the configuration of the 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, the temporary support 10, the photosensitive resin layer 12, and the cover film 14 are laminated in this order.
  • the components of the photosensitive film according to the present disclosure will be specifically described.
  • the components of the photosensitive film according to the present disclosure are not limited to the components shown below.
  • the photosensitive film according to the present disclosure preferably has a temporary support.
  • the temporary support is a support that can be peeled off from the photosensitive film.
  • the temporary support can support the photosensitive resin layer.
  • the temporary support preferably has light transmission. Since the temporary support has light transmission property, when the photosensitive resin layer is exposed, the photosensitive resin layer can be exposed through the temporary support.
  • “having light transmittance” means that the transmittance of light having a wavelength used for pattern exposure is 50% or more.
  • the transmittance of light having a wavelength (preferably a wavelength of 365 nm) used for pattern exposure is preferably 60% or more, preferably 70% or more, from the viewpoint of improving the exposure sensitivity of the photosensitive resin layer. More preferably.
  • the "transmittance" refers to a layer to be measured with respect to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer to be measured (that is, in the thickness direction). It is the ratio of the intensity of the emitted light that has passed through and emitted.
  • the transmittance is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • the haze of the temporary support is small.
  • the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and further 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 transmission.
  • the resin film examples include polyethylene terephthalate film (that is, PET film), cellulose triacetate film, polystyrene film, and polycarbonate film.
  • the resin film is preferably a PET film, 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, for example, according to the strength of the temporary support, the light transmittance, the material, and the flexibility required for bonding the photosensitive film and the substrate.
  • the average thickness of the temporary support is preferably 5 ⁇ m to 100 ⁇ m. Further, the average thickness of the temporary support is preferably 5 ⁇ m to 50 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m, and further preferably 10 ⁇ m to 20 ⁇ m from the viewpoint of ease of handling and versatility. It is particularly preferably 10 ⁇ m to 16 ⁇ m.
  • 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 scanning electron microscope (SEM) is used to observe the cross section in the direction perpendicular to the main surface of the photosensitive film (that is, the thickness direction). Based on the obtained observation image, the thickness of the target component is 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 ⁇ m, a biaxially stretched polyethylene terephthalate film having a film thickness of 12 ⁇ m, and a biaxially stretched polyethylene terephthalate film having a film thickness of 9 ⁇ m.
  • the arithmetic mean roughness Ra of the surface of the temporary support on which the photosensitive resin layer is arranged is preferably 0.1 ⁇ m or less. , 0.05 ⁇ m or less, and particularly preferably 0.02 ⁇ m or less.
  • the lower limit of the arithmetic mean roughness Ra is not limited.
  • the arithmetic mean roughness Ra of the surface of the temporary support on the side on which the photosensitive resin layer is arranged may be determined, for example, in the range of 0 ⁇ m or more.
  • Arithmetic mean roughness Ra is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), the surface profile of the object to be measured is obtained under the following conditions. As the measurement and analysis software, Microscope Application of MetroPro ver8.3.2 is used. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean 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 another layer, the arithmetic mean roughness Ra of the surface of the exposed object to be measured may be measured by peeling the object to be measured from the other layer. ..
  • the temporary support (particularly the resin film) is free from, for example, deformation (for example, wrinkles), scratches, and defects. From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, defects, and precipitates contained in the temporary support is small.
  • the number of fine particles, foreign substances, and defects having a diameter of 1 ⁇ m or more is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, and 3 pieces / It is more preferably 10 mm 2 or less, and particularly preferably 0/10 mm 2.
  • the temporary support may have a single-layer structure or a multi-layer structure.
  • a layer containing fine particles also referred to as “lubricant layer” may be provided on the surface of the temporary support.
  • the lubricant layer may be provided on one side of the temporary support, or may be provided on both sides of the temporary support.
  • the diameter of the particles contained in the lubricant layer is preferably 0.05 ⁇ m to 0.8 ⁇ m.
  • the thickness of the lubricant layer is preferably 0.05 ⁇ m to 1.0 ⁇ m.
  • the photosensitive film according to the present disclosure preferably has a photosensitive resin layer.
  • the photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developing solution is reduced by exposure and the non-exposed portion is removed by development.
  • the photosensitive resin layer is not limited to the negative photosensitive resin layer, and even if the photosensitive resin layer is a positive photosensitive resin layer in which the solubility of the exposed portion in the developing solution is improved by exposure and the exposed portion is removed by development. good.
  • the photosensitive resin layer preferably contains a polymer A, a polymerizable compound B, and a photopolymerization initiator.
  • the photosensitive resin layer comprises 10% by mass to 90% by mass of the polymer A, 5% by mass to 70% by mass of the polymerizable compound B, and 0, based on the total mass of the photosensitive resin layer. It is preferable to contain 0.01% by mass to 20% by mass of a photopolymerization initiator.
  • the polymer A, the polymerizable compound B, and the photopolymerization initiator will be described later.
  • the photosensitive resin layer preferably contains the polymer A.
  • the polymer A is preferably an alkali-soluble polymer.
  • Alkali-soluble polymers include polymers that are easily soluble in alkaline substances.
  • the acid value of the polymer A is preferably 220 mgKOH / g or less, and more preferably less than 200 mgKOH / g, from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer due to the developing solution. It is preferably less than 190 mgKOH / g, especially preferably less than 190 mgKOH / g.
  • the lower limit of acid value is not limited.
  • the acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and 170 mgKOH / g or more, from the viewpoint of more excellent developability. It is particularly preferable that it is g or more.
  • the acid value of the polymer A can be adjusted, for example, by the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.
  • the acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample.
  • the unit of 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. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolvability and the developability.
  • the weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.
  • the weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
  • the edge fuse property refers to the degree to which the photosensitive resin layer easily protrudes from the end face of the roll when the photosensitive film is wound into a roll.
  • the cut chip property refers to the degree of ease with which the chip flies when the unexposed film is cut with a cutter. For example, when the chip adheres to the surface of the photosensitive film, the chip is transferred to the mask in the exposure process, which causes a defective product.
  • the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0.0 to 3.0.
  • the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the polymer A preferably has a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of resolution.
  • aromatic hydrocarbon group examples include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
  • the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of the polymer A. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more.
  • the upper limit of the content ratio of the structural unit 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, preferably 85% by mass or less, based on the total mass of the polymer A. Is more preferable.
  • the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.
  • the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-). Vinyl benzoic acid, styrene dimer, and styrene trimmer).
  • the monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.
  • aralkyl group examples 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) acrylate having a benzyl group (for example, benzyl (meth) acrylate and chlorobenzyl (meth) acrylate), a vinyl monomer having a benzyl group (for example, vinylbenzyl chloride, and vinylbenzyl chloride). Vinyl benzyl alcohol).
  • the monomer having a benzyl group is preferably a benzyl (meth) acrylate.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from benzyl (meth) acrylate
  • the benzyl (meth) acrylate single amount in the polymer A is used.
  • the content ratio of the structural unit derived from the body is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and 70% by mass, based on the total mass of the polymer A. It is more preferably% to 90% by mass, and particularly preferably 75% by mass to 90% by mass.
  • the content ratio of the structural unit derived from styrene in the polymer A is determined. It is preferably 20% by mass to 50% by mass, more preferably 25 to 45% by mass, further preferably 30% by mass to 40% by mass, and 30% by mass, based on the total mass of the polymer A. It is particularly preferably from mass% to 35% by mass.
  • the photosensitive resin layer contains a plurality of types 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 includes a monomer having an aromatic hydrocarbon group, a first monomer described later, and a second simpler described later. It is preferably a copolymer obtained by polymerizing at least one selected from the group consisting of monomers.
  • 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 the monomer having an aromatic hydrocarbon group is at least one kind of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later. It is preferable that the polymer is obtained by polymerizing the above, and at least one of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later and the second simpler described later. More preferably, it is a copolymer obtained by polymerizing at least one kind of a polymer (excluding a monomer having an aromatic hydrocarbon group).
  • the polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and is preferably the same as at least one of the first monomers described below. It is more preferable that the copolymer is obtained by polymerizing with at least one of the second monomers described later.
  • the first monomer is a monomer having a carboxy group in the molecule.
  • the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester.
  • 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% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of the polymer A. Is more preferable, and 15% by mass to 30% by mass is particularly preferable.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • the second monomer include a (meth) acrylate compound, an ester compound of vinyl alcohol, and (meth) acrylonitrile.
  • (meth) acrylonitrile includes both acrylonitrile, methacrylonitrile, or 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, and isobutyl (meth) acrylate.
  • Examples thereof include tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • ester compound of vinyl alcohol examples include vinyl acetate.
  • 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 is preferably methyl (meth). More preferably, it is an acrylate.
  • the content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, and 15% by mass to 50% by mass, based on the total mass of the polymer A. Is more preferable, and 20% by mass to 45% by mass is particularly preferable.
  • the polymer A is composed of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of resolution. It is preferable to include at least one selected from the group.
  • the polymer A is a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, a structural unit derived from styrene, a structural unit derived from methacrylic acid, and methyl. It is preferably at least one selected from the group consisting of copolymers containing a structural unit derived from methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.
  • the polymer A contains 25% by mass to 40% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 20% by mass or more of a structural unit derived from a first monomer. It is preferably a polymer containing 35% by mass and 30% by mass to 45% by mass of a structural unit derived from the second monomer.
  • the polymer A contains 70% by mass to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% by mass of a structural unit derived from a first monomer. It is preferably a polymer containing up to 25% by mass.
  • the glass transition temperature (Tg) of the polymer A is preferably 30 ° C to 135 ° C.
  • Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the Tg of the polymer A is 30 ° C. or higher from the viewpoint of improving the edge fuse resistance.
  • the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. preferable.
  • the polymer A may be a commercially available product or a synthetic product.
  • Polymer A is synthesized, for example, by diluting at least one of the above-mentioned monomers with a solvent (for example, acetone, methyl ethyl ketone, or isopropanol) and a radical polymerization initiator (for example, benzoyl peroxide or azoisobuty). Butyronitrile) is preferably added in an appropriate amount, and then heated and stirred. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
  • a solvent may be further added to adjust the concentration to a desired level.
  • the synthesis means bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
  • the photosensitive resin layer may contain one type alone or two or more types of polymer A.
  • the photosensitive resin layer contains two or more kinds of polymers A
  • the photosensitive resin layer contains two or more kinds of polymers A having a structural unit derived from a monomer having an aromatic hydrocarbon group.
  • it may contain 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.
  • the content ratio of the polymer A having a structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total mass of the polymer A. It is more preferably mass% or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the content ratio of the polymer A is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and 40% by mass to the total mass of the photosensitive resin layer. It is particularly preferably 60% by mass. It is preferable that the content ratio of the polymer A to the photosensitive resin layer is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content ratio of the polymer A to the photosensitive resin layer is 10% by mass or more from the viewpoint of improving the edge fuse resistance.
  • the polymer A may have any of a linear structure, a branched structure, and an alicyclic structure in the side chain.
  • a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the 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.
  • the monomer containing a group having a branched structure in the side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and ( Isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate. And so on.
  • isopropyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl methacrylate are preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.
  • the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group.
  • (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned. More specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth).
  • (meth) acrylic acid esters (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid -2-adamantyl, fentyl (meth) acrylate, 1-mentyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferred, cyclohexyl (meth) acrylate, (nor) bornyl, (meth) acrylate, More preferred are isobornyl (meth) acrylate, -2-adamantyl (meth) acrylate, or tricyclodecane (meth) acrylate.
  • the photosensitive resin layer preferably contains a polymerizable compound B having a polymerizable group.
  • the "polymerizable compound” means a compound that polymerizes under 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 involved in the polymerization reaction.
  • Examples of the polymerizable group in the polymerizable compound B include a group containing an ethylenically unsaturated bond (for example, a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group), and a group having a cationically polymerizable group. (For example, an epoxy group and an oxetane group) can be mentioned.
  • the polymerizable group is preferably a group containing an ethylenically unsaturated bond (hereinafter, may be referred to as an "ethylenically unsaturated group”), and more preferably an acryloyl group or a metaacryloyl group.
  • the polymerizable compound B is preferably a compound having one or more ethylenically unsaturated groups in one molecule (that is, an ethylenically unsaturated compound) in that the photosensitive resin layer is more photosensitive. More preferably, it is a compound having two or more ethylenically unsaturated groups in one molecule (ie, a polyfunctional ethylenically unsaturated compound).
  • the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, and preferably 3 or less, in terms of being excellent in resolution and peelability. It is more preferable, and it is particularly preferable that the number is two or less.
  • the ethylenically unsaturated compound is preferably a (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule.
  • the polymerizable compound B is a compound having two ethylenically unsaturated groups in one molecule (that is, bifunctional ethylenically) from the viewpoint of having a better balance of photosensitivity, resolution, and peelability in the photosensitive resin layer. It is preferably at least one selected from the group consisting of unsaturated compounds) and compounds having three ethylenically unsaturated groups in one molecule (that is, trifunctional ethylenically unsaturated compounds), preferably in one molecule. More preferably, it is a compound having two ethylenically unsaturated groups.
  • the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is preferably 60% by mass or more from the viewpoint of excellent peelability of the photosensitive resin layer. It is more preferably more than 70% by mass, and particularly preferably 90% by mass or more.
  • the upper limit of the content ratio of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is not limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.
  • the photosensitive resin layer preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups in one molecule.
  • the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.
  • the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, preferably 50% by mass or more, from the viewpoint of better resolution. More preferably, it is more 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.
  • the ratio 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, and 90% by mass or less from the viewpoint of peelability. Is more preferable, and 85% by mass or less is particularly preferable.
  • Examples of the aromatic ring in the polymerizable compound B1 include an aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, and an anthracene ring), an aromatic heterocycle (for example, a thiophene ring, a furan ring, a pyrrole ring, and an imidazole ring. Triazole ring and pyridine ring), and fused rings thereof.
  • the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer due to the developing solution.
  • the bisphenol structure include a bisphenol A structure derived from bisphenol A (that is, 2,2-bis (4-hydroxyphenyl) propane) and bisphenol F (that is, 2,2-bis (4-hydroxyphenyl) methane).
  • Examples include a bisphenol F structure derived from bisphenol B and a bisphenol B structure derived from bisphenol B (that is, 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 a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may be directly attached to the bisphenol structure. Each polymerizable group may be attached to the bisphenol structure via one 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 alkyleneoxy groups added to the bisphenol structure is not limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14.
  • the polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162. The contents of the above gazette are incorporated herein by reference.
  • the polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. ..
  • Examples of 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.). Company), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, Shin-Nakamura Chemical Industry Co., Ltd.) , 2,2-Bis (4- (methacryloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane ( BPE-1300, Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, Shin-Nakamura
  • Examples of the polymerizable compound B1 include a compound represented by the following general formula (I).
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group
  • A represents C 2 H 4
  • B represents C 3 H 6
  • n. 1 and n 3 are independently integers from 1 to 39
  • n 1 + n 3 are integers from 2 to 40
  • n 2 and n 4 are independent integers from 0 to 29, respectively.
  • N 2 + n 4 is an integer of 0 to 30, and the sequence of repeating units of-(AO)-and-(BO)-is random or block. good.
  • ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
  • n 2 + n 4 is 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.
  • n 1 + n 2 + n 3 + n 4 is 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 one type alone or two or more types of polymerizable compound B1.
  • the content ratio of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, preferably 20% by mass or more, based on the total mass of the photosensitive resin layer from the viewpoint of better resolution. Is more preferable.
  • the upper limit of the content ratio of the polymerizable compound B1 is not limited.
  • the content ratio of the polymerizable compound B1 in the photosensitive resin layer is preferably 70% by mass or less, preferably 60% by mass, based on the total mass of the photosensitive resin layer from the viewpoint of transferability and edge fuse resistance. It is more preferable that it is as follows.
  • the photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1.
  • the polymerizable compound B other than the polymerizable compound B1 include a monofunctional ethylenically unsaturated compound (that is, a compound having one ethylenically unsaturated group in one molecule) and a bifunctional ethylenically having no aromatic ring.
  • Unsaturated compounds ie, compounds that do not have an aromatic ring in one molecule and have two ethylenically unsaturated groups
  • trifunctional or higher functional ethylenically unsaturated compounds ie, in one molecule. Compounds having 3 or more ethylenically unsaturated groups).
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
  • bifunctional ethylenically unsaturated compound having no aromatic ring examples include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
  • alkylene glycol di (meth) acrylate examples include tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Industry Co., Ltd.), and the like.
  • 1,9-Nonandiol diacrylate (A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Industry Co., Ltd.), Ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
  • polyalkylene glycol di (meth) acrylate examples 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 Industry Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Industry Co., Ltd.).
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and alkylene oxide modified products thereof.
  • (tri / tetra / penta / hexa) (meth) acrylate is a concept that includes tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. be.
  • (tri / tetra) (meth) acrylate” is a concept including tri (meth) acrylate and tetra (meth) acrylate.
  • alkylene oxide-modified product of the trifunctional or higher-functional ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) and Shin-Nakamura Chemical Industry Co., Ltd. A-9300-1CL), alkylene oxide-modified (meth) acrylate compound (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Shin-Nakamura Chemical Industry Co., Ltd.
  • Examples of the polymerizable compound B other than the polymerizable compound B1 include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.
  • the photosensitive resin layer preferably contains a polymerizable compound B1 and a trifunctional or higher functional ethylenically unsaturated compound, preferably the polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. More preferably, it contains a compound.
  • the mass ratio of the polymerizable compound B1 to the trifunctional or higher functional ethylenically unsaturated compound is In certain embodiments, it is preferably 1: 1 to 5: 1, more preferably 1.2: 1 to 4: 1, and particularly preferably 1.5: 1 to 3: 1.
  • the photosensitive resin layer preferably contains a polymerizable compound B1 and two or more trifunctional ethylenically unsaturated compounds.
  • the molecular weight of the polymerizable compound B (when the polymerizable compound B has a molecular weight distribution, it means the weight average molecular weight (Mw)) is preferably 200 to 3,000, and preferably 280 to 2,200. Is more preferable, and 300 to 2,200 is particularly preferable.
  • the photosensitive resin layer may contain one type alone or two or more types of polymerizable compound B.
  • the content ratio of the polymerizable compound B in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, based on the total mass of the photosensitive resin layer. It is preferably 20% by mass to 50% by mass, and particularly preferably 20% by mass.
  • the value of the ratio Mm / Mb of the content Mm of the ethylenically unsaturated compound and the content Mb of the polymer A in the photosensitive resin layer is 1.0 or less from the viewpoint of resolution and linearity. It is 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 resolvability.
  • the ethylenically unsaturated compound in the photosensitive resin layer contains a (meth) acrylic compound from the viewpoint of curability, resolution and linearity, and the total mass of the (meth) acrylic compound contained in the photosensitive resin layer.
  • the content ratio of the acrylic compound with respect to the amount of the acrylic compound is more preferably 60% by mass or less.
  • the photosensitive resin layer may contain components other than the above-mentioned components (hereinafter, may be referred to as “arbitrary components”).
  • Optional components include photopolymerization initiators, dyes, surfactants, and additives other than the above components.
  • the photosensitive resin layer preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is a compound that receives active light (for example, ultraviolet rays, visible light, and X-rays) to initiate polymerization of a polymerizable compound (for example, polymerizable compound B).
  • the photopolymerization initiator is not limited, and a known photopolymerization initiator can be used.
  • Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
  • the photosensitive resin layer is a 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed parts, visibility of non-exposed parts, and resolution. And at least one selected from the group consisting of derivatives of 2,4,5-triarylimidazole dimer.
  • the two 2,4,5-triarylimidazole dimers and their derivatives may have the same or different structures.
  • Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- Examples thereof include (p-methoxyphenyl) -4,5-diphenylimidazole dimer.
  • photoradical polymerization initiator examples include the polymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783A.
  • photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
  • DBE ethyl dimethylaminobenzoate
  • benzoin methyl ether examples include benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
  • photoradical polymerization initiators include, for example, TAZ-110 (Midori Chemical Co., Ltd.), TAZ-111 (Midori Chemical Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-Tetraphenyl-1,2'-biimidazole (Tokyo Kasei Kogyo Co., Ltd.), 1- [4- (Phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) ( Product name: IRGACURE (registered trademark) OXE-01, BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (Product name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (
  • Oxym ester-based photopolymerization initiator (trade name: Lunar 6, DKSH Japan Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole (2-) (2-Chlorophenyl) -4,5-diphenylimidazole dimer) (trade name: B-CIM, Hampton), and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name:) BCTB, Tokyo Kasei Kogyo Co., Ltd.).
  • a photocationic polymerization initiator (that is, a photoacid generator) is a compound that generates an acid by receiving active light.
  • a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm and generates an acid is preferable.
  • the chemical structure of the photocationic polymerization initiator is not limited.
  • a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
  • the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid having a pKa of 4 or less, and more preferably a photocationic polymerization initiator that generates an acid having a pKa of 3 or less.
  • a photocationic polymerization initiator that generates 2 or less acids is particularly preferable.
  • the lower limit of pKa is not limited.
  • the pKa of the acid generated from the photocationic polymerization initiator is preferably -10.0 or more, for example.
  • photocationic polymerization initiator examples include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • ionic photocationic polymerization initiator examples include onium salt compounds (for example, diaryliodonium salt compounds and triarylsulfonium salt compounds), and quaternary ammonium salt compounds.
  • Examples of the ionic photocationic polymerization initiator include the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149.
  • examples of the oxime sulfonate compound examples include the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.
  • the photosensitive resin layer preferably contains a photoradical polymerization initiator, and is selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives of 2,4,5-triarylimidazole dimers. It is more preferable to contain at least one of these.
  • the photosensitive resin layer may contain one type alone or two or more types of photopolymerization initiators.
  • 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, based on the total mass of the photosensitive resin layer. It is particularly preferably 1.0% by mass or more.
  • 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, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer has a maximum absorption wavelength of 450 nm in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, pattern visibility after development, and resolution. It is preferable to include a dye (hereinafter, may be referred to as "dye N") whose maximum absorption wavelength is changed by an acid, a base, or a radical. Although the detailed mechanism is unknown, the inclusion of the dye N in the photosensitive resin layer improves the adhesion to the layers adjacent to the photosensitive resin layer (for example, the temporary support and the intermediate layer), and the resolution is improved. Better in sex.
  • the term "maximum absorption wavelength changes depending on an acid, base, or radical" used with respect to a dye means a mode in which a dye in a color-developing state is decolorized by an acid, base, or radical, or a decolorized state. It may mean any aspect of a mode in which the dye in the above color is developed by an acid, a base or a radical, and a mode in which the dye in a color-developing state changes to a color-developing state of another hue.
  • the dye N may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize.
  • the dye N may be a dye whose color development or decolorization state is changed by the action of an acid, a base, or a radical generated by exposure.
  • the dye N may be a dye whose color development or decolorization state changes due to a change in the state (for example, pH) in the photosensitive resin layer due to an acid, a base, or a radical generated by exposure. good.
  • the dye N may be a dye whose color development or decolorization state changes by directly receiving an acid, a base, or a radical as a stimulus without exposure.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of an exposed portion, visibility of a non-exposed portion, and resolution, and the maximum absorption wavelength is changed by a radical. It is more preferable that the pigment is a radical.
  • the photosensitive resin layer contains both a dye whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator as the dye N from the viewpoints of visibility of the exposed part, visibility of the non-exposed part, and resolution. It is preferable to include it.
  • the dye N is preferably a dye that develops color with an acid, a base, or a radical from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion.
  • photoradical polymerization is carried out by exposing a photosensitive resin layer containing a photoradical polymerization initiator, a photocationic polymerization initiator (that is, a photoacid generator), or a photobase generator.
  • a photoradical polymerization initiator that is, a photoacid generator
  • a photobase generator that is, a photoacid generator
  • a mode in which a radical-reactive dye, an acid-reactive dye, or a base-reactive dye for example, leuco dye
  • a radical-reactive dye, an acid-reactive dye, or a base-reactive dye for example, leuco dye
  • the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development is preferably 550 nm or more, preferably 550 nm to 700 nm, from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. More preferably, it is particularly preferably 550 to 650 nm.
  • the dye N may have one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development.
  • the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the transmission spectrum of a solution containing dye N (liquid temperature 25 ° C.) is measured in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, Shimadzu Corporation) in an atmospheric atmosphere. Then, the measurement is performed by detecting the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength).
  • Examples of the dye that develops or decolorizes by exposure include leuco compounds.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
  • the dye N is preferably a leuco compound from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion.
  • the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • triarylmethane dye a leuco compound having a triarylmethane skeleton
  • spiropylan dye a leuco compound having a spiropylan skeleton
  • fluorane dye fluorane dye
  • diarylmethane skeleton examples include a diarylmethane skeleton having a diarylmethane skeleton.
  • leuco compound (diarylmethane dye) having a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indrill phthalide dye), and a leuco auramine skeleton.
  • Leuco compounds (leuco auramine dyes) can be mentioned.
  • the leuco compound is preferably a triarylmethane dye or a fluorane dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion.
  • a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator By reacting the lactone ring, sultin ring, or sulton ring contained in the leuco compound with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, the leuco compound is changed to a closed ring state.
  • the color can be decolorized, or the radical compound can be changed to a ring-opened state to develop a color.
  • the leuco compound is preferably a compound having a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color. It is more preferable that the compound has, and the lactone ring is opened by a radical or an acid to develop a color.
  • leuco compounds include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malakite green lactone, benzoyl leucomethylene blue, 2 -(N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6- Methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6
  • dye N examples include dyes. Specific examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl.
  • the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, pattern visibility after development, and resolution, and color is developed by radicals. It is more preferable that the pigment is a radical.
  • the dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate.
  • the photosensitive resin layer may contain one kind alone or two or more kinds of dyes N.
  • the content ratio of the dye N is 0.1 mass with respect to the total mass of the photosensitive resin layer from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. % Or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 1% by mass. It is particularly preferable to have.
  • the content ratio of the dye N means the content ratio of the dye when all of the dye N contained in the photosensitive resin layer is in a colored state.
  • a method for quantifying the content ratio of the dye N will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added as a photoradical polymerization initiator to each of the obtained solutions, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • IRGACURE OXE-01 BASF
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation) to prepare a calibration curve.
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the photosensitive resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.
  • the photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.
  • nonionic surfactant examples include a polyoxyethylene higher alkyl ether compound, a polyoxyethylene higher alkylphenyl ether compound, a higher fatty acid diester compound of polyoxyethylene glycol, a silicone-based nonionic surfactant, and a fluorine-based nonionic property.
  • Surfactants can be mentioned.
  • the photosensitive resin layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. It is considered that the photosensitive resin layer contains a fluorine-based nonionic surfactant to suppress the penetration of the etching solution into the photosensitive resin layer and reduce the side etching.
  • Commercially available products of the fluorine-based nonionic surfactant include, for example, Megafvck (registered trademark) F-551, F-552 (DIC Corporation), and Megafvck F-554 (DIC Corporation).
  • a nonionic surfactant a fluorine-based surfactant or a silicone-based surfactant is preferable.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
  • fluorine-based surfactants include, for example, Megafuck (trade names) 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, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90 , R-94, RS-72-K, DS-21 (above, manufactured by DIC Corporation), Florard (trade name) FC430, FC431, FC17
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
  • fluorine-based surfactants include Megafuck (trade name) DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)).
  • Megafuck (trade name) DS-21 can be mentioned.
  • the fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a structural unit derived from an acrylate compound can also be preferably used.
  • fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Megafvck (trade name) RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like can be mentioned.
  • fluorine-based surfactant for example, a compound having a linear perfluoroalkyl group having 7 or more carbon atoms may be used.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctanesulfonic acid
  • silicone-based surfactant examples include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.
  • silicone-based surfactants include DOWNSIL (trade name) 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400.
  • surfactant examples include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362.
  • the surfactants described in paragraphs 0060 to 0071 of the publication are also mentioned.
  • the photosensitive resin layer may contain one type alone or two or more types of surfactants.
  • the content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer may contain a known additive in addition to the above components, if necessary.
  • the additive include a heat-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 one kind alone or two or more kinds of additives.
  • the photosensitive resin layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the heat-crosslinkable compound having an ethylenically unsaturated group which will be described later, is not treated as an ethylenically unsaturated compound, but is treated as a heat-crosslinkable compound.
  • the heat-crosslinkable compound include a methylol compound and a blocked isocyanate compound. Of these, a blocked isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the blocked isocyanate compound reacts with the hydroxy group and the carboxy group, for example, when the polymer A and / or the ethylenically unsaturated compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film The property is lowered, and the function when a film obtained by curing the photosensitive resin layer is used as a protective film tends to be enhanced.
  • the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 150 ° C.
  • the dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter".
  • DSC Different scanning calorimeter
  • a differential scanning calorimeter model: DSC6200 manufactured by Seiko Instruments Inc. can be preferably used.
  • the differential scanning calorimeter is not limited to this.
  • the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. examples include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.)] and oxime compounds.
  • the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. preferably contains, for example, an oxime compound from the viewpoint of storage stability.
  • the blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred material.
  • the blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurate-forming and protecting hexamethylene diisocyanate.
  • a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and has a smaller development residue. It is preferable from the viewpoint of ease.
  • the blocked isocyanate compound may have a polymerizable group.
  • the polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferable.
  • the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group and a styryl group, and a group having an epoxy group such as a glycidyl group.
  • an ethylenically unsaturated group is preferable
  • a (meth) acryloxy group is more preferable
  • an acryloxy group is further preferable.
  • blocked isocyanate compound a commercially available product can be used.
  • examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by Showa Denko KK), block type.
  • Duranate series for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.
  • the blocked isocyanate compound a compound having the following structure can also be used.
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. Is more preferable.
  • the photosensitive resin layer may contain a radical polymerization inhibitor.
  • the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784.
  • the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, or 4-methoxyphenol.
  • the radical polymerization inhibitor other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive resin layer.
  • the photosensitive resin layer may contain a benzotriazole compound.
  • the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include 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.
  • the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene.
  • Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole.
  • Examples of commercially available carboxybenzotriazole compounds include CBT-1 (Johoku Chemical Industry Co., Ltd.).
  • the ratio of the total content of the radical polymerization inhibitor, the benzotriazol compound, and the carboxybenzotriazol compound may be 0.01% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer. It is preferably 0.05% by mass to 1% by mass, more preferably. It is preferable that the ratio of the total content of each of the above components is 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin layer. On the other hand, it is preferable that the ratio of the total content of each of the above-mentioned components is 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.
  • the photosensitive resin layer may contain a sensitizer.
  • a sensitizer a known sensitizer can be used without limitation.
  • dyes and pigments can also be used as the sensitizer.
  • 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, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclysin compounds.
  • the photosensitive resin layer may contain one type alone or two or more types of sensitizers.
  • the content ratio of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer. It is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass with respect to 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.
  • a plasticizer and a heterocyclic compound include the compounds described in paragraphs 097 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.
  • Resins other than polymer A include acrylic resins, styrene-acrylic copolymers (however, limited to copolymers having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, and polyamide resins. Examples thereof include polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the photosensitive resin layer may contain a solvent.
  • the solvent may remain in the photosensitive resin layer. The solvent will be described later.
  • the photosensitive resin layer may contain, for example, metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorbers. , At least one selected from the group consisting of thickeners, cross-linking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors. Additives are described, for example, in paragraphs 0165 to 0184 of JP2014-85643A. The contents of the above gazette are incorporated herein by reference.
  • the photosensitive resin layer may contain a predetermined amount of impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and ions thereof.
  • halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.
  • the content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, still more preferably 2 ppm or less on a mass basis.
  • the content of impurities can be 1 ppb or more, or 0.1 ppm or more, on a mass basis.
  • Examples of the method for keeping impurities in the above range include selecting a composition having a low content of impurities as a raw material, preventing impurities from being mixed during the production of the photosensitive resin layer, and cleaning and removing the impurities. Be done. By such a method, the amount of impurities can be kept within the above range.
  • the impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the photosensitive resin layer should be low. Is preferable.
  • the content of these compounds with respect to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
  • the lower limit can be 10 ppb or more and 100 ppb or more with respect to the total mass of the photosensitive resin layer on a mass basis.
  • the content of these compounds can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.
  • the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and laminateability. ..
  • the photosensitive resin layer may contain a residual monomer corresponding to each structural unit of the polymer A described above.
  • the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less, based on the total mass of the polymer A. The following is more preferable.
  • the lower limit is not particularly limited, but 1 mass ppm or more is preferable, and 10 mass ppm or more is more preferable.
  • the residual monomer of each structural unit of the polymer A is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, based on the total mass of the photosensitive resin layer from the viewpoint of patterning property and reliability. , 100 mass ppm or less is more preferable.
  • 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 amount of residual monomer of the monomer when the polymer A is synthesized by the polymer reaction is also preferably in the above range.
  • the content of glycidyl acrylate is preferably in the above range.
  • the amount of residual monomer can be measured by a known method such as liquid chromatography and gas chromatography.
  • the average thickness of the photosensitive resin layer is generally 0.1 ⁇ m to 300 ⁇ m.
  • the average thickness of the photosensitive resin layer is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, further preferably 0.5 ⁇ m, and particularly preferably 1 ⁇ m or more.
  • the average thickness of the photosensitive resin layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably 15 ⁇ m or less, and particularly preferably 8 ⁇ m 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.
  • the average thickness of the photosensitive resin layer is preferably 0.1 ⁇ m to 15 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m, and even more preferably 0.5 ⁇ m to 4 ⁇ m. It is particularly preferably 0.5 ⁇ m to 3 ⁇ m.
  • the transmittance of light having a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more, from the viewpoint of being more excellent in adhesion. ..
  • the upper limit of transmittance is not limited.
  • the transmittance of light having a wavelength of 365 nm is preferably 99.9% or less.
  • the method for forming the photosensitive resin layer is not limited as long as it is a method capable of forming a layer containing the above components.
  • Examples of the method for forming the photosensitive resin layer include a method of applying the photosensitive resin composition to the surface of the temporary support and then drying the coating film of the photosensitive resin composition.
  • the photosensitive resin composition examples include a composition containing a polymer A, a polymerizable compound B, an optional component, and a solvent.
  • the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.
  • 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.
  • the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (for example, methanol and ethanol), a ketone solvent (for example, acetone and methyl ethyl ketone), and an aromatic hydrocarbon solvent (for example, toluene).
  • examples include aprotonic polar solvents (eg, N, N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.
  • 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 comprises 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. It is more preferable to include it. It is particularly preferable that the photosensitive resin composition 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.
  • alkylene glycol ether solvent examples 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. Be done.
  • alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
  • the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used. These contents are incorporated herein by reference.
  • the photosensitive resin composition may contain one kind of solvent alone or two or more kinds of solvents.
  • the content ratio of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is a part.
  • the method for preparing the photosensitive resin composition is not limited.
  • a method for preparing the photosensitive resin composition for example, a photosensitive resin composition is prepared by preparing a solution in which each component is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio. The method can be mentioned.
  • the photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 ⁇ m to 30 ⁇ m before forming the photosensitive resin layer.
  • the method for 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 the photosensitive resin composition on a cover film described later and drying it.
  • the photosensitive film according to the present disclosure preferably has a cover film (also referred to as a protective film).
  • a cover film also referred to as a protective film.
  • the surface of the layer (for example, the photosensitive resin layer) in contact with the cover film can be protected.
  • the photosensitive film it is more preferable that the photosensitive film has a cover film that is in contact with the surface of the photosensitive resin layer opposite to the side on which the temporary support is arranged.
  • cover film examples include a resin film and paper.
  • the cover film is preferably a resin film from the viewpoint of strength and flexibility.
  • the resin film examples include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and 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 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m, and particularly preferably 10 ⁇ m to 20 ⁇ m.
  • the arithmetic mean roughness Ra of the surface of the cover film on the side where the photosensitive resin layer is arranged is 0.3 ⁇ m because it is superior in resolution. It is preferably less than or equal to, more preferably 0.1 ⁇ m or less, and particularly preferably 0.05 ⁇ m or less.
  • the lower limit of the arithmetic mean roughness Ra is not limited.
  • the arithmetic average roughness Ra of the surface of the cover film on the side on which the photosensitive resin layer is arranged is preferably 0.001 ⁇ m or more.
  • the arithmetic average roughness Ra of the surface of the cover film on the side on which the photosensitive resin layer is arranged is measured by a method according to the method for measuring the arithmetic average roughness Ra described in the above section "Temporary Support”.
  • the cured film obtained by curing the photosensitive resin layer has a breaking elongation at 120 ° C. of 15% or more, and the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side is 50 nm. It is preferable that the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side is 150 nm or less.
  • the photosensitive film according to the present disclosure preferably satisfies the following formula (R1).
  • X ⁇ Y ⁇ 1,500 Equation (R1)
  • X represents the value (%) of the elongation at break at 120 ° C. of the cured film obtained by curing the photosensitive resin layer
  • Y represents the surface of the temporary support on the photosensitive resin layer side.
  • X ⁇ Y is more preferably 750 or less.
  • the breaking elongation at 120 ° C. is twice or more larger than the breaking elongation at 23 ° C. of the cured film obtained by curing the photosensitive resin layer.
  • the elongation at break was determined by exposing a photosensitive resin layer having a thickness of 20 ⁇ m to 120 mJ / cm 2 with an ultra-high pressure mercury lamp and curing it, and then further exposing it to 400 mJ / cm 2 with a high pressure mercury lamp and heating it at 145 ° C. for 30 minutes.
  • the later cured film is used and measured by a tensile test.
  • the photosensitive film according to the present disclosure preferably satisfies the following formula (R2).
  • Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive resin layer side
  • Z represents the value (nm) of the surface of the protective film on the photosensitive resin layer side. It represents the value (nm) of the arithmetic mean roughness Ra of the surface.
  • the photosensitive film according to the present disclosure may have a layer other than the above-mentioned layer (hereinafter, referred to as "another layer”).
  • the other layer include a thermoplastic resin, an intermediate layer, and a contrast enhancement layer (also referred to as a refractive index adjusting layer).
  • the photosensitive film according to the present disclosure may have a thermoplastic resin layer.
  • the photosensitive film preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Since the photosensitive film has a thermoplastic resin layer between the temporary support and the photosensitive resin layer, the followability to the substrate in the process of being bonded to the substrate is improved, and the space between the substrate and the photosensitive film is improved. This is because, as a result of suppressing the mixing of air bubbles, the adhesion between layers is improved.
  • thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
  • alkali-soluble resin examples include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
  • alkali-soluble resin examples include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, and polyhydroxystyrene resin.
  • examples thereof include polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
  • the alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion to a layer adjacent to the thermoplastic resin layer.
  • the "acrylic resin” is selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one kind.
  • the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the ratio of the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass.
  • the ratio of the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. %, More preferably 50% by mass to 100% by mass.
  • the alkali-soluble resin is preferably a polymer having an acid group.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferable.
  • the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
  • the upper limit of acid value is not limited.
  • the acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not limited, and can be appropriately selected from known resins and used.
  • Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716. Described in paragraphs 0033 to 0052 of Japanese Patent Application Laid-Open No. 2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and paragraphs 0053 to 0068 of JP-A-2016-224162.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be mentioned.
  • the content ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total mass of the carboxy group-containing acrylic resin. It is more preferable, and it is particularly preferable that it is 12% by mass to 30% by mass.
  • 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 to 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.
  • Reactive groups include, for example, ethylenically unsaturated groups, polycondensable groups (eg, hydroxy and carboxy groups), and polyaddition reactive groups (eg, epoxy groups and (blocking) isocyanate groups). Be done.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.
  • the thermoplastic resin layer may contain one type alone or two or more types of alkali-soluble resins.
  • the content ratio of the alkali-soluble resin is 10% by mass to 99% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. It is more preferably 20% by mass to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.
  • thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, and the maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter referred to as “dye B”). In some cases), it is preferable to include.
  • the preferred embodiment of the dye B is the same as the preferred embodiment of the dye N described above, except for the points described later.
  • the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of an exposed portion, visibility of a non-exposed portion, and resolution, and the maximum absorption wavelength is changed by an acid. It is more preferable that the pigment is a dye.
  • the thermoplastic layer includes a dye whose maximum absorption wavelength is changed by an acid as the dye B and a compound which generates an acid by light, which will be described later, from the viewpoints of visibility of the exposed part, visibility of the non-exposed part, and resolution. , Are preferably included.
  • the thermoplastic resin layer may contain one type alone or two or more types of dye B.
  • the content ratio of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. It is more preferably% to 6% by mass, further preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.
  • the content ratio of the dye B means the content ratio of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
  • a method for quantifying the content ratio of the dye B will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added as a photoradical polymerization initiator to each of the obtained solutions, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • IRGACURE OXE-01 BASF
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation) to prepare a calibration curve.
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
  • the thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, may be referred to as “Compound C”).
  • Compound C is preferably a compound that receives active light (for example, ultraviolet rays and visible light) to generate an acid, a base, or a radical.
  • Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators).
  • Compound C is preferably a photoacid generator.
  • thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution.
  • the photoacid generator include a photocationic polymerization initiator that may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiments are the same except for the points described below.
  • the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and has sensitivity, resolution and adhesion. From the viewpoint, it is more preferable to contain an oxime sulfonate compound.
  • the photoacid generator is a photoacid generator having the following structure.
  • the thermoplastic resin layer may contain a photobase generator.
  • the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, and bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane , N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6
  • the thermoplastic resin layer may contain a photoradical polymerization initiator.
  • the photoradical polymerization initiator include a photoradical polymerization initiator which may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiment is also the same.
  • the thermoplastic resin layer may contain one kind alone or two or more kinds of compound C.
  • the content ratio of the compound C is 0.1% by mass to 10% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion, the visibility of the non-exposed portion, and the resolution. It is preferable, and it is more preferable that it is 0.5% by mass to 5% by mass.
  • thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.
  • the molecular weight of the plasticizer (the molecular weight of the oligomer or polymer is the weight average molecular weight (Mw); the same applies hereinafter 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 develops plasticity by being compatible with an alkali-soluble resin. 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.
  • the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to the layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
  • thermoplastic resin layer and the photosensitive resin layer are arranged in direct contact with each other in the photosensitive film, it is preferable that the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth) acrylate compound. .. This is because the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
  • the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer
  • the (meth) acrylate compound may not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. preferable.
  • the (meth) acrylate compound used as a plasticizer is composed of two or more (meth) acrylate compounds in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to a thermoplastic resin layer, and developability. It is preferably a (meth) acrylate compound having a meta) acryloyl group.
  • the (meth) acrylate compound used as a plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.
  • thermoplastic resin layer may contain one type alone or two or more types of plasticizers.
  • the content ratio of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability. It is preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.
  • thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include a surfactant that may be contained in the above-mentioned photosensitive resin layer, and the preferred embodiment is also the same.
  • thermoplastic resin layer may contain one type alone or two or more types of surfactants.
  • the content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.
  • thermoplastic resin layer may contain a sensitizer.
  • the sensitizer include sensitizers that may be contained in the above-mentioned photosensitive resin layer.
  • thermoplastic resin layer may contain one type alone or two or more types of sensitizers.
  • the content ratio of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed part, and the visibility of the non-exposed part. %, More preferably 0.05% by mass to 1% by mass.
  • thermoplastic resin layer may contain known additives in addition to the above components, if necessary.
  • thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of the above gazette are incorporated herein by reference.
  • the thickness of the thermoplastic resin layer is not limited.
  • the average thickness of the thermoplastic resin layer is preferably 1 ⁇ m or more, and more preferably 2 ⁇ m or more, from the viewpoint of adhesion to 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 resolvability, the average thickness of the thermoplastic resin layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components.
  • the method for forming the thermoplastic resin layer include a method in which the thermoplastic resin composition is applied to the surface of the temporary support and the coating film of the thermoplastic resin composition is dried.
  • thermoplastic resin composition examples include a composition 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 is a solvent capable of dissolving or dispersing the components contained in the thermoplastic resin layer.
  • the solvent include a solvent that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.
  • thermoplastic resin composition may contain one kind of solvent alone or two or more kinds of solvents.
  • the content ratio of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. It is more preferable that it is a part.
  • 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 described above. For example, it is obtained after preparing a thermoplastic resin composition by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio.
  • the thermoplastic resin layer can be formed by applying the thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition. Further, after forming the photosensitive resin layer on the cover film, the thermoplastic resin layer may be formed on the surface of the photosensitive resin layer.
  • the photosensitive film according to the present disclosure preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. According to the intermediate layer, it is possible to suppress the mixing of components when forming a plurality of layers and during storage.
  • the intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.
  • the intermediate layer examples include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724. Since the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved.
  • the oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers.
  • the oxygen blocking layer used as the intermediate layer is preferably an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.).
  • the intermediate layer preferably contains a resin.
  • the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and copolymers thereof. Can be mentioned.
  • the resin contained in the intermediate layer is preferably a water-soluble resin.
  • the resin contained in the intermediate layer is either polymer A contained in the photosensitive resin layer or thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer from the viewpoint of suppressing mixing of components between a plurality of layers. It is preferable that the resin is different from the above.
  • the intermediate layer preferably contains polyvinyl alcohol, and preferably contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. Is more preferable.
  • the intermediate layer may contain one kind of resin alone or two or more kinds of resins.
  • the content ratio of the resin in the intermediate layer is 50% by mass with respect to the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. It is preferably ⁇ 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass. preferable.
  • the intermediate layer may contain an additive if necessary.
  • 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 ⁇ m to 5 ⁇ m, and more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the oxygen blocking property is not deteriorated, the mixing of the components at the time of forming a plurality of layers and at the time of storage can be suppressed, and the intermediate layer at the time of development can be suppressed. The increase in removal time can be suppressed.
  • the method of forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above components.
  • Examples of the method for forming the intermediate layer include 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.
  • composition for the intermediate layer examples include a composition containing a resin and an arbitrary additive.
  • the composition for the intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for the intermediate layer and facilitate the formation of the intermediate layer.
  • the solvent is not limited as long as it is a solvent that can dissolve or disperse the resin.
  • the solvent is preferably at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.
  • water-miscible organic solvent examples include alcohol, acetone, ethylene glycol, and glycerin having 1 to 3 carbon atoms.
  • the water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.
  • the photosensitive film according to the present disclosure may have a contrast enhancement layer.
  • the contrast enhancement layer is described in, for example, paragraph 0134 of International Publication No. 2018/179640 and paragraphs 0194 to 0196 of JP2014-85643A. The contents of these gazettes are incorporated herein by reference.
  • the average thickness of the photosensitive film is preferably 5 ⁇ m to 55 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m, and particularly preferably 20 ⁇ m to 40 ⁇ m.
  • the average thickness of the photosensitive film is obtained 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 described above. That is, the average thickness of the photosensitive film is the thickness of the photosensitive film (T (x)) measured at a total of 48 points in the three regions described above (that is, the front end portion, the center portion, and the rear end portion). )) Arithmetic mean.
  • the length of the photosensitive film according to the present disclosure is not limited.
  • the length of the photosensitive film according to the present disclosure is preferably 500 m or more.
  • the length of the photosensitive film according to the present disclosure may be determined, for example, in the range of 10,000 m or less.
  • the shape of the photosensitive film according to the present disclosure is not limited.
  • the shape of the photosensitive film according to the present disclosure is preferably roll-shaped from the viewpoint of versatility and transportability. By winding the photosensitive film, the shape of the photosensitive film can be made into a roll.
  • ⁇ Manufacturing method In the method for producing a photosensitive film according to the present disclosure, 90% of the cases satisfy the relationship of Tg (x) ⁇ (98.8/100) ⁇ T (x) ⁇ Tg (x) ⁇ (101.2 / 100). It is not limited as long as it is a method capable of producing a photosensitive film of about 100%. In the method for producing a photosensitive film according to the present disclosure, for example, the method for forming each layer described in the above section "Components" can be used. Hereinafter, a preferable example of a method for producing a photosensitive film will be described with reference to FIG. However, the method for producing the photosensitive film is not limited to the method described below.
  • Examples of the method for producing the photosensitive film 100 shown in FIG. 2 include a step of forming a photosensitive resin layer 12 by applying a photosensitive resin composition on a temporary support 10, and the above-mentioned photosensitive resin. Examples thereof include a step of arranging the cover film 14 on the layer 12 and a method including the step of arranging the cover film 14.
  • the photosensitive resin composition applied on the temporary support 10 may be dried, if necessary.
  • the drying method is not limited, and a known drying method can be used.
  • an extrusion coating device in coating the photosensitive resin composition.
  • the extrusion coating device described in Japanese Patent Application Laid-Open No. 2011-189280 can be mentioned.
  • the variation in the thickness of the photosensitive film can be reduced, so that Tg (x) ⁇ (98.8) / 100) T (x) can be controlled so as to satisfy the relationship of ⁇ T (x) ⁇ Tg (x) ⁇ (101.2 / 100).
  • the height of the spacers for height adjustment installed at both ends of the die on which the coating liquid is discharged is set. It is preferable to adjust. Further, in order to apply the photosensitive resin composition thinly and uniformly, it is preferable to adjust the pressure of the decompression chamber for sucking the photosensitive resin composition on the side opposite to the application direction.
  • the distance between the die and the backup roll is usually set to 30 ⁇ m to 300 ⁇ m.
  • the distance between the die and the backup roll is set according to, for example, the coating thickness, the coating speed, and the physical characteristics (for example, viscosity) of the coating liquid.
  • Examples of the method of arranging the cover film 14 on the photosensitive resin layer 12 include a method of crimping the cover film 14 to the photosensitive resin layer 12.
  • 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 into a roll.
  • the roll-shaped photosensitive film 100 can be used, for example, in a process of bonding to a substrate by a roll-to-roll method.
  • the photosensitive film according to the present disclosure can be used, for example, for forming a resin pattern and forming a circuit wiring.
  • the use of the photosensitive film according to the present disclosure is not limited to the above-mentioned use.
  • the photosensitive film according to the present disclosure may be used, for example, as a photosensitive film for a wiring protective film.
  • Examples of the layer structure of the photosensitive film preferably used as the photosensitive film for the wiring protective film include the following (1) and (2).
  • the components of the photosensitive film preferably used as the photosensitive film for the wiring protective film will be described.
  • the components of the photosensitive film preferably used as the photosensitive film for the wiring protective film are not limited to the components shown below.
  • Temporal support Examples of the temporary support include the temporary support described in the above section "Components”. The preferred embodiment of the temporary support is the same as the preferred embodiment of the temporary support described in the section “Components” above.
  • Examples of the temporary support include the cover film described in the above section "Components”.
  • the preferred embodiment of the cover film is the same as the preferred embodiment of the cover film described in the above section "Components”.
  • the photosensitive resin layer preferably contains an alkali-soluble resin.
  • the alkali-soluble resin include (meth) acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, and reaction of epoxy resin with (meth) acrylic acid.
  • examples thereof include an epoxy acrylate resin obtained in 1 and an acid-modified epoxy acrylate resin obtained by reacting an epoxy acrylate resin with an acid anhydride.
  • the alkali-soluble resin is a (meth) acrylic resin in that it is excellent in alkali developability and film forming property.
  • the (meth) acrylic resin means a resin having a structural unit derived from the (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, still more preferably 90% by mass or more, based on all the structural units of the (meth) acrylic resin. ..
  • the (meth) acrylic resin may be composed of only structural units derived from the (meth) acrylic compound, or may have structural units derived from a polymerizable monomer other than the (meth) acrylic compound. .. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100% by mass or less with respect to all the structural units of the (meth) acrylic resin.
  • Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.
  • Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, and (meth) acrylic acid ester.
  • Acrylic acid glycidyl ester (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, and 2,2,3,3-tetrafluoropropyl (meth) acrylate.
  • Meta) Acrylic acid alkyl esters are preferred.
  • (meth) acrylamide include acrylamide such as diacetone acrylamide.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth).
  • (meth) acrylic acid ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
  • 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 that is copolymerizable with the (meth) acrylic compound, and is, for example, styrene, vinyltoluene, and ⁇ .
  • -Styrene compounds such as methylstyrene which may have a substituent at the ⁇ -position or aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic acid anhydride, monomethyl maleate, maleic acid Examples thereof include monoethyl and maleic acid monoesters such as monoisopropyl maleate, fumaric acid, silicic acid, ⁇ -cyanosilicic acid, itaconic acid, and crotonic acid. These polymerizable monomers may be used alone or in combination of two or more.
  • the (meth) acrylic resin preferably has a structural unit having an acid group from the viewpoint of improving the alkali developability.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
  • the (meth) acrylic resin more preferably has a structural unit having a carboxy group, and further preferably has a structural unit derived from the above-mentioned (meth) acrylic acid.
  • the content of the constituent unit having an acid group (preferably the constituent unit derived from (meth) acrylic acid) in the (meth) acrylic resin is excellent in developability with respect to the total mass of the (meth) acrylic resin. 10% by mass or more is preferable.
  • the upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, in terms of excellent alkali resistance.
  • the (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic acid alkyl ester.
  • the content of the structural unit derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic resin is preferably 50% by mass to 90% by mass, preferably 60% by mass or more, based on all the structural units of the (meth) acrylic resin. 90% by mass is more preferable, and 65% by mass to 90% by mass is further preferable.
  • the (meth) acrylic resin a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester is preferable, and the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid are preferable.
  • a resin composed only of structural units derived from the (meth) acrylic acid alkyl ester is more preferable.
  • 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.
  • the (meth) acrylic resin preferably has at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester from the viewpoint of resolvability, and methacrylic acid. It is preferable to have both a structural unit derived from an acid and a structural unit derived from an alkyl methacrylate ester.
  • the total content of the methacrylic acid-derived structural unit and the methacrylic acid alkyl ester-derived structural unit in the (meth) acrylic resin is 40 with respect to all the structural units of the (meth) acrylic resin from the viewpoint of resolution. It is preferably mass% or more, and more preferably 60% by mass or more.
  • the upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.
  • the (meth) acrylic resin is derived from at least one selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from methacrylic acid alkyl ester from the viewpoint of resolvability, and acrylic acid. It is also preferable to have at least one selected from the group consisting of a structural unit and a structural unit derived from an acrylic acid alkyl ester. From the viewpoint of resolution, the total content of the structural unit derived from methacrylic acid and the structural unit derived from methacrylic acid alkyl ester is the total content of the structural unit derived from acrylic acid and the structural unit derived from acrylic acid alkyl ester.
  • the mass ratio is preferably 60/40 to 80/20 with respect to the amount.
  • the (meth) acrylic resin preferably has an ester group at the end in that the photosensitive resin layer after transfer is excellent in developability.
  • the terminal portion of the (meth) acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis.
  • a (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.
  • the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, for example, from the viewpoint of developability.
  • the alkali-soluble resin is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with a crosslinked component by heating to form a strong film. It is more preferable that the resin is a (meth) acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth) acrylic resin).
  • the alkali-soluble resin is a resin having a carboxy group
  • the three-dimensional cross-linking density can be increased by adding a heat-crosslinkable compound such as a blocked isocyanate compound and heat-crosslinking.
  • a heat-crosslinkable compound such as a blocked isocyanate compound and heat-crosslinking.
  • the carboxy group of the resin having a carboxy group is anhydrous and hydrophobized, the wet heat resistance can be improved.
  • the carboxy group-containing (meth) acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known (meth) acrylic resins.
  • carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0025 of JP2011-095716A, carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and the polymers described in paragraphs 0033 to 0052 of JP2010-237589A.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.
  • the alkali-soluble resin is a styrene-acrylic copolymer.
  • the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and a structural unit derived from the styrene compound.
  • the total content of the structural units derived from the (meth) acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the 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 further preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer. preferable.
  • 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 20% by mass to 95% by mass, based on all the structural units of the copolymer. Mass% is more preferred.
  • the alkali-soluble resin preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint of moisture permeability and strength of the obtained cured film.
  • the monomer forming a structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and ⁇ -methylstyrene, and benzyl (meth) acrylate. Of these, styrene compounds are preferable, and styrene is more preferable.
  • the alkali-soluble resin more preferably has a structural unit (constituent unit derived from styrene) represented by the following formula (S) from the viewpoint of moisture permeability and strength of the obtained cured film.
  • the content of the structural unit having an aromatic ring structure is set with respect to all the structural units of the alkali-soluble resin from the viewpoint of the moisture permeability and strength of the obtained cured film. It is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and even more preferably 20% by mass to 60% by mass.
  • the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is 5 mol% to 70 mol% with respect to all the structural units of the alkali-soluble resin from the viewpoint of moisture permeability and strength of the obtained cured film.
  • 10 mol% to 60 mol% is more preferable, and 20 mol% to 60 mol% is further preferable.
  • the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is 5 mol% or more with respect to all the structural units of the alkali-soluble resin from the viewpoint of moisture permeability and strength of the obtained cured film. 70 mol% is preferable, 10 mol% to 60 mol% is more preferable, 20 mol% to 60 mol% is further preferable, and 20 mol% to 50 mol% is particularly preferable.
  • the above “constituent unit” is synonymous with the “monomer unit”.
  • the above-mentioned “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure from the viewpoint of suppressing development residue, strength of the obtained cured film, and adhesiveness of the obtained uncured film. That is, the alkali-soluble resin preferably has a structural unit having an aliphatic hydrocarbon ring structure. Above all, it is more preferable that the alkali-soluble resin has a ring structure in which two or more aliphatic hydrocarbon rings are fused.
  • Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
  • a ring in which two or more aliphatic hydrocarbon rings are fused is preferable from the viewpoint of suppressive development residue, strength of the obtained cured film, and adhesiveness of the obtained uncured film, and a tetrahydrodicyclopentadiene ring. (Tricyclo [5.2.1.0 2,6 ] decane ring) is more preferable.
  • the monomer forming a structural unit having an aliphatic hydrocarbon ring structure examples include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • the alkali-soluble resin more preferably has a structural unit represented by the following formula (Cy) from the viewpoint of suppressing development residue, strength of the obtained cured film, and adhesiveness of the obtained uncured film. It is more preferable to have a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).
  • R M represents a hydrogen atom or a methyl group
  • R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure
  • R M in the formula (Cy) is preferably a methyl group.
  • One R Cy in Formula (Cy), which has developed residual ⁇ system, strength of the obtained cured film, and, in view of the tackiness of the uncured film obtained, an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms It is preferably a valent group, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms. It is more preferable that it is a group of.
  • Aliphatic hydrocarbon cyclic structure in the R Cy of formula (Cy) can be a single ring structure or may be a polycyclic structure. Further, the aliphatic hydrocarbon cyclic structure in the R Cy of formula (Cy), the development residue ⁇ system, strength of the obtained cured film, and, in view of the tackiness of the uncured film obtained, a cyclopentane ring, cyclohexane A ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure is preferable, and a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure is more preferable, and a tetrahydrodicyclopentadiene ring structure is preferable.
  • aliphatic hydrocarbon cyclic structure in the R Cy of formula (Cy), the development residue ⁇ system, strength of the obtained cured film, and, in view of the tackiness of the uncured film obtained bicyclic or more aliphatic A ring structure in which the hydrocarbon ring is fused is preferable, and a ring in which 2 to 4 aliphatic hydrocarbon rings are fused is more preferable.
  • R Cy in the formula (Cy), the intensity of the development residual ⁇ system resistance, the resulting cured film, and, in view of the tackiness of the uncured film obtained, -C in the formula (Cy) ( O) O-
  • a group in which the oxygen atom of the above and the aliphatic hydrocarbon ring structure are directly bonded that is, an aliphatic hydrocarbon ring group is preferable, and a cyclohexyl group or a dicyclopentanyl group is more preferable. It is more preferably a pentanyl group.
  • the alkali-soluble resin may have one type of structural unit having an aliphatic hydrocarbon ring structure alone, or may have two or more types.
  • the content of the structural unit having an aliphatic hydrocarbon ring structure is the development residue inhibitory property, the strength of the obtained cured film, and the unobtained. From the viewpoint of the adhesiveness of the cured film, 5% by mass to 90% by mass is preferable, 10% by mass to 80% by mass is more preferable, and 20% by mass to 70% by mass is further based on all the constituent units of the alkali-soluble resin. preferable.
  • the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is determined from the viewpoint of suppressing development residue, strength of the obtained cured film, and adhesiveness of the obtained uncured film. 5 mol% to 70 mol% is preferable, 10 mol% to 60 mol% is more preferable, and 20 mol% to 50 mol% is further more preferable, based on all the constituent units of. Further, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is alkaline-soluble from the viewpoint of suppressing development residue, strength of the obtained cured film, and adhesiveness of the obtained uncured film. It is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 50 mol%, based on all the constituent units of the resin.
  • the alkali-soluble resin has 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 From the viewpoint of suppressing the development residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, 10% by mass to 90% by mass is preferable, and 20% by mass is based on all the constituent units of the alkali-soluble resin. -80% by mass is more preferable, and 40% by mass to 75% by mass is further preferable.
  • 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 the development residue inhibitory property, the strength of the obtained cured film, and the obtained uncured film. From the viewpoint of adhesiveness, 10 mol% to 80 mol% is preferable, 20 mol% to 70 mol% is more preferable, and 40 mol% to 60 mol% is further preferable with respect to all the constituent units of the alkali-soluble resin.
  • the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is the present development residue inhibitory property, the strength of the obtained cured film, and From the viewpoint of the adhesiveness of the obtained uncured film, 10 mol% to 80 mol% is preferable, 20 mol% to 70 mol% is more preferable, and 40 mol% to 60 mol% is preferable with respect to all the constituent units of the alkali-soluble resin. % Is more preferable.
  • the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the alkali-soluble resin are the development residue inhibitory property and the strength of the obtained cured film. From the viewpoint of the adhesiveness of the obtained uncured film, it is preferable to satisfy the relationship represented by the following formula (SCy), more preferably the following formula (SCy-1), and the following formula (SCy-2). It is more preferable to satisfy.
  • the alkali-soluble resin preferably has a structural unit having an acid group from the viewpoint of developability and adhesion to the substrate.
  • the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxy group is preferable.
  • the structural unit having the acid group the structural unit derived from (meth) acrylic acid, which is shown below, is preferable, and the structural unit derived from methacrylic acid is more preferable.
  • the alkali-soluble resin may have one type of constituent unit having an acid group alone or two or more types.
  • the content of the structural unit having an acid group is higher than that of all the structural units of the alkali-soluble resin from the viewpoint of developability and adhesion to the substrate.
  • 5% by mass to 50% by mass is preferable, 5% by mass to 40% by mass is more preferable, and 10% by mass to 30% by mass is further preferable.
  • the content of the constituent unit having an acid group in the alkali-soluble resin is preferably 5 mol% to 70 mol% with respect to all the constituent units of the alkali-soluble resin from the viewpoint of developability and adhesion to the substrate.
  • the content of the (meth) acrylic acid-derived structural unit in the alkali-soluble resin is 5 mol% to 70% with respect to all the structural units of the alkali-soluble resin from the viewpoint of developability and adhesion to the substrate.
  • Mol% is preferable, 10 mol% to 50 mol% is more preferable, and 20 mol% to 40 mol% is further preferable.
  • the alkali-soluble resin preferably has a reactive group, and more preferably has a structural unit having a reactive group, from the viewpoint of curability and the strength of the obtained cured film.
  • a reactive group a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable.
  • the alkali-soluble resin preferably has a structural unit having an ethylenically unsaturated group in the side chain.
  • the "main chain” represents a relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain” refers to an atomic group branched from the main chain. show.
  • an ethylenically unsaturated group an allyl group or a (meth) acryloxy group is more preferable.
  • the structural unit having a reactive group include, but are not limited to, those shown below.
  • the alkali-soluble resin may have one type of structural unit having a reactive group alone or two or more types.
  • the content of the structural unit having a reactive group is set to all the structural units of the alkali-soluble resin from the viewpoint of curability and the strength of the obtained cured film.
  • 5% by mass to 70% by mass is preferable, 10% by mass to 50% by mass is more preferable, and 20% by mass to 40% by mass is further preferable.
  • the content of the structural unit having a reactive group in the alkali-soluble resin is 5 mol% to 70 mol with respect to all the structural units of the alkali-soluble resin from the viewpoint of curability and the strength of the obtained cured film.
  • % Is preferred 10 mol% to 60 mol% is more preferred, and 20 mol% to 50 mol% is even more preferred.
  • a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a block are used.
  • a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, and a block
  • examples thereof include a method of reacting a compound such as an isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.
  • a polymer having a carboxy group is synthesized by a polymerization reaction, and then glycidyl (meth) is added to a part of the carboxy groups of the obtained resin by the polymer reaction.
  • examples include a means of reacting an acrylate to introduce a (meth) acryloxy group into a polymer.
  • an alkali-soluble resin having a (meth) acryloxy group in the side chain can be obtained.
  • the polymerization reaction is preferably carried out under a temperature condition of 70 ° C. to 100 ° C., and more preferably carried out under a temperature condition of 80 ° C. to 90 ° C.
  • an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferable.
  • the polymer reaction is preferably carried out under temperature conditions of 80 ° C. to 110 ° C.
  • a catalyst such as an ammonium salt.
  • the alkali-soluble resin the following resins are preferable because the effects in the present disclosure are more excellent.
  • the content ratios (a to d) and the weight average molecular weight Mw of each of the structural units shown below can be appropriately changed according to the purpose.
  • a is preferably 20% by mass to 60% by mass
  • b is preferably 10% by mass to 50% by mass
  • c is preferably 5.0% by mass to 25% by mass
  • d is preferably 10% by mass to 50% by mass. ..
  • a is preferably 20% by mass to 60% by mass
  • b is preferably 10% by mass to 50% by mass
  • c is preferably 5.0% by mass to 25% by mass
  • d is preferably 10% by mass to 50% by mass. ..
  • a is 30% by mass to 65% by mass
  • b is 1.0% by mass to 20% by mass
  • c is 5.0% by mass to 25% by mass
  • d is 10% by mass to 50% by mass. Is preferable.
  • a is 1.0% by mass to 20% by mass
  • b is 20% by mass to 60% by mass
  • c is 5.0% by mass to 25% by mass
  • d is 10% by mass to 50% by mass. Is preferable.
  • the alkali-soluble resin may contain a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as “polymer X”).
  • the carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
  • a cyclic carboxylic acid anhydride structure As the ring having a cyclic carboxylic acid anhydride structure, a 5-membered ring to a 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.
  • the structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or the following formula P-1. It is preferable that the monovalent group obtained by removing one hydrogen atom from the represented compound is a structural unit bonded to the main chain directly or via a divalent linking group.
  • R A1a represents a substituent
  • n 1a R A1a may be the same or different
  • Examples of the substituent represented by RA1a include an alkyl group.
  • Z 1a an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.
  • n 1a represents an integer of 0 or more.
  • Z 1a represents an alkylene group having 2 to 4 carbon atoms
  • n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
  • a plurality of RA1a may be the same or different. Further, the plurality of RA1a may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • a structural unit derived from an unsaturated carboxylic acid anhydride is preferable, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and an unsaturated aliphatic cyclic carboxylic acid is preferable.
  • a structural unit derived from an acid anhydride is more preferable, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferable, and a structural unit derived from maleic anhydride is most preferable.
  • Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or CF 3 groups
  • Me represents a methyl group.
  • the structural unit having the carboxylic acid anhydride structure in the polymer X may be one kind alone or two or more kinds.
  • the total content of the structural units having a carboxylic acid anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and 10 mol% with respect to all the structural units of the polymer X. It is more preferably ⁇ 35 mol%.
  • the photosensitive resin layer may contain only one type of polymer X, or may contain two or more types of polymer X.
  • the content of the polymer X is 0.1% by mass to 30% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of resolution and developability. Is more preferable, 0.2% by mass to 20% by mass is more preferable, 0.5% by mass to 20% by mass is further preferable, and 1% by mass to 20% by mass is further preferable.
  • 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 20 000 to 30,000 is particularly preferable.
  • the acid value of the alkali-soluble resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, further preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 60 mgKOH / g to 110 mgKOH / g. ..
  • the acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070: 1992.
  • the dispersity (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, and 1.0 to 4. 0 is more preferable, and 1.0 to 3.0 is particularly preferable.
  • the photosensitive resin layer may contain only one type of alkali-soluble resin, or may contain two or more types of alkali-soluble resin.
  • the content of the alkali-soluble resin is preferably 10% by mass to 90% by mass, preferably 20% by mass to 80% by mass, based on the total mass of the photosensitive resin layer from the viewpoint of photosensitive, resolution and developability. More preferably, 30% by mass to 70% by mass is further preferable.
  • the photosensitive resin layer may contain a polymerizable compound.
  • a polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically 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”).
  • ethylenically unsaturated compound a polymerizable compound having an ethylenically unsaturated group
  • a (meth) acryloxy group is preferable.
  • the ethylenically unsaturated compound in the present specification is a compound other than the binder polymer, and preferably has a molecular weight of less than 5,000.
  • the preferred embodiment of the ethylenically unsaturated compound is the same as the preferred embodiment of the ethylenically unsaturated compound described in the above section “Photosensitive resin layer”.
  • a compound represented by the following formula (M) (simply also referred to as “Compound M”) can be mentioned.
  • Q 1 and Q 2 each independently represent a (meth) acryloyloxy group
  • R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in the formula (M) from the viewpoint of ease of synthesis, it is preferred that Q 1 and Q 2 are the same group. Further, Q 1 and Q 2 in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
  • the R 1 in the formula (M), the development residue ⁇ system resistance, rust resistance, from the viewpoint of bending resistance of the obtained cured film, an alkylene group, an alkylene oxyalkylene group (-L 1 -O-L 1 - ), or polyalkylene oxyalkylene group (- (L 1 -O) p -L 1 -) are preferable, hydrocarbon groups having 2 to 20 carbon atoms, or, more preferably polyalkylene oxyalkylene group having 4 to 20 carbon atoms An alkylene group is more preferable, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferable.
  • the hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited, and is, for example, branched chain, cyclic, or having 1 to 1 to carbon atoms. It may be any of 5 linear alkylene groups, arylene groups, ether bonds, and combinations thereof, and alkylene groups or groups in which two or more alkylene groups and one or more arylene groups are combined are preferable. , The alkylene group is more preferable, and the linear alkylene group is further preferable.
  • the above L 1 independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group.
  • p represents an integer of 2 or more, and is preferably an integer of 2 to 10.
  • the atomic number of the connecting chain of the shortest for connecting the Q 1, Q 2 in the compound M is developing residual ⁇ system resistance, rust resistance, from the viewpoint of bending resistance of the obtained cured film, 3 to 50 Is preferable, 4 to 40 pieces are more preferable, 6 to 20 pieces are further preferable, and 8 to 12 pieces are particularly preferable.
  • the "Q 1, Q atoms linking chain shortest connecting between the 2" connecting the atoms in R 1 be linked to Q 1 to atom in R 1 be linked to Q 2 It is the shortest number of atoms.
  • the compound M examples include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • the ester monomer can also be used as a mixture.
  • 1,9-Nonandiol di (meth) acrylate and at least one compound selected from the group consisting of 1,10-decanediol di (meth) acrylate, more preferably 1,9-nonane. More preferably, it is at least one compound selected from the group consisting of diol di (meth) acrylate and 1,10-decanediol di (meth) acrylate.
  • a bifunctional or higher functional ethylenically unsaturated compound can be mentioned.
  • the term "bifunctional or higher functional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth) acryloyl group is preferable.
  • a (meth) acrylate compound is preferable.
  • the bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1,4-cyclohexanediol di (meth) acrylate.
  • bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (trade name: NK ester A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimenanol dimethacrylate (commodity).
  • NK ester DCP manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • 1,9-nonanediol diacrylate (trade name: NK ester A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
  • 1,6-hexanediol Diacrylate (trade name: NK ester A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
  • the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
  • Examples thereof include ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compound having a glycerin 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 Industry Co., Ltd., etc.), (Meta ) Acrylate compound alkylene oxide-modified compound (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 of Daicel Ornex Co., Ltd. Etc.), ethoxylated glycerin triacrylate (NK ester A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can also be mentioned.
  • KYARAD registered trademark
  • DPCA-20 manufactured by Nippon Kayaku Co., Ltd.,
  • Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds.
  • examples of the urethane (meth) acrylate include urethane di (meth) acrylate, and examples thereof include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • a urethane (meth) acrylate having trifunctionality or higher can also be mentioned.
  • As the lower limit of the number of functional groups 6-functionality or more is more preferable, and 8-functionality or more is further preferable.
  • the upper limit of the number of functional groups is preferably 20 functional or less.
  • trifunctional or higher functional urethane (meth) acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and 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.
  • One of the preferred embodiments of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group.
  • the acid group include a phosphoric acid group, a sulfo group, and a carboxy group.
  • the carboxy group is preferable as the acid group.
  • ethylenically unsaturated compound having an acid group a trifunctional to tetrafunctional ethylenically unsaturated compound having an acid group [pentaerythritol tri and tetraacrylate (PETA) having a carboxy group introduced into the skeleton (acid value: 80 mgKOH) / G to 120 mgKOH / g)], a pentafunctional to hexafunctional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA)) with a carboxy group introduced into the skeleton [acid value: 25 mgKOH / g] ⁇ 70 mgKOH / g)] and the like.
  • PETA pentafunctional to hexafunctional ethylenically unsaturated compound having an acid group
  • DPHA dipentaerythritol penta and hexaacrylate
  • the ethylenically unsaturated compound having an acid group at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof is preferable.
  • the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof, the developability and film strength are higher. Increase.
  • the bifunctional or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of bifunctional or higher functional ethylenically unsaturated compounds having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark).
  • a registered trademark) M-510 manufactured by Toagosei Co., Ltd. can be mentioned.
  • the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 is preferable, and the contents described in this publication are incorporated in the present specification. Is done.
  • Examples of the ethylenically unsaturated compound include a compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid, and a compound obtained by reacting a glycidyl group-containing compound with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • Urethane monomers such as (meth) acrylate compounds with urethane bonds, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyl Examples thereof include phthalic acid compounds such as oxyethyl-o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters. These are used alone or in combination of two or more.
  • Examples of the compound obtained by reacting a polyvalent alcohol with ⁇ , ⁇ -unsaturated carboxylic acid include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis.
  • Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acryloxypolypropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane , Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, and 2 to 14 ethylene oxide groups.
  • an ethylene unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and a tetramethylolmethanetri (meth) acrylate, a tetramethylolmethanetetra (meth) acrylate, a trimethylolpropane tri (meth) acrylate, or a di (Trimethylolpropane) Tetraacrylate is more preferable.
  • ethylenically unsaturated compound examples 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 Industry Co., Ltd., etc.).
  • Ethylene unsaturated compound alkylene oxide-modified compound for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd. Etc.
  • ethoxylated glycerin triacrylate A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • ethylenically unsaturated compound those containing an ester bond are 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, ethylene having a tetramethylolmethane structure or a trimethylolpropane structure is used.
  • Unsaturated compounds are preferred, and tetramethylolmethanetri (meth) acrylates, tetramethylolmethanetetra (meth) acrylates, trimethylolpropane tri (meth) acrylates, or di (trimethylolpropane) tetraacrylates are more preferred.
  • the ethylenically unsaturated compound includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the above-mentioned ethylene unsaturated compound having a tetramethylol methane structure or a trimethylol propane structure. It preferably contains a compound.
  • 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 tricyclodecanedimethanoldi. Examples include (meth) acrylate.
  • One of the preferred embodiments of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).
  • the ethylenically unsaturated compound is ethylenically having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure).
  • Unsaturated compounds are preferable, bifunctional ethylenically unsaturated compounds having a ring structure in which two or more aliphatic hydrocarbon rings are fused are more preferable, and tricyclodecanedimethanol di (meth) acrylate is further preferable.
  • the aliphatic hydrocarbon ring structure includes a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, and a tricyclodecene from the viewpoint of the moisture permeability and bending resistance of the obtained cured film and the adhesiveness of the obtained uncured film.
  • a structure, a norbornane structure, or an isoborone structure is preferable.
  • the molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the ratio of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less to the content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer is based on the content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer. 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.
  • the photosensitive resin layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound, and more preferably contains a trifunctional or higher functional ethylenically unsaturated compound. More preferably, it contains a functional or tetrafunctional ethylenically unsaturated compound.
  • the photosensitive resin layer is an alkali-soluble compound having a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a structural unit having an aliphatic hydrocarbon ring. It preferably contains a resin.
  • the photosensitive resin layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group
  • 1,9 -It is more preferable to contain nonandiol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and 1,9-nonanediol diacrylate and tricyclodecandi More preferably, it contains a methanol diacrylate and a succinic acid-modified compound of dipentaerythritol pentaacrylate.
  • the photosensitive resin layer comprises a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a heat-crosslinkable compound described later. It is preferable to include the compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.
  • the photosensitive resin layer is a bifunctional ethylenically unsaturated compound (preferably a bifunctional (preferably bifunctional)) from the viewpoint of suppressing development residue and preventing rust. It is preferable to contain a (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher (meth) acrylate compound).
  • the mass ratio of the contents of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
  • the content of the bifunctional ethylenically unsaturated compound is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, based on the total amount of all the ethylenically unsaturated compounds.
  • the content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 40% by mass, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer contains compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. Is preferable. Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer is not ethylenically having compound M and an acid group from the viewpoints of substrate adhesion, development residue inhibitory property, and rust prevention property.
  • the photosensitive resin layer contains 1,9-nonanediol diacrylate and carboxylic acid from the viewpoints of substrate adhesion, development residue inhibitory property, and rust prevention property.
  • It preferably contains a polyfunctional ethylenically unsaturated compound having an acid group, and includes 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. It is more preferable to contain 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, more preferably 1,9-.
  • nonanediol diacrylate tricyclodecanedimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.
  • the photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the content of the bifunctional or higher functional ethylenically unsaturated compound in the above ethylenically unsaturated compound is 60% by mass to 100% by mass with respect to the total content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.
  • 80% by mass to 100% by mass is more preferable, and 90% by mass to 100% by mass is further preferable.
  • the ethylenically unsaturated compound may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, and 5% by mass, based on the total mass of the photosensitive resin layer. It is more preferably from 60% by mass to 50% by mass, and particularly preferably from 5% by mass to 50% by mass.
  • the photosensitive resin layer may contain a polymerization initiator.
  • a photopolymerization initiator is preferable.
  • the preferred embodiment of the photopolymerization initiator is the same as the preferred embodiment of the photopolymerization initiator described in the above section “Photosensitive resin layer”.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more, based on the total mass of the photosensitive resin layer. Is more preferable.
  • the upper limit of the value is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.
  • the photosensitive resin layer may contain a heterocyclic compound.
  • the heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.
  • 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 the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a nitrogen atom.
  • heterocyclic compound examples include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, and a pyrimidine compound.
  • the heterocyclic compound is at least one selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzoimidazole compound, and a benzoxazole compound.
  • heterocyclic compound A preferable specific example of the heterocyclic compound is shown below.
  • examples of the triazole compound and the benzotriazole compound include the following compounds.
  • Examples of the tetrazole compound include the following compounds.
  • thiadiazole compounds include the following compounds.
  • Examples of the triazine compound include the following compounds.
  • rhodanine compound examples include the following compounds.
  • Examples of the thiazole compound include the following compounds.
  • benzothiazole compound examples include the following compounds.
  • Examples of the benzimidazole compound include the following compounds.
  • benzoxazole compound examples include the following compounds.
  • the heterocyclic compound may be used alone or in combination of two or more.
  • the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, preferably 0.10% by mass, based on the total mass of the photosensitive resin layer. It is more preferably ⁇ 10.0% by mass, further preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass.
  • the photosensitive resin layer may contain an aliphatic thiol compound.
  • the photosensitive resin layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with an ethylenically unsaturated compound, so that curing shrinkage of the formed film is suppressed and stress is relaxed. Will be done.
  • aliphatic thiol compound a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound) is preferable.
  • a polyfunctional aliphatic thiol compound is more preferable from the viewpoint of adhesion of the formed pattern (particularly, adhesion after exposure).
  • the term "polyfunctional aliphatic thiol compound” means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups”) in the molecule.
  • the polyfunctional aliphatic thiol compound a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.
  • bifunctional to 10 functional is preferable, bifunctional to 8 functional is more preferable, and bifunctional to 6 functional is further preferable. preferable.
  • polyfunctional aliphatic thiol compound examples include trimethylolpropanthris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.
  • the polyfunctional aliphatic thiol compounds include trimethylolpropane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris. At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.
  • Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and n-. Examples thereof include octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
  • the photosensitive resin layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.
  • the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, based on the total mass of the photosensitive resin layer. 5, 5% by mass to 30% by mass is more preferable, and 8% by mass to 20% by mass is particularly preferable.
  • the photosensitive resin layer preferably contains a heat-crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
  • the heat-crosslinkable compound include the heat-crosslinkable compounds described in the above section “Photosensitive resin layer”.
  • the heat-crosslinkable compound may be used alone or in combination of two or more.
  • the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. Is more preferable.
  • the photosensitive resin layer may contain a surfactant.
  • the surfactant include the surfactant described in the above section "Photosensitive resin layer".
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, preferably 0.01% by mass, based on the total mass of the photosensitive resin layer. It is more preferably from 1.0% by mass, further preferably from 0.05% by mass to 0.80% by mass.
  • the photosensitive resin layer may contain a radical polymerization inhibitor.
  • the radical polymerization inhibitor include the radical polymerization inhibitor described in the above section “Photosensitive resin layer”.
  • the radical polymerization inhibitor may be used alone or in combination of two or more.
  • the content of the radical polymerization inhibitor is preferably 0.01% by mass to 3% by mass, preferably 0.05% by mass, based on the total mass of the photosensitive resin layer. ⁇ 1% by mass is more preferable.
  • the content is 0.01% by mass or more, the storage stability of the photosensitive resin layer is more excellent.
  • the content is 3% by mass or less, the maintenance of sensitivity and the suppression of dye decolorization are more excellent.
  • the photosensitive resin layer may contain a hydrogen donating compound.
  • the hydrogen-donating compound has actions such as further improving the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound by oxygen.
  • Examples of the hydrogen donating compound include amines and amino acid compounds.
  • Examples of amines include M.I. R. "Journal of Polymer Society" by Sander et al., Vol. 10, p. 3173 (1972), JP-A-44-02018, JP-A-51-081022, JP-A-52-134692, JP-A-59-138205. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 60-084305, Japanese Patent Application Laid-Open No. 62-018537, Japanese Patent Application Laid-Open No. 64-033104, Research Disclosure No. 33825, and the like.
  • 4,4'-bis (diethylamino) benzophenone tris (4-dimethylaminophenyl) methane (also known as leucocrystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl.
  • examples thereof include dimethylaniline and p-methylthiodimethylaniline.
  • the amines are at least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane. Seeds are preferred.
  • amino acid compound examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • N-phenylglycine is preferable as the amino acid compound from the viewpoint of sensitivity, curing rate, and curability.
  • Examples of the hydrogen donating compound include an organometallic compound (tributyltin acetate, etc.) described in JP-A-48-042465, a hydrogen donor described in JP-A-55-0344414, and JP-A-6. Sulfur compounds (Tritian and the like) described in JP-A-308727 are also mentioned.
  • the hydrogen donating compound may be used alone or in combination of two or more.
  • the content of the hydrogen donating compound is based on the total mass of the photosensitive resin layer in terms of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. , 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, still more preferably 0.03% by mass to 5.0% by mass.
  • the photosensitive resin layer may contain a predetermined amount of impurities.
  • impurities include the impurities described in the above section "Photosensitive resin layer”.
  • the photosensitive resin layer may contain a residual monomer corresponding to each structural unit of the polymer A described above.
  • Examples of the residual monomer corresponding to each structural unit of the polymer A in the photosensitive resin layer include the residual monomer corresponding to each structural unit of the polymer A described in the above section “Photosensitive resin layer”.
  • the photosensitive resin layer may contain components other than the components described above (hereinafter, also referred to as “other components”).
  • Other components include, for example, colorants, antioxidants, and particles (eg, metal oxide particles).
  • other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 can also be mentioned.
  • metal oxide particles are preferable.
  • the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, for example, from the viewpoint of transparency of the cured film.
  • the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.
  • the photosensitive resin layer When the photosensitive resin layer contains particles, it may contain only one type of particles having different metal types and sizes, or may contain two or more types of particles.
  • the photosensitive resin layer does not contain particles, or when the photosensitive resin layer contains particles, the content of the particles is more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive resin layer. Is preferable, particles are not contained, or the content of particles is more preferably more than 0% by mass and 10% by mass or less with respect to the total mass of the photosensitive resin layer, and particles are not contained or the particles are contained.
  • the amount is more preferably more than 0% by mass and 5% by mass or less based on the total mass of the photosensitive resin layer, and either does not contain particles or the content of particles is 0% by mass based on the total mass of the photosensitive resin layer. Ultra 1% by mass or less is more preferable, and it is particularly preferable that particles are not contained.
  • the photosensitive resin layer may contain a colorant (pigment, dye, etc.), but for example, from the viewpoint of transparency, it is preferable that the photosensitive resin layer contains substantially no colorant.
  • the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive resin layer.
  • the antioxidant examples include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-.
  • 3-Pyrazoridones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorhydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Be done.
  • 3-pyrazolidones are preferable, and 1-phenyl-3-pyrazolidone is more preferable as the antioxidant from the viewpoint of storage stability and curability.
  • the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total mass of the photosensitive resin layer. 0.01% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 1% by mass or less.
  • the thickness (layer thickness) of the photosensitive resin layer is not particularly limited, but from the viewpoint of developability and resolvability, it is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, further preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less. Most preferably 5.0 ⁇ m or less. As the lower limit, 0.60 ⁇ m or more is preferable, and 1.5 ⁇ m or more is more preferable, because the strength of the film obtained by curing the photosensitive resin layer is excellent.
  • the refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
  • the photosensitive resin layer is preferably achromatic. Specifically, the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has an L * value of 10 to 90 in the CIE1976 (L * , a * , b * ) color space.
  • the a * value is preferably ⁇ 1.0 to 1.0
  • the b * value is preferably ⁇ 1.0 to 1.0.
  • the pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer is preferably achromatic.
  • the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) has a pattern L * value of 10 to 90 in the CIE1976 (L * , a * , b * ) color space.
  • the a * value of the pattern is preferably ⁇ 1.0 to 1.0
  • the b * value of the pattern is preferably ⁇ 1.0 to 1.0.
  • Moisture permeability in the layer thickness 40 ⁇ m pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) is that from the viewpoint of corrosion resistance, it is 500g / (m 2 ⁇ 24hr) or less preferably, more preferably not more than 300g / (m 2 ⁇ 24hr) , and more preferably 100g / (m 2 ⁇ 24hr) or less.
  • the moisture permeability is a cured film obtained by curing the photosensitive resin layer by exposing the photosensitive resin layer with an i-ray at an exposure amount of 300 mJ / cm 2 and then performing post-baking at 145 ° C. for 30 minutes. Measure with.
  • the photosensitive transfer material preferably has a refractive index adjusting layer.
  • a known refractive index adjusting layer can be applied.
  • the material contained in the refractive index adjusting 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 for example, 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. There is a method using.
  • alkali-soluble resin and the ethylenically unsaturated compound examples include the alkali-soluble resin and the ethylenically unsaturated compound described in the above section "Photosensitive resin layer".
  • the particles include metal oxide particles and metal particles.
  • the type of the metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles.
  • the metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle size of the particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, for example, from the viewpoint of transparency of the cured film.
  • the average primary particle size of the particles is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particle is not spherical, the longest side is the particle diameter.
  • the metal oxide particles include zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), silicon dioxide particles (SiO 2 particles), and a composite thereof. At least one selected from the group consisting of particles is preferable. Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable from the viewpoint that the refractive index can be easily adjusted.
  • metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F74).
  • Calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT% -F76), zirconium oxide particles (Nano Teen OZ-S30M, Nissan) (Made by Chemical Industry Co., Ltd.) and zirconium oxide particles (Nano Teen OZ-S30K, manufactured by Nissan Chemical Industry Co., Ltd.) can be mentioned.
  • the particles may be used alone or in combination of two or more.
  • the content of particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 40% by mass to 85% by mass with respect to the total mass of the refractive index adjusting layer. More preferred.
  • the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, based on the total mass of the refractive index adjusting layer. , 40% by mass to 85% by mass is more preferable.
  • the refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive resin layer.
  • the refractive index of the refractive index adjusting 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 of the refractive index adjusting 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 adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and even more preferably 60 nm to 100 nm.
  • the refractive index adjusting layer is formed by using, for example, the refractive index adjusting layer.
  • the composition for forming the refractive index adjusting layer preferably contains various components forming the above-mentioned refractive index adjusting layer and a solvent.
  • the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the refractive index adjusting layer described above. be.
  • the solvent is not particularly limited as long as the components contained in the refractive index adjusting layer can be dissolved or dispersed, and at least one selected from the group consisting of water and a water-miscible organic solvent is preferable, and water or water and water.
  • a mixed solvent with a water-miscible organic solvent is more preferable.
  • the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. Alcohols having 1 to 3 carbon atoms are preferable, and methanol or ethanol is more preferable.
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition.
  • the portion is more preferable.
  • the method for forming the refractive index adjusting layer is not particularly limited as long as it can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). Be done.
  • the photosensitive film preferably used as the photosensitive film for the wiring protective film also satisfies the relationship of the temporary support, the photosensitive resin layer and the cover film described above.
  • the method for producing a resin pattern according to the present disclosure is not limited as long as it is a method for producing a resin pattern using the photosensitive film according to the present disclosure.
  • the method for producing a resin pattern according to the present disclosure is a photosensitive film and a substrate (preferably a conductive substrate) according to the present disclosure. )
  • a step of bringing the substrate into contact with the surface of the photosensitive resin layer opposite to the side on which the temporary support is arranged hereinafter, may be referred to as a "bonding step").
  • Exposure step a step of pattern-exposing the photosensitive resin layer
  • development step a step of developing the photosensitive resin layer to form a resin pattern
  • the method for manufacturing the circuit wiring according to the present disclosure is not limited as long as it is the method for manufacturing the circuit wiring using the photosensitive film according to the present disclosure.
  • the resin pattern is arranged in a laminate in which resin patterns formed by using a base material, a conductive layer, and the photosensitive film according to the present disclosure are laminated in this order. It is preferable to include a step of etching the conductive layer in the non-existing region (hereinafter, may be referred to as an “etching step”).
  • the resin pattern manufacturing method according to the present disclosure and the circuit wiring manufacturing method according to the present disclosure are each performed by a roll-to-roll method.
  • the roll-to-roll method is a structure in which a substrate that can be wound and unwound is used as the substrate, and the substrate or the substrate is included before any of the steps included in the resin pattern manufacturing method or the circuit wiring manufacturing method. It includes a step of unwinding a body (also referred to as a “unwinding step”) and a step of winding a substrate or a structure including the substrate (also referred to as a “winding step”) after any of the steps.
  • the unwinding method in the unwinding step and the winding method in the winding step are not limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.
  • a photosensitive film and a substrate are provided with a temporary support for a photosensitive resin layer in the photosensitive film. It is preferable to include a step of bringing the surface opposite to the side (hereinafter, may be referred to as “first surface”) into contact with the substrate and bonding them together.
  • the first surface of the photosensitive resin layer and the substrate (or the conductive layer when the conductive layer is provided on the surface of the substrate) are brought into contact with each other, and the photosensitive film and the substrate are pressure-bonded.
  • the formed resin pattern can be suitably used as an etching resist.
  • the photosensitive film and the substrate may be bonded after removing the cover film from the photosensitive film.
  • the first of the photosensitive resin layers When a layer other than the cover film (for example, a high refractive index layer and / or a low refractive index layer) is arranged on the first surface of the photosensitive resin layer in the photosensitive film, the first of the photosensitive resin layers.
  • the surface and the substrate may be bonded to each other via a layer other than the cover film.
  • the method of crimping the photosensitive film and the substrate is not limited, and a known transfer method and laminating method can be used.
  • the bonding of the photosensitive film and the substrate is preferably performed by superimposing the first surface of the photosensitive resin layer and the substrate, and applying pressure and heating by means such as a roll. Further, for bonding, a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
  • 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 material and a conductive layer on a part or the entire surface of the base material.
  • the substrate may have any layer other than the conductive layer, if necessary.
  • Examples of the base material include glass, silicon, and film.
  • the base material is preferably transparent.
  • transparent means that the transmittance of light having a wavelength of 400 to 700 nm is 80% or more.
  • the refractive index of the base material is preferably 1.50 to 1.52.
  • the transparent glass base material examples include tempered glass represented by Corning's gorilla glass.
  • the transparent glass substrate for example, the materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used.
  • a film base material When a film base material is used as the base material, it is preferable to use a film base material having low optical distortion and / or high transparency.
  • the film substrate as described above include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • the base material constituting the substrate used in the roll-to-roll method is preferably a film base material. Further, when the circuit wiring for the touch panel is manufactured by the roll-to-roll method, the base material is preferably a sheet-like resin composition.
  • the conductive layer examples include a conductive layer used for general circuit wiring or touch panel wiring.
  • the conductive layer may be at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property.
  • a metal layer is more preferable, and a copper layer or a silver layer is particularly preferable.
  • the substrate may have one layer alone or two or more conductive layers.
  • a substrate having two or more conductive layers preferably has a plurality of conductive layers made of different materials.
  • Examples of the material of the conductive layer include metals and conductive metal oxides.
  • 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 .
  • conductive means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm.
  • the volume resistivity of the conductive metal oxide is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • At least one of the plurality of conductive layers contains a conductive metal oxide.
  • an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or wiring of the peripheral extraction part is preferable.
  • a substrate having at least one of a transparent electrode and a routing wiring is preferable.
  • the above-mentioned substrate can be suitably used as a touch panel substrate.
  • the transparent electrode can function suitably as a touch panel electrode.
  • the transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a fine metal wire such as a metal nanowire.
  • the thin metal wire include thin wires such as silver and copper. Of these, silver conductive materials such as silver mesh and silver nanowires are preferable.
  • Metal is preferable as the material of the routing wiring.
  • the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements.
  • copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.
  • the method for producing a resin pattern according to the present disclosure preferably includes a step of pattern-exposing the photosensitive resin layer after the above-mentioned bonding step.
  • the detailed arrangement and specific size of the pattern in the pattern exposure are not limited. At least a part (preferably) of the pattern so as to improve the display quality of a display device (for example, a touch panel) provided with an input device having a circuit wiring manufactured by a circuit wiring manufacturing method and to reduce the area occupied by the take-out wiring.
  • the electrode pattern and / or the portion of the take-out wiring of the touch panel preferably includes a thin wire having a width of 20 ⁇ m or less, and more preferably contains a thin wire having a width of 10 ⁇ m or less.
  • the light source used for exposure may be a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm).
  • Specific examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).
  • the exposure amount is preferably 5 mJ / cm 2 to 200 mJ / cm 2 , and more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
  • the temporary support may be peeled off from the photosensitive resin layer and then pattern-exposed, or the temporary support may be peeled off after pattern-exposure through the temporary support.
  • the pattern exposure may be an exposure through a mask or a direct exposure using an exposure means such as a laser.
  • the method for producing a resin pattern according to the present disclosure preferably includes a step of developing a photosensitive resin layer to form a resin pattern after the above exposure step.
  • the photosensitive resin layer can be developed using a developing solution.
  • the type of developer is not limited as long as the image portion (exposed portion) or non-image portion (non-exposed portion) of the photosensitive resin layer can be removed.
  • As the developing solution a known developing solution (for example, the developing solution described in JP-A-5-72724) can be used.
  • the developer is preferably an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L.
  • the developer may contain a water-soluble organic solvent and / or a surfactant.
  • the developing solution the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.
  • the development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development.
  • shower development is a development process in which an exposed portion or a non-exposed portion is removed by spraying a developing solution onto the photosensitive resin layer after exposure by a shower.
  • the cleaning agent After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
  • the temperature of the developer is not limited.
  • the liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.
  • the photosensitive film contains a thermoplastic resin and an intermediate layer
  • the thermoplastic resin and the non-exposed portion together with the image portion (exposed portion) or the non-image portion (non-exposed portion) of the photosensitive resin layer in the developing step.
  • the intermediate layer is also removed.
  • the thermoplastic resin layer and the intermediate layer may be removed by dissolution or dispersion in a developing solution.
  • the resin pattern is arranged in a laminate in which resin patterns formed by using a base material, a conductive layer, and the photosensitive film according to the present disclosure are laminated in this order. It is preferable to include a step of etching the conductive layer in the non-existing region.
  • 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.
  • the conductive layer is etched by using the resin pattern as an etching resist.
  • a method of etching treatment a known method can be applied.
  • the etching treatment method include the methods described in paragraphs 0209 to 0210 of JP-A-2017-120435, the methods described in paragraphs 0048 to paragraph 0054 of JP-A-2010-152155, and immersion in an etching solution.
  • Examples include a wet etching method and a dry etching (for example, plasma etching) method.
  • an acidic or alkaline etching solution may be appropriately selected according to the etching target.
  • the acidic etching solution examples include an aqueous solution of an acidic component alone selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, an acidic component, and ferric chloride.
  • an acidic component alone selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid
  • an acidic component and ferric chloride.
  • ferric chloride examples include a mixed aqueous solution with a salt selected from the group consisting of ammonium fluoride and potassium permanganate.
  • the acidic component may be a component in which a plurality of acidic components are combined.
  • the alkaline etching solution examples include an aqueous solution of an alkaline component alone selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (for example, tetramethylammonium hydroxide). , A mixed aqueous solution of an alkaline component and a salt (for example, potassium permanganate).
  • the alkaline component may be a component in which a plurality of alkaline components are combined.
  • the circuit wiring manufacturing method according to the present disclosure 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.
  • Examples of the method for removing the remaining resin pattern include a method for removing the remaining resin pattern by chemical treatment.
  • the method for removing the remaining resin pattern is preferably a method for removing the remaining resin pattern using a removing liquid.
  • a method of using the removing liquid for example, a substrate having a residual resin pattern is added to the removing liquid during stirring at a liquid temperature of preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to 30 ° C.
  • a method of immersing for a minute can be mentioned.
  • Examples of the removing solution include a removing solution in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide.
  • Examples of the organic alkali 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 remaining resin pattern using the removing liquid is not limited to the dipping method, and may be a known method other than the dipping method (for example, a spray method, a shower method, and a paddle method).
  • the circuit wiring manufacturing method according to the present disclosure may include an arbitrary process (hereinafter, may be referred to as “another process”) other than the above-mentioned process.
  • Examples of the exposure step, the developing step, and other steps applicable to the method for manufacturing the circuit wiring according to the present disclosure include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.
  • examples of other steps include the steps shown below. However, the other steps are not limited to the steps shown below.
  • the method for producing a resin pattern according to the present disclosure 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.
  • the method for manufacturing a circuit wiring according to the present disclosure may include a step of reducing the reflectance of a part or all of the conductive layer on the substrate.
  • Examples of the treatment for reducing the visible light reflectance of the conductive layer include an oxidation treatment.
  • the visible light reflectance of the conductive layer can be lowered by converting copper into copper oxide by an oxidation treatment and blackening the conductive layer.
  • the method for manufacturing a circuit wiring according to the present disclosure preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
  • the method of forming the insulating film is not limited.
  • the insulating film may be formed by a known method for forming a permanent film.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • circuit wiring manufacturing method it is also preferable to use a substrate having conductive layers on both surfaces of the base material, and to form circuits on each of the conductive layers sequentially or simultaneously.
  • a touch panel circuit wiring having a first conductive pattern formed on one surface of the base material and a second conductive pattern formed on the other surface of the base material can be formed.
  • the circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure can be applied to various devices.
  • Examples of the device provided with the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure include an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable.
  • the input device can be applied to various display devices (for example, an organic EL display device and a liquid crystal display device).
  • the method for manufacturing a touch panel according to the present disclosure is not limited as long as it is a method for manufacturing a touch panel using the photosensitive film according to the present disclosure.
  • the resin pattern is arranged in a laminate in which resin patterns formed by using a base material, a conductive layer, and the photosensitive film according to the present disclosure are laminated in this order. It is preferable to include a step of forming the touch panel wiring by etching the conductive layer in the non-existing area.
  • 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.
  • the mode of each step in the touch panel manufacturing method according to the present disclosure is as described in the above section "Manufacturing method of resin pattern and manufacturing method of circuit wiring", and the preferred mode is also the same.
  • a known method for manufacturing the touch panel may be referred to except that the wiring for the touch panel is formed by the above method.
  • the touch panel manufacturing method according to the present disclosure may include any process other than the above-mentioned process.
  • FIG. 3 is a schematic view showing an example of a pattern of a mask for manufacturing a touch panel.
  • FIG. 4 is a schematic view showing another example of the pattern of the touch panel manufacturing mask.
  • DL indicates a frame for alignment
  • G indicates a non-image portion (light-shielding portion).
  • SL indicates a non-image portion (light-shielding portion).
  • the touch panel can be manufactured by the method shown in FIG. 1 of International Publication No. 2016/190405.
  • G is a portion where a transparent electrode (that is, a touch panel electrode) is formed
  • SL is a portion where wiring of a peripheral take-out portion is formed.
  • a touch panel having at least touch panel wiring is manufactured.
  • the touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
  • Examples of the detection method on the touch panel include a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method.
  • the detection method is preferably a capacitance method.
  • the touch panel type includes a so-called in-cell type (for example, the configuration shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517501), and a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125).
  • in-cell type for example, the configuration shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517501
  • on-cell type for example, Japanese Patent Application Laid-Open No. 2013-168125.
  • the configuration shown in FIG. 19 and the configurations shown in FIGS. 1 and 5 of JP2012-89102A), OGS (One Glass Solution) type, and TOR (Touch-on-Lens) type for example, JP-A-2012.
  • TOR Touch-on-Lens
  • PGMEA 116.5 parts by mass was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked flask at 90 ° C ⁇ 2 ° C, St (52.0 parts by mass), MMA (19.0 parts by mass), MAA (29.0 parts by mass) were added to the three-necked flask. Parts), V-601 (4.0 parts by mass), and PGMEA (116.5 parts by mass) were added dropwise over 2 hours. After completion of the dropping, the mixed solution was stirred for 2 hours while maintaining the liquid temperature at 90 ° C. ⁇ 2 ° C. to obtain a composition containing 30.0% by mass of the polymer A-1.
  • the acid value of polymer A-1 is 189 mgKOH / g.
  • ⁇ Polymerizable compound B> The following compounds were prepared as the polymerizable compound B.
  • C-1 B-CIM (photoradical polymerization initiator, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, manufactured by Hampford)
  • C-2 EAB-F (photoradical polymerization initiator (sensitizer), 4,4'-bis (diethylamino) benzophenone, Tokyo Chemical Industry Co., Ltd.)
  • ⁇ Dye> The following compounds were prepared as dyes.
  • thermoplastic resin composition was prepared by mixing the following components. ⁇ Copolymer of benzyl methacrylate, methacrylic acid, and acrylic acid (solid content concentration: 30.0% by mass, Mw: 30,000, acid value: 153 mgKOH / g): 42.85 parts by mass ⁇ NK ester A-DCP (tri) Cyclodecane dimethanol diacrylate, Shin-Nakamura Chemical Industry Co., Ltd.): 4.63 parts by mass ⁇ 8UX-015A (polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.): 2.31 parts by mass ⁇ Aronix TO-2349 (carboxy group) Polyfunctional acrylate compound having : 0.32 parts by mass
  • composition for an intermediate layer was prepared by mixing the following components.
  • -Ion exchanged water 38.12 parts by mass-Methanol (Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts by mass-Kuraray Poval PVA-205 (polyvinyl alcohol, Kuraray Co., Ltd.): 3.22 parts by mass-Polyvinylpyrrolidone K- 30 (Nippon Catalyst Co., Ltd.): 1.49 parts by mass-Megafuck F-444 (Fluorine-based nonionic surfactant, DIC Co., Ltd.): 0.0015 parts by mass
  • a photosensitive resin composition was prepared by mixing the following components.
  • -Polymer A-1 solid content concentration 30.0%
  • 21.87 parts by mass-B-1 4.85 parts by mass-B-2: 0.51 parts by mass-C-1: 0.89 parts by mass Parts
  • ⁇ C-2 0.05 parts by mass ⁇ D-1: 0.053 parts by mass ⁇ E-1: 0.02 parts by mass ⁇
  • Phenothiazine Flujifilm Wako Pure Chemical Industries, Ltd.
  • 0.025 parts by mass ⁇ 1 -Phenyl-3-pyrazolidone Flujifilm Wako Pure Chemical Industries, Ltd.
  • 0.001 parts by mass ⁇ Methyl ethyl ketone (Sankyo Chemical Co., Ltd.): 30.87 parts by mass ⁇ PGMEA: 33.92 parts by mass ⁇ tetrahydrofuran (THF, Mitsubishi) Chemical Co., Ltd.): 6.93 parts by mass
  • a PET film (Lumirror 16QS62, Toray Industries, Inc., arithmetic mean roughness (Ra value): 0.02 ⁇ m, thickness: 16 ⁇ m) was prepared.
  • the width of the PET film is 1.54 m.
  • thermoplastic resin composition is applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width of the thermoplastic resin composition is 1.53 m and the thickness after drying is 2.0 ⁇ m. bottom.
  • the formed thermoplastic resin composition was dried at 80 ° C. for 40 seconds to form a thermoplastic resin layer. At this time, the pressure in the decompression chamber was set to ⁇ 200 Pa.
  • the composition for the intermediate layer was applied to the surface of the formed thermoplastic resin layer using a slit-shaped nozzle so that the coating width was 1.53 m and the thickness after drying was 1.0 ⁇ m.
  • the coating film of the composition for the intermediate layer was dried at 80 ° C. for 40 seconds to form an intermediate layer. At this time, the pressure in the decompression chamber was set to -1,000 Pa.
  • a photosensitive resin composition was applied to the surface of the formed intermediate layer using a slit-shaped nozzle so that the coating width was 1.53 m and the thickness after drying was 2.0 ⁇ m.
  • the photosensitive resin layer was formed by drying the coating film of the photosensitive resin composition at 80 ° C. for 40 seconds. At this time, the pressure in the decompression chamber was set to -500 Pa.
  • a PET film (Lumirror 16QS62, Toray Co., Ltd., arithmetic average roughness (Ra value): 0.02 ⁇ m, thickness: 16 ⁇ m, width: 1.54 m) is pressure-bonded to the surface of the formed photosensitive resin layer as a cover film. By doing so, a photosensitive film was produced.
  • the produced photosensitive film was wound up in a roll shape at 4,000 m.
  • the average thickness of the photosensitive film measured according to the method described above was 35.7 ⁇ m.
  • the average thickness of each layer of the photosensitive film measured according to the method described above is shown below.
  • Example 2 A photosensitive film was produced by the same procedure as in Example 1 except that the pressure of the decompression chamber when forming the photosensitive resin layer was changed to -1,000 Pa.
  • the average thickness of the photosensitive film was 35.9 ⁇ m.
  • the average thickness of each layer of the photosensitive film measured according to the method described above is shown below.
  • Example 3 The width of the PET film (Lumilar 16QS62, Toray Co., Ltd., arithmetic average roughness (Ra value): 0.02 ⁇ m, thickness: 16 ⁇ m) used as the temporary support and cover film was changed to 0.53 m, respectively.
  • Example 4 The width of the PET film used as the temporary support and cover film (Lumilar 16QS62, Toray Co., Ltd., arithmetic average roughness (Ra value): 0.02 ⁇ m, thickness: 16 ⁇ m) was changed to 0.25 m, and Photosensitive according to the same procedure of Example 1 except that the coating width of the thermoplastic resin composition, the coating width of the intermediate layer composition, and the coating width of the photosensitive resin composition were changed to 0.24 m, respectively. A film was made. The average thickness of the photosensitive film was 35.8 ⁇ m.
  • Temporary support PET film (Lumirror 16QS62, Toray Co., Ltd., Arithmetic Mean Roughness (Ra value): 0.02 ⁇ m, Thickness: 16 ⁇ m) is used for PET film B (Lumirror 12QS62, Toray Co., Ltd., Arithmetic Mean Roughness (Ra)).
  • a photosensitive film was prepared by the same procedure as in Example 1 except that the value) was changed to 0.03 ⁇ m and the thickness was changed to 12 ⁇ m).
  • the average thickness of the photosensitive film was 32.5 ⁇ m. The average thickness of each layer of the photosensitive film measured according to the method described above is shown below.
  • 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 ⁇ m. The average thickness of the photosensitive film was 44.2 ⁇ m. The average thickness of each layer of the photosensitive film measured according to the method described above is shown below.
  • Example 7 On the surface of PET film B (Lumirror 12QS62, Toray Industries, Inc., arithmetic average roughness (Ra value): 0.03 ⁇ m, thickness: 12 ⁇ m) as a temporary support without forming a thermoplastic resin layer and an intermediate layer. , The photosensitive resin layer was formed by applying the photosensitive resin composition, and the thickness of the photosensitive resin layer was changed to 1.1 ⁇ m. A film was made. The average thickness of the photosensitive film was 28.7 ⁇ m. The average thickness of each layer of the photosensitive film measured according to the method described above is shown below.
  • ⁇ Comparative example 1> The photosensitive film was formed by the same procedure as in Example 1 except that the pressure in the pressure reducing chamber when forming the photosensitive resin layer was changed to atmospheric pressure (that is, the photosensitive resin composition was not sucked). Was produced.
  • the average thickness of the photosensitive film was 35.8 ⁇ m. The average thickness of each layer of the photosensitive film measured according to the method described above is shown below.
  • ⁇ Comparative example 2> The pressure of the decompression chamber when forming the photosensitive resin layer, the thermoplastic resin layer and the intermediate layer was all changed to atmospheric pressure (that is, the photosensitive resin composition and the thermoplastic resin composition were not sucked). Except for the above, a photosensitive film was produced by the same procedure as in Example 1. The average thickness of the photosensitive film was 35.8 ⁇ m. The average thickness of each layer of the photosensitive film measured according to the method described above is shown below.
  • Examples 1 and 2 also satisfied the relationship of Tg (x) ⁇ (99.2 / 100) ⁇ T (x) ⁇ Tg (x) ⁇ (100.8 / 100). Specifically, in Example 1 and Example 2, the ratio of satisfying the above relationship was 100%.
  • FIGS. 5, 6 and 7, are graph showing the thickness distribution of the tip portion of the photosensitive film of Comparative Example 1.
  • FIG. 6 is a graph showing the thickness distribution of the central portion 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.
  • 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
  • the vertical axis represents the photosensitive film. It represents the thickness of the film (T (x)).
  • FIGS. 5 is a graph showing the thickness distribution of the tip portion of the photosensitive film of Comparative Example 1.
  • FIG. 6 is a graph showing the thickness distribution of the central portion 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.
  • the horizontal axis represents the distance (x) from one end of the photosensitive film in the width direction
  • P-1 solution a solid content 36.3% by mass solution (solvent: propylene glycol monomethyl ether acetate) of the polymer P-1 having the following structure was used.
  • Polymer P-1 is an alkali-soluble resin.
  • the numerical value at the lower right of each structural unit indicates the content ratio (mol%) of each structural unit.
  • the P-1 solution was prepared by the polymerization step and the addition step shown below.
  • methacrylic acid manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryester M
  • methyl methacrylate manufactured by Mitsubishi Gas Chemical Company, Inc., trade name MMA
  • cyclohexyl methacrylate manufactured by Mitsubishi Gas Chemical Company, Inc., trade name CHMA
  • the dropping liquid (2) dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name V-601) (9.637 g) was added to PGM-Ac (9,637 g).
  • the dropping liquid (2) was obtained by dissolving with 136.56 g).
  • the dropping liquid (1) and the dropping liquid (2) were simultaneously added dropwise to the above-mentioned 2000 mL flask (specifically, a 2000 mL flask containing a liquid heated to 90 ° C.) over 3 hours.
  • the container of the dropping liquid (1) was washed with PGM-Ac (12 g), and the washing liquid was dropped into the 2000 mL flask.
  • the container of the dropping liquid (2) was washed with PGM-Ac (6 g), and the washing liquid was dropped into the 2000 mL flask.
  • the reaction solution in the 2000 mL flask was kept at 90 ° C. and stirred at a stirring speed of 250 rpm. Further, as a post-reaction, the mixture was stirred at 90 ° C. for 1 hour.
  • V-601 (2.401 g) was added to the reaction solution after the post-reaction as the first additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour.
  • V-601 (2.401 g) was added to the reaction solution as the second additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 1 hour. Next, V-601 (2.401 g) was added to the reaction solution as the third additional addition of the initiator. Further, the container of V-601 was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, the mixture was stirred at 90 ° C. for 3 hours.
  • glycidyl methacrylate manufactured by NOF CORPORATION, trade name Blemmer G (manufactured by NOF CORPORATION, trade name Blemmer G) (76.03 g) was added dropwise to the reaction solution over 1 hour.
  • the container of Blemmer G was washed with PGM-Ac (6 g), and the washing liquid was introduced into the reaction liquid. Then, as an addition reaction, the mixture was stirred at 100 ° C. for 6 hours.
  • the reaction solution was cooled and filtered through a mesh filter (100 mesh) for removing dust to obtain a solution (1158 g) of the polymer P-1 (solid content concentration: 36.3% by mass).
  • the obtained polymer P-1 had a weight average molecular weight of 27,000, a number average molecular weight of 15,000, and an acid value of 95 mgKOH / g.
  • the structure of the polymer P-1 is shown below.
  • the molar ratio of the repeating units in the formula was 51.5: 2: 26.5: 20 in order from the repeating unit on the left side.
  • P-2 solution A solution having a solid content of 36.5% by mass of the polymer P-2 was prepared as a P-2 solution according to the following method.
  • the polymer P-2 is an alkali-soluble resin. 82.4 g of propylene glycol monomethyl ether was placed in a flask and heated to 90 ° C. under a nitrogen stream.
  • the weight average molecular weight in terms of standard polystyrene in GPC was 17,000, the dispersity was 2.4, and the acid value was 95 mgKOH / g.
  • the amount of residual monomer measured by gas chromatography was less than 0.1% by mass with respect to the solid content of the polymer P-2 in all the monomers.
  • the structure of the polymer P-2 is shown below.
  • the molar ratio of the repeating units in the formula was 41.0: 15.2: 23.9: 19.9 in order from the repeating unit on the left side.
  • P-3 solution A 36.2% by mass solid content solution of the polymer P-3 was prepared as the P-3 solution according to the following method.
  • the polymer P-3 is an alkali-soluble resin.
  • 113.5 g of propylene glycol monomethyl ether was placed in a flask and heated to 90 ° C. under a nitrogen stream.
  • a solution in which 172 g of styrene, 4.7 g of methyl methacrylate, and 112.1 g of methacrylic acid were dissolved in 30 g of propylene glycol monomethyl ether in this solution, and a polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 27.
  • a solution prepared by dissolving 6 g in 57.7 g of propylene glycol monomethyl ether was simultaneously added dropwise over 3 hours. After completion of the dropping, 2.5 g of V-601 was added three times every hour. After that, it was reacted for another 3 hours. Then, it was diluted with 160.7 g of propylene glycol monomethyl ether acetate and 233.3 g of propylene glycol monomethyl ether. The temperature of the reaction solution was raised to 100 ° C. under an air flow, and 1.8 g of tetraethylammonium bromide and 0.86 g of p-methoxyphenol were added.
  • compositions B-1 to B-4 for forming a refractive index adjusting layer having the compositions shown in the following table were prepared.
  • the numerical values in the table below represent "parts by mass”.
  • Polymer A Polymer A in the above table was synthesized as follows. 1-Methylenepropanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (270.0 g) was introduced into a 1 L three-necked flask, and the temperature was raised to 70 ° C. under a nitrogen stream while stirring. On the other hand, allyl methacrylate (45.6 g) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and methacrylic acid (14.4 g) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are 1-methoxypropanol (Tokyo Chemical Industry Co., Ltd.).
  • 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% by mass / 24% by mass.
  • the weight average molecular weight Mw was 38,000.
  • ⁇ Preparation of photosensitive films 1 to 16> Polyethylene terephthalate film with a thickness of 16 ⁇ m (Lumirror 16KS40, Toray ( Using a slit-shaped nozzle on the temporary support of (manufactured by Co., Ltd.), the coating amount is adjusted to a coating amount at which the film thickness after drying becomes the thickness shown in the table below, and is described in the table below. Any one of the photosensitive resin compositions A-1 to A-10 was applied to form a photosensitive resin layer.
  • compositions B-1 to B-4 After volatilizing the solvent in a drying zone at 100 ° C., use any one of the compositions B-1 to B-4 for forming a refractive index adjusting layer in the combination shown in the table below using a slit-shaped nozzle.
  • the coating amount is adjusted so that the film thickness after drying becomes the film thickness shown in the table below, and the film is applied onto the photosensitive resin layer, and then dried at a drying temperature of 80 ° C. to adjust the refractive index.
  • a layer was formed.
  • a protective film (Lumirror 16KS40, manufactured by Toray Industries, Inc.) was pressure-bonded onto the refractive index adjusting layer to prepare photosensitive films 1 to 16.

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Abstract

La présente divulgation utilise un film photosensible et une application associée. Le film photosensible vérifie, à hauteur de 90 % à 100 %, la relation Tg(x)×(98,8/100)<T(x)<Tg (x)×(101,2/100), où (W) indique, en millimètres, la largeur du film ; où (x) indique, en millimètres, la distance, selon la direction de largeur du film, d'une extrémité du film à la position du film où son épaisseur est mesurée ; où (Ta) indique, en millimètres, l'épaisseur moyenne du film mesurée selon la direction de largeur du film ; où Tg(x) indique, en millimètres, une valeur cible pour l'épaisseur du film exprimée par l'équation suivante ; et où T(x) indique, en millimètres, l'épaisseur du film mesurée à une distance (x) de ladite extrémité du film selon la direction de largeur du film.
PCT/JP2021/004621 2020-02-13 2021-02-08 Film photosensible et procédé de fabrication associé WO2021161965A1 (fr)

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CN202180013363.7A CN115087927A (zh) 2020-02-13 2021-02-08 感光性薄膜以及感光性薄膜的制造方法
JP2022500405A JP7332780B2 (ja) 2020-02-13 2021-02-08 感光性フィルム、及び感光性フィルムの製造方法

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0653132A (ja) * 1992-07-31 1994-02-25 Nippon Telegr & Teleph Corp <Ntt> 有機薄膜の製造方法及び有機薄膜作製装置
JP2007264187A (ja) * 2006-03-28 2007-10-11 Toppan Printing Co Ltd 塗布装置および塗布方法
JP2008233778A (ja) * 2007-03-23 2008-10-02 Fujifilm Corp 離画壁用感光性樹脂膜の形成方法、感光性転写材料、離画壁付基板、カラーフィルタ及びその製造方法、並びに表示装置
JP2010198032A (ja) * 2003-03-28 2010-09-09 Hoya Corp マスクブランクス及び転写用マスク
WO2018047688A1 (fr) * 2016-09-09 2018-03-15 東レ株式会社 Composition de résine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0653132A (ja) * 1992-07-31 1994-02-25 Nippon Telegr & Teleph Corp <Ntt> 有機薄膜の製造方法及び有機薄膜作製装置
JP2010198032A (ja) * 2003-03-28 2010-09-09 Hoya Corp マスクブランクス及び転写用マスク
JP2007264187A (ja) * 2006-03-28 2007-10-11 Toppan Printing Co Ltd 塗布装置および塗布方法
JP2008233778A (ja) * 2007-03-23 2008-10-02 Fujifilm Corp 離画壁用感光性樹脂膜の形成方法、感光性転写材料、離画壁付基板、カラーフィルタ及びその製造方法、並びに表示装置
WO2018047688A1 (fr) * 2016-09-09 2018-03-15 東レ株式会社 Composition de résine

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